Ton-type zeolite and method for producing ton-type zeolite

Abstract

The present invention provides: a novel method for producing TON-type zeolite which is suitable as a base material for an isomerization reaction catalyst; and / or a TON-type zeolite that can be produced via said method. Provided is a TON-type zeolite wherein: the molar ratio of silica to alumina is 70-110; the average maximum particle size is less than 1.5 μm; and in an NMR spectrum measured with 27Al-MAS-NMR, the ratio of the area intensity of a peak with a peak top at a chemical shift of 55±5 ppm to the area intensity of a peak with a peak top at a chemical shift of 0±5 ppm is not less than 13 but less than 30.

Description

TON-type zeolite and method for producing TON-type zeolite

[0001] The present invention relates to a method for producing TON-type zeolite, and to TON-type zeolite that can be produced by this method.

[0002] TON-type zeolites are zeolites having a one-dimensional pore with 10 oxygen rings, and their main use is as a base material for catalysts used in the reaction of isomerizing straight-chain paraffins (normal paraffins) into branched paraffins (hereinafter also referred to as "isomerization reaction catalysts"). (For example, Patent Document 1).

[0003] In recent years, methods have been investigated to improve the activity of isomerization catalysts in order to produce branched paraffins more efficiently. One such method involves reducing the particle size of the TON-type zeolite, which serves as the substrate for the isomerization catalyst, and thereby increasing the contact area with the reactants.

[0004] Japanese Patent Publication No. 2011-206649

[0005] However, because TON-type zeolites have a one-dimensional pore with 10 oxygen rings, the crystals tend to grow in one direction, making it difficult to produce TON-type zeolites with a small maximum particle size.

[0006] This disclosure aims to provide a novel method for producing TON-type zeolite suitable as a substrate for isomerization reaction catalysts, and at least one of the TON-type zeolites that can be produced by this method.

[0007] The inventors have discovered that by adjusting the composition of the raw material composition and using FER-type zeolite as a seed crystal added to the raw material composition, a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm can be produced, thus completing the present invention.

[0008] In other words, the present invention is as described in the claims, and the gist of this disclosure is as follows: [1] A TON-type zeolite having a molar ratio of silica to alumina of 70 or more and 110 or less, an average maximum particle size of less than 1.5 μm, and in an NMR spectrum measured by 27Al-MAS-NMR, the ratio of the area intensity of a peak having a peak top at a chemical shift of 55 ± 5 ppm to the area intensity of a peak having a peak top at a chemical shift of 0 ± 5 ppm is 13 or more and less than 30. [2] The TON-type zeolite according to [1], wherein the average maximum particle size is 0.1 μm or more and less than 1.5 μm. [3] A TON-type zeolite according to [1] or [2], wherein the MFI-type zeolite intensity ratio, which is the ratio of the height intensity of the XRD peak having a peak top at a diffraction angle 2θ = 23.1 ± 0.3° to the height intensity of the XRD peak having a peak top at a diffraction angle 2θ = 20.4 ± 0.3° in a powder X-ray diffraction pattern, is less than 0.05. [4] A TON-type zeolite according to any one of [1] to [3], wherein the cristobalite intensity ratio, which is the ratio of the height intensity of the XRD peak having a peak top at a diffraction angle 21.4 ± 0.3° (2θ) to the height intensity of the XRD peak having a peak top at a diffraction angle 20.4 ± 0.3° (2θ) in a powder X-ray diffraction pattern, is less than 0.05. [5] A TON-type zeolite according to any one of [1] to [4], wherein the acid content is 0.200 mmol / g or more and 1.000 mmol / g or less. [6] BET specific surface area is 100 m ２ / g or more 500m ２ A TON-type zeolite according to any one of [1] to [5], having a surface area of ​​10 m² or less. [7] ２ / g or more 200m ２[1] to [2] a TON-type zeolite according to any one of [1] to [2], wherein the amount of material is less than or equal to / g. [3] A TON-type zeolite according to any one of [1] to [2], wherein the particle diameter D50 at which the cumulative volume from the small particle side in the volume particle size distribution accounts for 50% is 20 μm or more and 150 μm or less. [4] A method for producing a TON-type zeolite, comprising the step of crystallizing a raw material composition containing a silica source, an alumina source, an alkali source, a structure-directing agent source and water in the presence of a seed crystal, wherein the raw material composition has a molar ratio of silica to alumina of 70 or more and 110 or less, and a molar ratio of water to silica of 8 or more and 15 or less, and the seed crystal is a FER-type zeolite. [5] A method for producing a TON-type zeolite according to [1], wherein the structure-directing agent source is 1,6-diaminohexane. [6] A method for producing a TON-type zeolite according to [1] or [2], wherein the raw material composition substantially contains no organic compounds other than the structure-directing agent source.

[0009] This disclosure provides a novel method for producing TON-type zeolites suitable as substrates for isomerization reaction catalysts, and at least one of the TON-type zeolites that can be produced by this method.

[0010] The method for producing the TON-type zeolite described herein will be explained below with reference to an example of an embodiment.

[0011] The terms used in this embodiment are as follows:

[0012] A "zeolite" is a compound in which the skeletal atoms (hereinafter also referred to as "T atoms") have a regular structure mediated by oxygen (O), and the T atoms consist of at least one of a metallic atom and a metalloid atom. Examples of metallic atoms include one or more selected from the group consisting of aluminum (Al), titanium (Ti), iron (Fe), zinc (Zn), gallium (Ga), and tin (Sn). Examples of metalloid atoms include one or more selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0013] A "zeolite-like substance" is a compound in which the T atom has a regular structure mediated by oxygen, and which contains at least one atom other than a metal or metalloid in the T atom. Examples of zeolite-like substances include aluminophosphate (AlPO) and silicoaluminophosphate (SAPO), which are complex phosphorus compounds containing phosphorus (P) as the T atom. In this embodiment, for convenience, a "zeolite-like substance" is distinguished from a "zeolite" in which the T atom consists of at least one of a metal atom and a metalloid atom.

[0014] The "regular structure" in zeolites and zeolite-like substances refers to zeolites that have a skeletal structure specified by the structural code (hereinafter simply referred to as the "structural code") defined by the Structure Commission of the International Zeolite Association (hereinafter also referred to as "IZA"). For example, "TON-type zeolite" and "FER-type zeolite" are zeolites that have a skeletal structure specified by the structural codes "TON" and "FER," respectively. The skeletal structure of each zeolite can be identified, for example, by comparing it with the XRD pattern (hereinafter also referred to as the "reference pattern") described in Zeolite Framework Types on the International Zeolite Society's website (http: / / www.iza-structure.org / databases / ). Note that, in relation to the skeletal structure of zeolites, the terms skeletal structure, crystalline structure, and crystalline phase are used synonymously.

[0015] In this embodiment, the XRD pattern can be obtained from an XRD measurement under the following conditions. The XRD pattern can be measured using a general powder X-ray diffractometer (e.g., Ultima IV, manufactured by Rigaku). Acceleration current / voltage: 40 mA / 40 kV Radiation source: CuKα rays (λ = 1.54178 Å) Measurement mode: Continuous scan Scan conditions: 10° / min Measurement range: 2θ = 5° to 40° Scattering slit: 1 / 3° Diverging slit: 1 / 3° Receiving slit: 0.3 mm Filter: Ni filter

[0016] Aluminosilicate is a composite oxide having a structure consisting of repeating networks of aluminum (Al) and silicon (Si) mediated by oxygen (O). Among aluminosilicates, those having crystalline XRD peaks in their XRD pattern are called "crystalline aluminosilicates," and those not having crystalline XRD peaks are called "amorphous aluminosilicates." Zeolites in which the T atoms are substantially composed of aluminum (Al) and silicon (Si) are considered crystalline aluminosilicates. Here, "substantially composed of aluminum (Al) and silicon (Si)" means not only that the T atoms consist only of aluminum (Al) and silicon (Si), but also that they may contain T atoms other than aluminum (Al) and silicon (Si) to the extent that the effects of the present invention are achieved.

[0017] XRD pattern analysis can be performed using general analysis software (e.g., SmartLab Studio II, Rigaku Corporation). Crystalline XRD peaks are those whose peak top 2θ is identified and detected during XRD pattern analysis. Examples of crystalline XRD peaks with a full width at half maximum (FMAX) of 2θ = 0.50° or less are shown. The following conditions can be used for XRD pattern analysis: Fitting conditions: Automatic, background refined, dispersed pseudo-Voigt function (peak shape); Background removal method: Fitting method; Kα2 removal method: Kα1 / Kα2 ratio = 0.497; Smoothing method: B-Spline curve; Smoothing conditions: Second derivative method, σ cut value = 3, χ threshold = 1.5

[0018] The composition in this embodiment, such as the molar ratio of silica to aluminum (alumina equivalent) (molar ratio of silica to alumina), can be determined by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using a general inductively coupled plasma atomic emission spectrometer (ICP instrument) (for example, instrument name: OPTIMA5300DV, manufactured by PerkinElmer). For compositional analysis, a sample solution obtained by dissolving the sample in a mixed aqueous solution of hydrofluoric acid and nitric acid can be used.

[0019] The method for producing TON-type zeolite according to this embodiment will be described below. This disclosure includes any combination of each configuration and parameter disclosed herein, and the upper and lower limits of the values ​​disclosed herein also include any combination.

[0020] The method for producing TON-type zeolite according to this embodiment (hereinafter also referred to as "the method of production of this embodiment") includes a step of crystallizing a raw material composition containing a silica source, an alumina source, an alkali source, a structure-directing agent source, and water in the presence of a seed crystal (hereinafter also referred to as "the crystallization step"). The raw material composition used in the method of production of this embodiment is SiO ２ / Al ２ O ３ The molar ratio is between 70 and 110, and moreover, the molar ratio of water to silica (the molar ratio of water to silica (hereinafter referred to as "H２ O / SiO ２ (also referred to as the molar ratio) is 8 or more and 15 or less. In addition, the seed crystal used in the production method of the present embodiment is FER-type zeolite. According to such a production method of the present embodiment, single-phase TON-type zeolite having an average maximum particle size of less than 1.5 µm can be produced.

[0021] Note that in the present embodiment, the average maximum particle size is the average value of the maximum particle sizes of the primary particles contained in the zeolite. The primary particles contained in the zeolite are the smallest unit particles that are observed independently (observed without interruption of their contours) under observation by a scanning electron microscope (hereinafter also referred to as "SEM") under the following conditions, and are different from aggregated particles (aggregates) formed by aggregation of a plurality of particles (a plurality of primary particles). SEM observation may be performed using a general scanning electron microscope (for example, JSM-IT200, manufactured by JEOL Ltd.). Acceleration voltage: 10±5 kV Magnification: 10,000±5,000 times

[0022] For the measurement of the average maximum particle size, first, 50±10 primary particles, whose contours are observed without interruption in the SEM observation image, are randomly extracted. The distance between the two parallel lines that is the longest when each extracted primary particle is sandwiched between the two parallel lines in contact with the contour (maximum particle size) is measured, and the average value thereof may be taken as the average maximum particle size. The number of SEM observation images only needs to be sufficient to observe the above-mentioned number of primary particles, and one or more SEM observation images may be used.

[0023] In addition, in the present embodiment, the single-phase TON-type zeolite refers to a zeolite that is substantially composed only of TON-type zeolite. The expression "substantially composed only of TON-type zeolite" does not only mean that the zeolite is composed exclusively of TON-type zeolite, but also allows that in addition to TON-type zeolite, a trace amount of at least one of MFI-type zeolite and cristobalite, which tend to be by-produced together with TON-type zeolite, is permitted to be contained.

[0024] Here, "trace amount of MFI-type zeolite" refers to an amount of MFI-type zeolite such that the MFI-type zeolite intensity ratio is 0.05 or less. The MFI-type zeolite intensity ratio is the ratio (p(2θ=23.1°) / p(2θ=20.4°)) of the height intensity of the XRD peak with a peak top at a diffraction angle of 2θ = 23.1 ± 0.3° (hereinafter also referred to as "p(2θ=23.1°)"), which is the main XRD peak of TON-type zeolite, with a peak top at a diffraction angle of 2θ = 20.4 ± 0.3° (hereinafter also referred to as "p(2θ=20.4°)"), and functions as a parameter indicating the mass ratio of MFI-type zeolite to TON-type zeolite.

[0025] Furthermore, trace amounts of cristobalite refer to amounts of cristobalite such that the cristobalite intensity ratio is 0.05 or less. The cristobalite intensity ratio is the ratio (p(2θ=21.4°) / p(2θ=20.4°)) of the height intensity p(2θ=20.4°) of the main XRD peak of cristobalite, which has its peak top at a diffraction angle of 2θ = 21.4 ± 0.3° (hereinafter also referred to as "p(2θ=21.4°)") to the height intensity p(2θ=20.4°) of the main XRD peak of TON-type zeolite, and functions as a parameter indicating the mass ratio of cristobalite to TON-type zeolite.

[0026] In other words, in this embodiment, the single-layer TON-type zeolite is a TON-type zeolite in which the MFI-type zeolite intensity ratio is 0.05 or less and the cristobalite intensity ratio is also 0.05 or less.

[0027] The raw material composition that crystallizes in the crystallization process contains a silica source. The silica source contained in the raw material composition is silica (SiO₂). ２) or a silicon-containing compound that is a precursor thereof, for example, one or more selected from the group consisting of colloidal silica, amorphous silica, sodium silicate, tetraethyl orthosilicate, precipitated silica, fumed silica, crystalline aluminosilicate, and amorphous aluminosilicate. From the viewpoint of making the average maximum particle size of the TON type produced smaller and further suppressing the by-production of cristobalite and MFI type zeolite, it is preferable that the silica source included in the raw material composition be one or more selected from the group consisting of colloidal silica, tetraethyl orthosilicate, crystalline aluminosilicate, amorphous aluminosilicate, and sodium silicate, more preferably at least one of colloidal silica and amorphous aluminosilicate, and even more preferably amorphous aluminosilicate.

[0028] The raw material composition that crystallizes in the crystallization process includes an alumina source. The alumina source included in the raw material composition is alumina (Al ２ O ３ ) or a compound containing aluminum that is a precursor thereof, for example, one or more selected from the group consisting of aluminum sulfate, sodium aluminate, aluminum hydroxide, aluminum hydroxide gel, aluminum chloride, amorphous aluminosilicate, crystalline aluminosilicate, and metallic aluminum. From the viewpoint of making the average maximum particle size of the TON type produced smaller and further suppressing the by-production of cristobalite and MFI type zeolite, it is preferable that the alumina source contained in the raw material composition be one or more selected from the group consisting of sodium aluminate, aluminum hydroxide, aluminum sulfate, crystalline aluminosilicate, and amorphous aluminosilicate, more preferably at least one of aluminum sulfate and amorphous aluminosilicate, and even more preferably amorphous aluminosilicate.

[0029] Furthermore, if other starting materials in the raw material composition besides the alumina source contain aluminum, these can be considered as alumina sources. For example, if the silica source is a substance containing aluminum, such as crystalline aluminosilicate or amorphous aluminosilicate, then this silica source can be considered both a silica source and an alumina source.

[0030] The raw material composition crystallized in the crystallization process contains an alkali source. The alkali source in the raw material composition may be any compound containing an alkali metal element, for example, at least one of alkali metal hydroxides and halides. From the viewpoint of reducing the average maximum particle size of the TON-type material produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, the alkali metal element in the alkali source is preferably one or more selected from the group consisting of lithium, sodium, potassium, rubidium, and cesium, more preferably at least one of sodium and potassium, and even more preferably potassium.

[0031] The raw material composition crystallized in the crystallization process includes a structure-directing agent source. The structure-directing agent source included in the raw material composition is a substance capable of generating a structure-directing agent (hereinafter also referred to as "SDA") that directs to TON-type zeolite within the raw material composition, and can be exemplified as at least one of SDA and a salt of SDA. From the viewpoint of reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-generation of cristobalite and MFI-type zeolite, the SDA source included in the raw material composition is preferably one or more selected from the group consisting of diethylamine, diethanolamine, 1,6-diaminohexane, and 1,8-diaminooctane, and more preferably 1,6-diaminohexane.

[0032] It is preferable that the raw material composition crystallized in the crystallization process substantially contains organic compounds other than the structure-directing agent source. Substantially containing organic compounds other than the structure-directing agent source means, for example, that the content of organic compounds other than the structure-directing agent source is 5 mol% or less relative to the structure-directing agent source, preferably 3 mol% or less, and more preferably 0 mol% relative to the structure-directing agent source. Note that a content of 0 mol% of organic compounds other than the structure-directing agent source means that no organic compounds other than the structure-directing agent source are detected.

[0033] The raw material composition that crystallizes in the crystallization process contains water. The water in the raw material composition may be one or more selected from the group consisting of distilled water, deionized water, and pure water. The water in the raw material composition may also originate from other starting materials contained in the raw material composition, such as solvents or aqueous compounds.

[0034] The raw material composition to be crystallized in the crystallization process may consist only of the silica source, alumina source, alkali source, structure-directing agent source, and water as described above, or it may contain other substances in addition to these.

[0035] The raw material composition that crystallizes in the crystallization process is SiO ２ / Al ２ O ３ The molar ratio is between 70 and 110. The raw material composition contains SiO ２ / Al ２ O ３ By having a molar ratio of 70 to 110, it is possible to produce a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm. On the other hand, the SiO of the raw material composition ２ / Al ２ O ３ If the molar ratio is less than 70 or more than 110, at least one of cristobalite or MFI-type zeolite is more likely to be produced as a by-product, making it impossible to manufacture single-phase TON-type zeolite.

[0036] SiO of the raw material composition ２ / Al ２ O ３The molar ratio can be between 70 and 110, but from the viewpoint of further suppressing the by-product formation of cristobalite and MFI-type zeolite, it is preferable to have a molar ratio of 80 or higher, 85 or higher, or 90 or higher, and preferably 105 or lower, 100 or lower, or 95 or lower. ２ / Al ２ O ３ The combination of the upper and lower molar ratios is arbitrary, but from the viewpoint of further suppressing the by-generation of cristobalite and MFI-type zeolite, the SiO of the raw material composition is ２ / Al ２ O ３ The molar ratio is preferably 80 to 105, more preferably 85 to 100, and even more preferably 90 to 95.

[0037] The raw material composition that crystallizes in the crystallization process is H ２ O / SiO ２ The molar ratio is 8 to 15. ２ O / SiO ２ By having a molar ratio of 8 to 15, a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm can be produced. On the other hand, the H of the raw material composition ２ O / SiO ２ If the molar ratio is less than 8, at least one of cristobalite and MFI-type zeolite is more likely to be produced as a by-product, making it impossible to produce single-phase TON-type zeolite. Also, the H of the raw material composition ２ O / SiO ２ When the molar ratio exceeds 15, the crystal growth rate becomes dominant over the nucleation rate in the crystallization of TON-type zeolite, which tends to increase the average maximum particle size of the manufactured TON-type zeolite. Furthermore, the H of the raw material composition ２ O / SiO ２ When the molar ratio exceeds 15, at least one of cristobalite or MFI-type zeolite is more likely to be produced as a by-product.

[0038] H of the raw material composition ２ O / SiO ２The molar ratio can be between 8 and 15, but from the viewpoint of further suppressing the by-product formation of cristobalite and MFI-type zeolite, it is preferable to have a ratio of 9 or higher, or 10 or higher, and from the viewpoint of further reducing the average maximum particle size, it is preferable to have a ratio of 13 or lower, or 12 or lower. ２ O / SiO ２ The combination of the upper and lower molar ratios is arbitrary, but from the viewpoint of further suppressing the by-product formation of cristobalite and MFI-type zeolite and further reducing the average maximum particle size, the H of the raw material composition is ２ O / SiO ２ The molar ratio is preferably 9 to 13, and more preferably 10 to 12.

[0039] The raw material composition to be crystallized in the crystallization process has a molar ratio of SDA to silicon in silica terms (hereinafter referred to as "SDA / SiO ２ The SDA / SiO ratio (also called the molar ratio) is not particularly limited. From the viewpoint of making the average maximum particle size of the TON type manufactured smaller and further suppressing the by-product formation of cristobalite and MFI type zeolite, the SDA / SiO ratio of the raw material composition is important. ２ The molar ratio is preferably 0.010 or higher, 0.020 or higher, or 0.040 or higher, and preferably 0.500 or lower, 0.300 or lower, or 0.100 or lower. ２ The combination of upper and lower molar ratios is arbitrary, but from the viewpoint of reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, the SDA / SiO ratio of the raw material composition is recommended. ２ The molar ratio is preferably 0.010 or more and 0.500 or less, more preferably 0.020 or more and 0.300 or less, and even more preferably 0.040 or more and 0.100 or less.

[0040] The raw material composition that crystallizes in the crystallization process has a molar ratio of alkali metal to silica-based silicon (hereinafter referred to as "M / SiO2") ２The molar ratio (also called the molar ratio) is not particularly limited. From the viewpoint of making the average maximum particle size of the TON type manufactured smaller, and further suppressing the by-product formation of cristobalite and MFI type zeolite, the M / SiO ratio of the raw material composition is important. ２ The molar ratio is preferably 0.010 or higher, 0.050 or higher, or 0.100 or higher, and preferably 0.500 or lower, 0.200 or lower, or 0.150 or lower. ２ The combination of upper and lower molar ratios is arbitrary, but from the viewpoint of reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, the M / SiO ratio of the raw material composition is important. ２ The molar ratio is preferably 0.010 to 0.500, more preferably 0.050 to 0.200, and even more preferably 0.100 to 0.150. ２ In the ratio, M is the total amount of alkali metals, and when the alkali metals are potassium, or when the alkali metals are sodium and potassium, the ratio is M / SiO ２ The ratios are K / SiO ２ Molar ratio, or (Na + K) / SiO ２ This will be the molar ratio.

[0041] The raw material composition to be crystallized in the crystallization process has a molar ratio of hydroxide ions to silica-based silicon (hereinafter referred to as "OH / SiO") ２ The molar ratio (also called the molar ratio) is not particularly limited. From the viewpoint of making the average maximum particle size of the TON type manufactured smaller, and further suppressing the by-product formation of cristobalite and MFI type zeolite, the OH / SiO ratio of the raw material composition is important. ２ The molar ratio is preferably 0.010 or higher, 0.050 or higher, or 0.100 or higher, and preferably 0.500 or lower, 0.200 or lower, or 0.150 or lower. ２ The combination of the upper and lower molar ratios is arbitrary, but from the viewpoint of reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, the OH / SiO ratio of the raw material composition is important. ２The molar ratio is preferably 0.010 or more and 0.500 or less, more preferably 0.050 or more and 0.200 or less, and even more preferably 0.100 or more and 0.150 or less.

[0042] In the manufacturing method of this embodiment, the raw material composition is preferably the following molar composition, from the viewpoint of reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite: SiO ２ / Al ２ O ３ Molar ratio = 80 to 105, more preferably 90 to 95 SDA / SiO ２ Molar ratio = 0.010 or more, 0.500 or less, more preferably 0.040 or more, 0.100 or less M / SiO ２ Molar ratio = 0.010 or more, 0.500 or less, more preferably 0.100 or more, 0.150 or less OH / SiO ２ Molar ratio = 0.010 or more, 0.500 or less, more preferably 0.100 or more, 0.150 or less H ２ O / SiO ２ Mole ratio = 9 or more and 13 or less, more preferably 10 or more and 12 or less

[0043] In the crystallization process, the raw material composition is crystallized in the presence of a seed crystal, which is a FER-type zeolite. To crystallize the raw material composition in the presence of a seed crystal (FER-type zeolite), the mixture obtained by mixing the raw material composition and the seed crystal (FER-type zeolite) is crystallized. By crystallizing the raw material composition in the presence of a seed crystal (FER-type zeolite), a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm can be produced. On the other hand, if the crystallization of the raw material composition is carried out in the absence of seed crystals, or in the presence of seed crystals other than FER-type zeolite (for example, one or more seed crystals selected from the group consisting of MFI-type zeolite, TON-type zeolite, FAU-type zeolite, zeolite beta, and MOR-type zeolite), the average maximum particle size of the produced TON-type zeolite will be 1.5 μm or more, or at least one of cristobalite and MFI-type zeolite will be more likely to be produced as by-products, making it impossible to produce single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm.

[0044] The amount of seed crystal (FER-type zeolite) used in the crystallization process is not particularly limited, as long as it is sufficient to produce a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm. From the viewpoint of further reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, the silicon and aluminum in the raw material composition (without seed crystal) are each composed of silica (SiO₂). ２ ) and alumina (Al ２ O ３ When converted to a total mass of 100% by mass, the silicon and aluminum in the seed crystal (FER-type zeolite) are respectively calculated as silica (SiO ２ ) and alumina (Al ２ O ３The percentage of the total mass when converted to (hereinafter also referred to as "seed crystal content") is preferably 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, and preferably 5.0% by mass or less, 3.0% by mass or less, or 2.0% by mass or less. The above-mentioned combination of upper and lower limits for seed crystal content is arbitrary, but from the viewpoint of making the average maximum particle size of the TON type manufactured smaller and further suppressing the by-generation of cristobalite and MFI type zeolite, the seed crystal content is preferably 0.1% by mass or more and 5.0% by mass or less, more preferably 0.3% by mass or more and 3.0% by mass or less, and even more preferably 0.5% by mass or more and 2.0% by mass or less.

[0045] The FER-type zeolite used as seed crystal may be a commercially available product or one manufactured by a conventionally known manufacturing method. The composition of the FER-type zeolite used as seed crystal is not limited, but from the viewpoint of reducing the average maximum particle size of the TON-type zeolite produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, SiO ２ / Al ２ O ３ Preferably, it is a crystalline aluminosilicate with a molar ratio of 10 to 200, and SiO ２ / Al ２ O ３ It is more preferable that the material is a crystalline aluminosilicate with a molar ratio of 15 to 100.

[0046] Crystallization of the raw material composition can be carried out by hydrothermal treatment of the raw material composition in the presence of the seed crystal (FER-type zeolite) described above. Hydrothermal treatment can be performed by placing the raw material composition and seed crystal (FER-type zeolite) in a sealed pressure-resistant container and heating it. Examples of hydrothermal treatment conditions include the following: Treatment temperature: 80°C or higher or 140°C or higher, and 190°C or lower or 180°C or lower Treatment time: 2 hours or more and 500 hours or less Treatment pressure: Self-crystallization pressure

[0047] The crystallization of the raw material composition may be carried out under standing conditions or under stirring conditions, but from the viewpoint of reducing the average maximum particle size of the TON-type material produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, it is preferable to carry out the crystallization under stirring conditions.

[0048] The manufacturing method of this embodiment may include a post-treatment step after the crystallization step, in addition to the crystallization step described above. Examples of post-treatment steps include one or more steps selected from the group consisting of a washing step, a drying step, an SDA removal step, and an ion exchange step.

[0049] In the washing process, the TON-type zeolite is washed. The washing method is arbitrary, but one example is to bring the TON-type zeolite into contact with a sufficient amount of pure water.

[0050] In the drying process, moisture is removed from the TON-type zeolite. The drying method is arbitrary, but one example is drying by heating. The drying conditions are also arbitrary, but one example is treating the TON-type zeolite in an air atmosphere at a temperature between 100°C and 150°C for between 2 and 24 hours.

[0051] In the SDA removal process, SDA is removed from the TON-type zeolite. In the SDA removal process, all of the SDA contained in the TON-type zeolite may be removed, or only a portion of the SDA contained in the TON-type zeolite may be removed. The method for removing SDA can be any conventionally known method and is not particularly limited, but examples include a method using at least one of acid treatment and calcination treatment.

[0052] The acid treatment for removing SDA involves contacting TON-type zeolite with an acid. This acid treatment can remove not only SDA contained in the TON-type zeolite but also alkali metal elements. The method of contacting the TON-type zeolite with the acid is not particularly limited, but one example is mixing the TON-type zeolite with the acid. For example, hydrochloric acid can be used as the acid to contact the TON-type zeolite, and it is preferable to use hydrochloric acid with a concentration of 0.1 mol / L to 6.0 mol / L. The conditions for acid treatment are not particularly limited, but the higher the mass ratio of acid to TON-type zeolite (hereinafter also referred to as the "acid / zeolite mass ratio"), the easier it is to remove SDA from TON-type zeolite. The longer the contact time between TON-type zeolite and acid (hereinafter also referred to as the "acid contact time"), the easier it is to remove SDA from TON-type zeolite. The higher the contact temperature between TON-type zeolite and acid (hereinafter also referred to as the "acid contact temperature"), the easier it is to remove SDA from TON-type zeolite. For this reason, it is preferable to adjust the acid / zeolite mass ratio, acid contact time, and acid contact temperature as appropriate, taking into consideration the above-mentioned characteristics, to obtain the desired SDA content.

[0053] The calcination process to remove SDA involves calcining TON-type zeolite. For example, conditions such as calcination in an air atmosphere at a temperature between 450°C and 700°C for 1 to 4 hours can be used.

[0054] The ion exchange process is a process of converting TON-type zeolite to an arbitrary cation type. For example, converting the cation type of TON-type zeolite to an ammonium type (hereinafter referred to as "NH") ４ ＋ To convert the cation type of the TON-type zeolite to a proton-type (H) type, a treatment can be used in which an aqueous solution containing ammonium ions (hereinafter also referred to as "ammonium aqueous solution") is brought into contact with the TON-type zeolite at a temperature of 20°C to 60°C. Examples of ammonium aqueous solutions used in ion exchange treatment include aqueous ammonium chloride solutions. ＋ To make it a type, for example, NH ４ ＋A treatment of heating a TON-type zeolite in an air atmosphere at a temperature of 500°C or more and 600°C or less for 1 hour or more and 2 hours or less can be used.

[0055] In the production method of the present embodiment, the aforementioned post-treatment steps (washing step, drying step, SDA removal step, and ion exchange step) can be performed in any order, and the same post-treatment step may be performed two or more times.

[0056] According to the production method of the present embodiment described above, a single-phase TON-type zeolite having an average maximum particle diameter of less than 1.5 µm can be produced. Further, the TON-type zeolite produced by the production method of the present embodiment has an average maximum particle diameter of less than 1.5 µm and is a TON-type zeolite with a small particle diameter. Therefore, compared with a TON-type zeolite having a large particle diameter with an average maximum particle diameter of 1.5 µm or more, the contact area with a reactant can be increased, and the TON-type zeolite is suitable as a base material for an isomerization reaction catalyst.

[0057] Hereinafter, the TON-type zeolite that can be produced by the production method of the present embodiment (hereinafter also referred to as "the TON-type zeolite of the present embodiment") will be described.

[0058] The TON-type zeolite of the present embodiment (hereinafter also referred to as "the TON-type zeolite of the present embodiment") has an average maximum particle diameter of less than 1.5 µm, and the molar ratio of silica to alumina (hereinafter referred to as "SiO ２ / Al ２ O ３ molar ratio") is 70 or more and 110 or less, and furthermore, in an NMR spectrum measured by 27Al-MAS-NMR, relative to the area intensity of a peak having a peak top at a chemical shift of 0±5 ppm (hereinafter also referred to as "s （０ｐｐｍ） "), the ratio of the area intensity of a peak having a peak top at a chemical shift of 55±5 ppm (hereinafter also referred to as "s （５５ｐｐｍ） ") (hereinafter also referred to as "s （５５ｐｐｍ） / s （０ｐｐｍ） ") is 13 or more and less than 30, which is a characteristic feature of the zeolite.

[0059] The TON-type zeolite of the present embodiment has an average maximum particle diameter of less than 1.5 μm. Since the TON-type zeolite of the present embodiment has an average maximum particle diameter of less than 1.5 μm, the contact area with reactants can be increased compared to large-particle-diameter TON-type zeolite having an average maximum particle diameter of 1.5 μm or more, and thus the TON-type zeolite of the present embodiment is suitable as a base material for catalysts for isomerization reactions. From the perspective of obtaining a base material that is more suitable as a catalyst for isomerization reactions, the average maximum particle diameter of the TON-type zeolite of the present embodiment is preferably 1.2 μm or less, or 1.0 μm or less, and is preferably 0.1 μm or more, or 0.3 μm or more. Any combination of the above-described upper and lower limits for the average maximum particle diameter is permissible, but from the perspective of obtaining a base material that is more suitable as a catalyst for isomerization reactions, the average maximum particle diameter of the TON-type zeolite of the present embodiment is preferably 0.1 μm or more and less than 1.5 μm, more preferably 0.1 μm or more and 1.2 μm or less, and even more preferably 0.3 μm or more and 1.0 μm or less.

[0060] The TON-type zeolite of the present embodiment has SiO ２ / Al ２ O ３ molar ratio of 70 or more and 110 or less. From the perspective of obtaining a base material that is more suitable as a catalyst for isomerization reactions, the SiO ２ / Al ２ O ３ molar ratio of the TON-type zeolite of the present embodiment is preferably 80 or more, 85 or more, or 90 or more, and is preferably 105 or less, 100 or less, or 95 or less. Any combination of the above-described upper and lower limits for the SiO ２ / Al ２ O ３ molar ratio is permissible, but from the perspective of obtaining a base material that is more suitable as a catalyst for isomerization reactions, the SiO ２ / Al ２ O ３ molar ratio of the TON-type zeolite of the present embodiment is preferably 80 or more and 105 or less, more preferably 85 or more and 100 or less, and even more preferably 90 or more and 95 or less.

[0061] The TON-type zeolite of the present embodiment has SiO ２ / Al ２O ３ If the molar ratio is between 70 and 110, the skeletal structure may contain T atoms other than aluminum (Al) and silicon (Si) as T atoms. From the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, it is more preferable that the TON-type zeolite of this embodiment consists substantially of aluminum (Al) and silicon (Si) T atoms. In other words, it is more preferable that the TON-type zeolite of this embodiment is a TON-type crystalline aluminosilicate.

[0062] The TON-type zeolite of this embodiment is s （５５ｐｐｍ） / s （０ｐｐｍ） The s of the TON-type zeolite in this embodiment is 13 or more and less than 30. From the viewpoint of making it a more suitable substrate as a catalyst for isomerization reactions, （５５ｐｐｍ） / s （０ｐｐｍ） It is preferable that it is 15 or more, 18 or more, or 20 or more, and preferably 28 or less, 25, or 23 or less. （５５ｐｐｍ） / s （０ｐｐｍ） The combination of the upper and lower limits is arbitrary, but from the viewpoint of making it a more suitable substrate as a catalyst for isomerization reactions, the s of the TON-type zeolite in this embodiment （５５ｐｐｍ） / s （０ｐｐｍ） It is preferably 15 to 28, more preferably 15 to 25, even more preferably 18 to 25, and particularly preferably 20 to 23.

[0063] Here, 27Al-MAS-NMR is known as a means of analyzing the local structure around aluminum atoms in zeolites. In the NMR spectrum measured by 27Al-MAS-NMR, it is known that among the aluminum (Al) contained in the zeolite, four-coordinate aluminum (hereinafter referred to as "four-coordinate Al") belongs to a peak with a peak top at a chemical shift of 55 ± 5 ppm, and six-coordinate aluminum (hereinafter referred to as "six-coordinate Al") belongs to a peak with a peak top at a chemical shift of 0 ± 5 ppm (for example, International Publication No. 2017 / 090751). Therefore, s （５５ｐｐｍ） / s （０ｐｐｍ）This functions as an indicator of the ratio of 4-coordinate Al to 6-coordinate Al contained in the zeolite. 4-coordinate Al is the active site of zeolite, but it has been difficult to increase its ratio in TON-type zeolites with large particle sizes, where the average maximum particle size is 1.5 μm or more. On the other hand, the TON-type zeolite of this embodiment has a smaller average maximum particle size than such large-particle-sized TON-type zeolites, and also has a higher ratio of 4-coordinate Al (i.e., s （５５ｐｐｍ） / s （０ｐｐｍ） Since it also has a high isomerization rate, it is presumed that the reaction to isomerize linear paraffins into branched paraffins proceeds efficiently, making it suitable as a base material for isomerization reaction catalysts.

[0064] 27Al-MAS-NMR measurements of zeolites can be performed using a general nuclear magnetic resonance spectrometer (e.g., AVANCE NEO 700, Bruker). Zeolites kept in a vacuum atmosphere, in the presence of saturated ammonium chloride aqueous solution, and at 80% relative humidity for 24 hours can be used as the measurement sample. The following conditions can be used for 27Al-MAS-NMR measurements: Nucleus observed: 27Al (182.4 MHz) Rotation frequency: 24 kHz Pulse width: 2.1 μs Waiting time: 2 seconds Number of integrations: 3500

[0065] s （５５ｐｐｍ） / s （０ｐｐｍ） This refers to a peak with a peak top at a chemical shift of 0 ± 5 ppm (hereinafter referred to as "P"), obtained from the NMR spectrum measured by 27Al-MAS-NMR. ０ｐｐｍ (Also called "P") and a peak with a peak top at a chemical shift of 55 ± 5 ppm (hereinafter referred to as "P") ５５ｐｐｍ (also called "") separates P ５５ｐｐｍ Area intensity (s （５５ｐｐｍ） ) to P ０ｐｐｍ Area intensity (s （０ｐｐｍ） It can be found by dividing by ).

[0066] 27. From the NMR spectrum measured by Al-MAS-NMR, P ０ｐｐｍ and P ５５ｐｐｍTo separate them, conventionally known waveform separation methods (peak fitting) can be used. Specifically, from the NMR spectrum measured by 27Al-MAS-NMR (hereinafter also referred to as the "measured NMR spectrum"), P ０ｐｐｍ and P ５５ｐｐｍ To separate them, the least squares method can be used, with a Gaussian function as the function representing the peak. ０ｐｐｍ and P ５５ｐｐｍ The separation of is one P ０ｐｐｍ and two P ５５ｐｐｍ To separate them, one P is added to the measured NMR spectrum. ０ and two P ５５ It is preferable to proceed under the assumption that it includes P. ０ｐｐｍ and P ５５ｐｐｍ The separation is preferably performed such that the NMR spectrum obtained by recombining each separated peak (hereinafter also referred to as the "calculated NMR spectrum") has a relative error of less than 5% with respect to the measured NMR spectrum at any point (ppm). ０ｐｐｍ and P ５５ｐｐｍ The area intensity of each is P ０ｐｐｍ and P ５５ｐｐｍ The integrated intensity of P can be used. ０ｐｐｍ Two or more peaks are separated as P ５５ｐｐｍ If two or more peaks are separated, the area intensity can be calculated using the sum of the integrated intensities of the two or more separated peaks. For baseline correction, the points at -50 ppm and 150 ppm in the measured NMR spectrum can be connected by a straight line and corrected to zero.

[0067] The TON-type zeolite in this embodiment is not particularly limited, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the acid content is preferably 0.200 mmol / g or more, 0.300 mmol / g or more, or 0.400 mmol / g or more, and preferably 1.000 mmol / g or less, 0.800 mmol / g or less, or 0.600 mmol / g or less. The combination of the upper and lower limits of the acid content described above is arbitrary, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the acid content of the TON-type zeolite in this embodiment is preferably 0.200 mmol / g or more and 1.000 mmol / g or less, more preferably 0.300 mmol / g or more and 0.800 mmol / g or less, and even more preferably 0.400 mmol / g or more and 0.600 mmol / g or less.

[0068] The acid content is the amount of acid sites present per unit mass of zeolite. The acid content can be measured using the ammonia-TPD method with a general catalyst analyzer (for example, instrument name: BELCAT II, ​​manufactured by Microtrac-Bell Co., Ltd.). After saturating the zeolite with ammonia adsorbed at 100°C, an inert gas is passed through it at 100°C for 0.5 hours to remove ammonia not adsorbed on the zeolite from the treatment atmosphere. Then, the temperature is raised from 100°C to 700°C at a heating rate of 10°C / min, and the amount of ammonia released from the zeolite during the heating process (hereinafter also referred to as "released ammonia amount") [ mmol] is measured. Assuming that the released ammonia amount [ mmol] is the amount of acid sites present in the zeolite [ mmol] (amount of ammonia adsorbed on the acid sites of the zeolite [ mmol]), the acid content can be calculated from the following formula (1) using the amount of acid sites present in the zeolite [ mmol] (released ammonia amount [ mmol]) and the mass [ g] of the zeolite used for ammonia adsorption. Furthermore, the zeolite used for saturated adsorption of ammonia (the sample to be measured) can be one that has been pre-treated at 500°C for 1 hour in an inert gas. In the ammonia-TPD method, at least one of helium and argon can be used as the inert gas, with helium being preferred.

[0069] Acid amount [mmol / g] = W ＮＨ３ / W Ｚ ... (1) In the above formula (1), W ＮＨ３ This indicates the amount of ammonia released [mol], W Ｚ The value [g] indicates the mass of the zeolite used for ammonia adsorption. Ｚ For the mass of the zeolite used for ammonia adsorption (in grams), use the mass (in grams) of the sample being measured (the sample before ammonia adsorption) after being treated in an air atmosphere at 600°C for 1 hour.

[0070] The TON-type zeolite in this embodiment is not particularly limited, but from the viewpoint of providing a more suitable substrate as a catalyst for isomerization reactions, the BET specific surface area is 100 m². ２ / g or more, 150m ２ / g or more, or 200m ２ Preferably, it is 1 / g or more, and 500m ２ / g or less, 400m ２ / g or less, or 300m ２ It is preferable that it be less than or equal to / g. The combination of the upper and lower limits of the BET specific surface area as described above is arbitrary, but from the viewpoint of making it a more suitable substrate as a catalyst for isomerization reactions, the BET specific surface area of ​​the TON-type zeolite in this embodiment is 100 m². ２ / g or more 500m ２ It is preferable that the amount is less than or equal to 150m ２ / g or more 400m ２ It is more preferable that it be less than or equal to 200m ２ / g or more 300m ２ It is even more preferable that the amount is less than or equal to / g.

[0071] The BET specific surface area can be determined by measuring the amount of nitrogen gas adsorbed using a constant volume method with a general gas adsorption device (e.g., BELSORP-MAXII, manufactured by Microtrac-Bel), and then analyzing the resulting adsorption isotherm using the Type I BET method in accordance with ISO 9277:2020. The following measurement conditions can be used for measuring the amount of nitrogen gas adsorbed: Adsorbate gas: Nitrogen Measurement temperature: -196°C Pretreatment: Vacuum drying at 350°C for 2 hours

[0072] The TON-type zeolite in this embodiment is not particularly limited, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the outer surface area is 10 m². ２ / g or more, 15m ２ / g or more, or 20m ２ Preferably, it is 1 / g or more, and 200m ２ / g or less, 100m ２ / g or less, or 50m ２ It is preferable that the amount is less than or equal to / g. The combination of the upper and lower limits of the external surface area as described above is arbitrary, but from the viewpoint of making it a more suitable substrate as a catalyst for isomerization reactions, the external surface area of ​​the TON-type zeolite in this embodiment is 10 m². ２ / g or more 200m ２ It is preferable that it be less than or equal to 15m ２ / g or more 100m ２ It is more preferable that it be less than or equal to 20m ２ / g or more 50m ２ It is even more preferable that the amount is less than or equal to / g.

[0073] The external surface area can be determined by analyzing the adsorption isotherm, obtained using the same method as for determining the BET specific surface area, with the t-plot method.

[0074] Furthermore, for the analysis of adsorption isotherms to determine the BET specific surface area and outer surface area, general analysis software (for example, BELMaster) is used. ＴＭ Standard isotherms (manufactured by Microtrac-Bell, Inc.) can be used for t-plot analysis. In addition, standard isotherms registered in general analysis software (for example, BELMaster) can be used as standard isotherms for t-plot analysis. ＴＭ You can use Silica-BEL. t) which is registered in [location].

[0075] The TON-type zeolite of this embodiment is not particularly limited, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the particle diameter at which the cumulative volume from the small particle side in the volume particle size distribution accounts for 50% (hereinafter also referred to as "D50") is preferably 20 μm or more, 40 μm or more, or 60 μm or more, and preferably 150 μm or less, 100 μm or less, or 80 μm or less. The combination of the upper and lower limits of D50 described above is arbitrary, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the D50 of the TON-type zeolite of this embodiment is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 100 μm or less, and even more preferably 60 μm or more and 80 μm or less.

[0076] The TON-type zeolite of this embodiment is not particularly limited, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the particle diameter at which the cumulative volume from the small particle side in the volume particle size distribution accounts for 90% (hereinafter also referred to as "D90") is preferably 50 μm or more, 70 μm or more, or 100 μm or more, and preferably 300 μm or less, 200 μm or less, or 150 μm or less. The combination of the upper and lower limits of D90 described above is arbitrary, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the D90 of the TON-type zeolite of this embodiment is preferably 50 μm or more and 300 μm or less, more preferably 70 μm or more and 200 μm or less, and even more preferably 100 μm or more and 150 μm or less.

[0077] The volume particle size distribution used to determine D50 and D90 is a volume-based particle size distribution measured using a general laser diffraction / scattering particle size distribution analyzer (e.g., Microtrac MT3300EXII, manufactured by Microtrac-Bell Co., Ltd.), and represents the particle size distribution of zeolite. Since zeolite generally contains not only independently existing primary particles (non-aggregated primary particles) but also secondary particles such as aggregated particles, D50 and D90 do not necessarily correlate with the average maximum particle size (the average value of the maximum particle size of primary particles). The following conditions can be used for measuring the volume particle size distribution: Measurement range: 0.02 to 2000 μm Particle refractive index: 1.66 Particle permeability: Permeable Particle shape: Non-spherical Solvent refractive index: 1.333 Ultrasonic pretreatment: None

[0078] In the TON-type zeolite of this embodiment, the MFI-type zeolite intensity ratio (p(2θ=23.1°) / p(2θ=20.4°)) may be 0.05 or less, but from the viewpoint of providing a more suitable substrate as a catalyst for isomerization reactions, it is preferable that it be less than 0.05. In the TON-type zeolite of this embodiment, the lower limit of the MFI-type zeolite intensity ratio is not particularly limited, but it can be said that it is 0 or greater. In other words, in the TON-type zeolite of this embodiment, the MFI-type zeolite intensity ratio may be 0 or more and 0.05 or less, but from the viewpoint of providing a more suitable substrate as a catalyst for isomerization reactions, it is preferable that it is 0 or more and less than 0.05.

[0079] In the TON-type zeolite of this embodiment, the cristobalite intensity ratio (p(2θ=21.4°) / p(2θ=20.4°)) may be 0.05 or less, but from the viewpoint of providing a more suitable substrate as a catalyst for isomerization reactions, it is preferable that it be less than 0.05. In the TON-type zeolite of this embodiment, the lower limit of the cristobalite intensity ratio is not particularly limited, but it can be said that it is 0 or greater. In other words, in the TON-type zeolite of this embodiment, the cristobalite intensity ratio may be 0 or more and 0.05 or less, but from the viewpoint of providing a more suitable substrate as a catalyst for isomerization reactions, it is preferable that it is 0 or more and less than 0.05.

[0080] The TON-type zeolite of this embodiment described above can be used as a substrate for a catalyst for isomerization reactions to isomerize linear paraffins into branched paraffins. The TON-type zeolite of this embodiment has an average maximum particle size of less than 1.5 μm, and since it is a TON-type zeolite with a small particle size, a catalyst for isomerization reactions using it as a substrate can have a larger contact area with the reactants compared to a catalyst for isomerization reactions using a TON-type zeolite with a large particle size (average maximum particle size of 1.5 μm or more) as a substrate. Furthermore, the TON-type zeolite of this embodiment is s （５５ｐｐｍ） / s （０ｐｐｍ） Since the value is 13 or more and less than 30, the isomerization reaction catalyst that uses it as a base material is s （５５ｐｐｍ） / s （０ｐｐｍ） Compared to isomerization catalysts using TON-type zeolites with a ratio of less than 13, the isomerization reaction of linear paraffins to branched paraffins can proceed more efficiently. Therefore, the isomerization catalyst using TON-type zeolites as a base material of this embodiment facilitates the isomerization reaction of linear paraffins (normal paraffins) to branched paraffins (hereinafter also simply referred to as the "isomerization reaction") and can improve the branched paraffin yield. Furthermore, the preferred isomerization catalyst using TON-type zeolites as a base material of this embodiment can improve the branched paraffin yield, as well as the selectivity of single-branched paraffins (hereinafter also referred to as the "single-branch selectivity").

[0081] Straight-chain paraffins are a type of paraffin in which the carbon chain is in a straight line molecular structure, branched paraffins are a type of paraffin in which the carbon chain has side chains, and simply branched paraffins are paraffins in which the carbon chain has only one side chain attached to it.

[0082] The conversion rate (%) of linear paraffins can be determined by multiplying the volume ratio of converted linear paraffins to the linear paraffins used as reaction raw materials by 100. The branched paraffin yield (%) can be determined by multiplying the volume ratio of branched paraffins to the total products produced by the isomerization of linear paraffins by the conversion rate of the linear paraffins used as reaction raw materials. The single-branched selectivity can be determined by multiplying the volume ratio of single-branched paraffins to the total branched paraffins produced by the isomerization of linear paraffins by 100.

[0083] The following describes the isomerization reaction catalyst using the TON-type zeolite of this embodiment as a base material (hereinafter also referred to as "the isomerization reaction catalyst according to this embodiment"). In this embodiment, the base material is the material that forms the basis of the catalyst, and may be used as a catalyst on its own, or as a carrier for supporting predetermined components.

[0084] The isomerization catalyst according to this embodiment includes the TON-type zeolite of this embodiment as a substrate. In other words, the isomerization catalyst according to this embodiment may consist only of the TON-type zeolite of this embodiment, or it may contain, in addition to the TON-type zeolite of this embodiment, a predetermined component supported on the TON-type zeolite of this embodiment. From the viewpoint of further improving the branched paraffin yield, it is preferable that the isomerization catalyst according to this embodiment contains, in addition to the TON-type zeolite of this embodiment, a predetermined component supported on the TON-type zeolite of this embodiment.

[0085] In the isomerization reaction catalyst according to this embodiment, the predetermined component that can be supported on the TON-type zeolite of this embodiment is preferably a metallic element from the viewpoint of further improving the branched paraffin yield. Examples of metallic elements that can be supported on the TON-type zeolite of this embodiment include one or more metallic elements selected from the group consisting of platinum, nickel, cobalt, ruthenium, iridium, molybdenum, tungsten, and palladium, with platinum being more preferable. The state of the metallic element that can be supported on the TON-type zeolite of this embodiment is not particularly limited and may be a compound (e.g., oxide), ion, complex, or elemental (metal), with metal being preferable. Note that the TON-type zeolite of this embodiment may have multiple metallic elements in different states supported on it.

[0086] The content of metal elements can be set appropriately within the range in which the isomerization reaction proceeds, and is not particularly limited. However, from the viewpoint of further improving the branched paraffin yield, it is preferable that the content is 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and preferably 5.0% by mass or less, 2.0% by mass or less, or 1.0% by mass or less, based on 100% by mass of the isomerization reaction catalyst. The combination of the upper and lower limits of the metal element content mentioned above is arbitrary, but from the viewpoint of further improving the branched paraffin yield, it is preferable that the metal element content of the isomerization reaction catalyst be 0.01% by mass or more and 5.0% by mass or less, more preferably 0.1% by mass or more and 2.0% by mass or less, and even more preferably 0.2% by mass or more and 1.0% by mass or less. Note that the metal element content refers to the content assuming that all supported metal elements are in a metal (elemental) state.

[0087] The method for supporting the metal element on the TON-type zeolite of this embodiment is not particularly limited, and conventionally known methods can be used. For example, an aqueous solution containing the metal element (hereinafter also referred to as "metal aqueous solution") can be impregnated into the TON-type zeolite of this embodiment and then dried.

[0088] The metal aqueous solution impregnated into the TON-type zeolite in this embodiment is an aqueous solution obtained by dissolving a metal salt in water. Examples of metal salts contained in the metal aqueous solution include one or more selected from the group consisting of hexachloride platinum(IV) acid, chloride, sulfate, and nitrate, and it is preferable that it be at least one of hexachloride platinum(IV) acid and nitrate, with hexachloride platinum(IV) acid being more preferable. The concentration of the metal element in the metal aqueous solution is not particularly limited and can be set appropriately considering the content of the metal element in the catalyst for the isomerization reaction.

[0089] To impregnate the TON-type zeolite of this embodiment with a metal aqueous solution, a contact treatment can be used, in which the TON-type zeolite of this embodiment is brought into contact with the metal aqueous solution. The contact conditions are not particularly limited and can be set appropriately considering the content of the metal element in the catalyst for the isomerization reaction.

[0090] The drying of the TON-type zeolite impregnated with a metal aqueous solution in this embodiment is not particularly limited, as long as it can remove water from the TON-type zeolite in this embodiment. For example, one possible condition is heating in air at a temperature of 60°C to 180°C for 0.1 hours to 10 hours.

[0091] By drying the TON-type zeolite of this embodiment, which has been impregnated with a metal aqueous solution, the metal element can be supported on the TON-type zeolite of this embodiment. The TON-type zeolite of this embodiment, on which the metal element is supported, may be used as is as a catalyst for the isomerization reaction according to this embodiment, but it is preferable to perform a calcination treatment before using it as a catalyst for the isomerization reaction according to this embodiment. By performing the calcination treatment, the detachment of the metal element can be suppressed. The calcination conditions are not particularly limited, but conditions such as calcination in air at a temperature of 300°C to 600°C for 0.5 hours to 10 hours can be cited.

[0092] The isomerization reaction of linear paraffins using the isomerization catalyst according to this embodiment can be carried out by contacting the isomerization catalyst according to this embodiment with a fluid containing linear paraffins and hydrogen (hereinafter also referred to as "linear paraffin-containing fluid"). When the isomerization catalyst according to this embodiment comes into contact with the linear paraffin-containing fluid, the linear paraffins in the linear paraffin-containing fluid are isomerized to produce branched paraffins.

[0093] The method of contacting the isomerization catalyst and the linear paraffin-containing fluid according to this embodiment is not particularly limited, but examples include a method in which the isomerization catalyst according to this embodiment is packed into a fixed-bed flow-type reaction tube and the linear paraffin-containing fluid is flowed through it (flow method), or a method in which the inside of a reaction vessel containing the isomerization catalyst according to this embodiment is filled with the linear paraffin-containing fluid (batch reaction method).

[0094] The linear paraffin-containing fluid that is brought into contact with the isomerization catalyst according to this embodiment contains at least linear paraffin and hydrogen. Examples of linear paraffin contained in the linear paraffin-containing fluid include linear paraffin having 4 to 100 carbon atoms. From the viewpoint of further improving the branched paraffin yield, the linear paraffin contained in the linear paraffin-containing fluid is preferably linear paraffin having 5 to 80 carbon atoms, more preferably linear paraffin having 7 to 50 carbon atoms, even more preferably linear paraffin having 9 to 20 carbon atoms, and particularly preferably n-decane (n-decane).

[0095] The linear paraffin-containing fluid brought into contact with the isomerization catalyst according to this embodiment may consist only of linear paraffin and hydrogen, or it may further contain components other than linear paraffin and hydrogen. However, from the viewpoint of further improving the branched paraffin yield, it is preferable that it consists only of linear paraffin and hydrogen.

[0096] The linear paraffin-containing fluid brought into contact with the isomerization catalyst according to this embodiment may be a liquid, a gas, or a mixture of liquid and gas.

[0097] The contact conditions between the isomerization catalyst and the linear paraffin-containing fluid according to this embodiment can be adjusted as appropriate within the range in which the isomerization reaction of the linear paraffin proceeds, but preferred contact conditions include the following.

[0098] The contact temperature between the isomerization reaction catalyst and the linear paraffin-containing fluid according to this embodiment is not particularly limited, but from the viewpoint of further improving the branched paraffin yield, it is preferably 200°C or higher, 250°C or higher, or 300°C or higher, and preferably 500°C or lower, 450°C or lower, or 400°C or lower. The combination of the upper and lower limits of the contact temperature described above is arbitrary, but from the viewpoint of further improving the branched paraffin yield, it is preferably 200°C or higher and 500°C or lower, more preferably 250°C or higher and 450°C or lower, and even more preferably 300°C or higher and 400°C or lower.

[0099] The pressure (gauge pressure) of the atmosphere into which the isomerization reaction catalyst and the linear paraffin-containing fluid are brought into contact according to this embodiment is not particularly limited, but from the viewpoint of further improving the branched paraffin yield, it is preferably 0.01 MPaG or higher, 0.1 MPaG or higher, or 0.15 MPaG or higher, and preferably 5.0 MPaG or lower, 2.0 MPaG or lower, or 1.0 MPaG or lower. The combination of the upper and lower limits of the contact atmosphere pressure (gauge pressure) described above is arbitrary, but from the viewpoint of further improving the branched paraffin yield, the pressure (gauge pressure) of the contact atmosphere is preferably 0.01 MPaG or higher and 5.0 MPaG or lower, more preferably 0.1 MPaG or higher and 2.0 MPaG or lower, and even more preferably 0.15 MPaG or higher and 1.0 MPaG or lower. Note that gauge pressure is the pressure with atmospheric pressure set to 0 MPaG.

[0100] From the viewpoint of further improving the branched paraffin yield, the weight space velocity (WHSV) of the linear paraffin in the linear paraffin-containing fluid that comes into contact with the isomerization reaction catalyst according to this embodiment is 0.10 h. －１ That's all, 0.50h －１ Above, or 1.00h －１ Preferably, it is 5.00h or more. －１ Below, 3.00h－１ The following, or 2.00h －１ The following is preferable. The combination of the upper and lower limits of the WHSV for the linear paraffin mentioned above is arbitrary, but from the viewpoint of further improving the branched paraffin yield, 0.10h －１ The above is 5.00h －１ Preferably, it is 0.50h －１ The above is 3.00h －１ It is more preferable that it be 1.00h －１ Total 2.00h －１ The following is even more preferable. Note that the WHSV of linear paraffin is a parameter that represents the amount of linear paraffin supplied per hour per unit mass of isomerization catalyst ([g (isomerization catalyst)] / [g (linear paraffin) / h] = [h －１ )]))

[0101] The volume ratio of hydrogen to linear paraffin in the linear paraffin-containing fluid that comes into contact with the isomerization catalyst according to this embodiment (hereinafter also referred to as the "hydrogen / linear paraffin volume ratio") is preferably 100 or more, 200 or more, or 500 or more, and preferably 1000 or less, 900 or less, or 800 or less, from the viewpoint of further improving the branched paraffin yield. The combination of the upper and lower limits of the hydrogen / linear paraffin volume ratio described above is arbitrary, but from the viewpoint of further improving the branched paraffin yield, it is preferably 100 or more and 1000 or less, more preferably 200 or more and 900 or less, and even more preferably 500 or more and 800 or less.

[0102] The contact time between the isomerization reaction catalyst and the linear paraffin-containing fluid according to this embodiment may be set appropriately according to the amount of branched paraffin to be produced.

[0103] By contacting the isomerization catalyst according to this embodiment with a linear paraffin-containing fluid, the linear paraffin is isomerized, yielding a branched paraffin (a branched paraffin with the same composition as the linear paraffin atoms used as the raw material) in which the arrangement of linear paraffin atoms has changed. The resulting branched paraffin varies depending on the linear paraffin used as the raw material, but for example, when n-decane is used as the linear paraffin, 4-methylnonane (single-branched paraffin) is produced as the branched paraffin.

[0104] The present disclosure will be described in more detail below with reference to examples. However, the present disclosure is not limited to these examples.

[0105] (Compositional Analysis) For compositional analysis, a sample solution was prepared by dissolving the sample in a mixed aqueous solution of hydrofluoric acid and nitric acid. The sample solution was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES) using a general ICP instrument (instrument name: OPTIMA5300DV, manufactured by PerkinElmer). From the obtained Si and Al measurements, the SiO of the sample was determined. ２ / Al ２ O ３ The molar ratio was calculated.

[0106] (Identification of Crystal Phase) XRD measurements were performed on the sample using a general powder X-ray diffractometer (instrument name: Ultima IV, manufactured by Rigaku Corporation). The measurement conditions were as follows: The crystal phase of the sample was identified by comparing the obtained XRD pattern with a reference pattern. Acceleration current / voltage: 40 mA / 40 kV Radiation source: CuKα line (λ = 1.54178 Å) Measurement mode: Continuous scan Scan conditions: 10° / min Measurement range: 2θ = 5° to 40° Scattering slit: 1 / 3° Divergence slit: 1 / 3° Receiving slit: 0.3 mm Filter: Ni filter

[0107] (Evaluation of crystallinity) From the XRD patterns obtained by the above measurements, the height intensity p of the XRD peak with a peak top at a diffraction angle 2θ = 20.4 ± 0.3° (2θ = 20.4°), the height intensity p of the XRD peak with a peak top at a diffraction angle 2θ = 21.4 ± 0.3° (2θ = 21.4°), and the height intensity p of the XRD peak with a peak top at a diffraction angle 2θ = 23.1 ± 0.3° (2θ = 23.1°) were determined. The MFI-type zeolite intensity ratio (p(2θ=23.1°) / p(2θ=20.4°)) was calculated from the obtained values ​​of p(2θ=20.4°) and p(2θ=23.1°), and the cristobalite intensity ratio (p(2θ=21.4°) / p(2θ=20.4°)) was calculated from the obtained values ​​of p(2θ=20.4°) and p(2θ=21.4°).

[0108] The detection and height intensity of p(2θ=20.4°), p(2θ=21.4°), and p(2θ=23.1°) were calculated by analyzing the obtained XRD patterns using analysis software (software name: SmartLab Studio II, manufactured by Rigaku Corporation). The following conditions were used for the analysis: Fitting conditions: Automatic, background refined, dispersed pseudo-Voigt function (peak shape) Background removal method: Fitting method Kα2 removal method: Kα1 / Kα2 ratio = 0.497 Smoothing method: Smoothing by B-Spline Smoothing conditions: Second derivative method, σ cut value = 3, χ threshold = 1.5

[0109] Furthermore, for products with an MFI-type zeolite intensity ratio of less than 0.05, it was determined that MFI-type zeolite was not substantially present, and this was indicated as less than 0.05 (<0.05). Similarly, for products with a cristobalite intensity ratio of less than 0.05, it was determined that cristobalite was not substantially present, and this was indicated as less than 0.05 (<0.05).

[0110] (27Al-MAS-NMR analysis) 27Al-MAS-NMR measurement was performed, s （５５ｐｐｍ） / s （０ｐｐｍ）The (4-coordinate Al / 6-coordinate Al intensity ratio) was determined. A general nuclear magnetic resonance spectrometer (product name: AVANCE NEO 700, manufactured by Bruker) was used for the measurement. As a pretreatment, the sample and saturated ammonium chloride aqueous solution were placed together in a vacuum-sealed desiccator at room temperature (25°C) and maintained at a relative humidity of 80% for 24 hours to be used as the measurement sample. The 27Al-MAS-NMR measurement was performed under the following conditions: Observed nucleus: 27Al (182.4 MHz) Rotation frequency: 24 kHz Pulse width: 2.1 μs Waiting time: 2 seconds Number of integrations: 3500 times

[0111] 27. From the NMR spectrum (measured NMR spectrum) obtained by Al-MAS-NMR measurement, P ５５ｐｐｍ and P ０ｐｐｍ The waveform is separated, P ５５ｐｐｍ Area intensity s （５５ｐｐｍ） And, P ０ｐｐｍ Area intensity s （０ｐｐｍ） We sought s. （５５ｐｐｍ） and s （０ｐｐｍ） From the measurement sample, （５５ｐｐｍ） / s （０ｐｐｍ） They sought it.

[0112] Note, s （５５ｐｐｍ） and s （０ｐｐｍ） Detection and area intensity calculation were performed using analysis software (software name: GRAMS / AI ver8.0, manufactured by Thermo Fisher Scientific). ５５ｐｐｍ and P ０ｐｐｍ Waveform separation was performed using the least squares method with a Gaussian function as the function representing the peak. ５５ｐｐｍ and P ０ｐｐｍ Waveform separation is performed by taking one P from the NMR spectrum. ０ｐｐｍ and two P ５５ｐｐｍ To separate them, one P is added to the NMR spectrum. ０ｐｐｍ and two P ５５ｐｐｍ This was done assuming that it included two P ５５ｐｐｍWaveform separation was performed assuming a half-width of 2.3 ppm. The NMR spectrum obtained by recombining each separated peak (calculated NMR spectrum) showed a relative error of less than 5% compared to the measured NMR spectrum at any given point (ppm). Furthermore, for baseline correction, the points of -50 ppm and 150 ppm in the measured NMR spectrum were connected by a straight line and corrected to zero.

[0113] (Measurement of average maximum particle size) SEM observation was performed using a general scanning electron microscope (device name: JSM-IT200, manufactured by JEOL Ltd.) under the following conditions: Acceleration voltage: 6kV Magnification: 10,000±5,000x

[0114] From the obtained SEM observation image, 50 ± 10 primary particles whose contours were observed without interruption were arbitrarily selected. The distance between the two parallel lines that were tangent to the contour of each selected primary particle was measured to obtain the longest distance (maximum particle size), and the average of these distances was calculated and defined as the average maximum particle size.

[0115] (Measurement of BET specific surface area) Nitrogen gas adsorption amount was measured using a constant volume method with a general gas adsorption apparatus (apparatus name: BELSORP-MAXII, manufactured by Microtrac-Bel). The measurement conditions are as follows: Adsorbate gas: Nitrogen Measurement temperature: -196°C Pretreatment: Vacuum drying at 350°C for 2 hours

[0116] By analyzing the adsorption isotherm obtained by measuring the amount of nitrogen gas adsorption using the Type I BET method (ISO 9277:2022), the BET specific surface area [m²] of the measured sample can be determined. ２ / g] (hereinafter referred to as “a ＢＥＴ It is also called ''. ) was calculated. In addition, in the analysis using the BET method, the relative pressure (P / P ０ The data with a value between 0.001 and 0.990 was plotted using the BET method. A general analysis software (software name: BELMaster) was used for the BET method analysis. ＴＭ (Microtrac manufactured by Bell) was used.

[0117] (Measurement of external surface area by t-plot method) The adsorption isotherm of nitrogen gas obtained by the above measurement is analyzed by the t-plot method to determine the external surface area [m²] of the sample. ２ / g] (hereinafter referred to as “a ｅｘ It is also called ''.) was calculated. For the calculation, analysis software (software name: BELMaster) was used. ＴＭ A microtrac-BEL (manufactured by Microtrac) was used. The standard isotherm was selected from "Silica-BEL.t" registered in the analysis software, and the outer surface area of ​​the sample was obtained from the straight line connecting two points at t = 0.6 and 1.0 nm.

[0118] (Measurement of D50 and D90) D50 and D90 were determined from the integrated curve of the volume particle size distribution (particle size distribution based on volume) obtained by measurement using a laser diffraction / scattering particle size distribution analyzer (device name: Microtrac MT3300EXII, manufactured by Microtrac-Bell Co., Ltd.). The measurement conditions were as follows: Measurement range: 0.02 to 2000 μm Particle refractive index: 1.66 Particle permeability: permeable Particle shape: non-spherical Solvent refractive index: 1.333 Ultrasonic pretreatment: None

[0119] (Measurement of Acid Content) The acid content was measured using the ammonia TPD (Temperature Programmed Desorption) method with an online gas analyzer (BELCAT II, ​​Microtrac-Bel). First, 0.05 g of the sample was pre-treated by heating in a helium flow atmosphere at 500°C for 1 hour, and this was used as the measurement sample. After pre-treatment, the temperature was lowered to 100°C, and the flow gas was changed to a helium-ammonia mixed gas containing 99% helium by volume and 1% ammonia by volume, and the mixture was allowed to flow for 0.5 hours to allow ammonia to saturate adsorbed onto the sample. After saturation adsorption, the flow gas was switched back to helium gas, and the helium gas was allowed to flow for 0.5 hours to remove any remaining ammonia in the atmosphere (ammonia not adsorbed on the zeolite).

[0120] After ammonia removal, the ammonia temperature-induced desorption spectrum was obtained by heating under the following conditions: Atmosphere: Helium flow atmosphere (flow rate 30 mL / min) Heating rate: 10°C / min Treatment temperature: 100°C to 700°C

[0121] Furthermore, after the temperature has been raised from 100°C to 700°C, a mixed gas of ammonia and helium with a known ammonia content (hereinafter referred to as "NH") is used. ３ A mixture of NH40 (also called "-He mixed gas") was passed to the detector via a route that did not pass through the sample being measured (a separate line), and a spectrum for correcting the detector's sensitivity was obtained. The spectrum for sensitivity correction was obtained for a first NH40 with an ammonia concentration of 0.206 volume%. ３ -He mixed gas and a second NH with an ammonia concentration of 0.137 volume% ３ -He mixed gas and a third NH with an ammonia concentration of 0.069 volume% ３ - The NH was obtained by circulating three types of gases, including a mixed gas of He and four types of gases, including helium gas alone. ３ -He mixed gas and helium gas alone were each passed through at a flow rate of 30 mL / min, a flow time of 15 minutes, and a temperature of 100°C.

[0122] The obtained ammonia temperature-controlled desorption spectrum was subjected to background correction. Background correction was performed using multi-point correction. Specifically, points were used at the point immediately before the start of the temperature increase from 100°C to 700°C (100°C point), the point immediately after the temperature increase from 100°C to 700°C was completed (700°C point), and NH to correct the detector sensitivity. ３ - The correction was made by connecting a total of four points: the point just before the start of the He mixed gas flow and the point just before the end of the helium-only gas flow.

[0123] From the background-corrected ammonia temperature-induced desorption spectrum, a peak with a peak top at 200 ± 20°C (hereinafter referred to as "P") was observed. ２００℃ It is also called "P".) and a peak with its peak top at 420±20℃ (hereinafter referred to as "P ４２０℃ It is also called ". ) Separate P ２００℃ The integral value of (hereinafter referred to as "w") （２００℃）It is also called ", and P ４２０℃ The integral value of (hereinafter referred to as "w") （４２０℃） The total value of the peak intensity of the peaks included in the spectrum for sensitivity correction and the NH used to obtain the spectrum for sensitivity correction were calculated. ３ - From the amount of ammonia contained in the He mixed gas, the relationship between the integrated value of the peak intensity and the amount of ammonia is determined, and based on this relationship, w （２００℃） and w （４２０℃） The sum of these values ​​is converted to the amount of ammonia, and this is the amount of detached ammonia [ mmol] that detaches from the sample during the heating process (hereinafter referred to as "w ＡＬＬ It is also called "..."

[0124] Note P ２００℃ and P ４２０℃ Waveform separation was performed using the least squares method with a Gaussian function as the function representing the peaks. Furthermore, the spectrum obtained by recombining each separated peak showed a relative error of less than 5% compared to the measured ammonia temperature-induced desorption spectrum at any given point (ppm). Background processing, as well as peak detection (waveform separation) and calculation of their integral values, were performed using analysis software (software name: ChemMaster, manufactured by Microtrac-Bell).

[0125] The amount of acid is equal to the amount of ammonia released (W) ＮＨ３ ) and the mass (W) of the zeolite used for ammonia adsorption. Ｚ ) was obtained from the above equation (1) using ). Note that W in the above equation (1) Ｚ For the mass of zeolite used for ammonia adsorption [g], the mass (dry mass) [g] of the sample after treatment with air at 600°C for 1 hour was used.

[0126] Example 1 A raw material composition was obtained by mixing pure water, 1,6-diaminohexane, a 48% by mass aqueous solution of potassium hydroxide, and amorphous aluminosilicate to the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0127] To the obtained raw material composition, FER-type zeolite (product name: HSZ(registered trademark)-720NHA, SiO2) is added so that the seed crystal content is 1% by mass. ２ / Al ２ O ３ A seed crystal (molar ratio = 18) was added. Then, 3600 g of the raw material composition was packed into a sealed container with a volume of 4000 mL, and crystallized by heating at 160°C for 36 hours while stirring at 400 rpm. After crystallization, the recovered crystals were filtered, washed with pure water, and dried in an air atmosphere at 110°C for 12 hours or more to obtain a dry powder. The obtained dry powder was calcined in an air atmosphere at 600°C for 4 hours to obtain calcined powder. The calcined powder was dispersed in pure water and filtered to make a cake, which was washed with a 20% by mass aqueous solution of ammonium chloride. Then, it was washed again with pure water, dried in an air atmosphere at 120°C for 12 hours or more, and calcined at 550°C for 2 hours to obtain the zeolite of this example.

[0128] The zeolite in this embodiment, based on its XRD pattern, is a single-phase TON-type zeolite (crystalline aluminosilicate), with a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of <0.05. Furthermore, the zeolite in this embodiment is SiO ２ / Al ２ O ３ The molar ratio is 95.1, the average maximum particle size is 0.9 μm, s （５５ｐｐｍ） / s （０ｐｐｍ） The (4-coordinate Al / 6-coordinate Al intensity ratio) was 17.8. The characteristics of the zeolite in this example are shown in Tables 1 to 3.

[0129] Example 2 A raw material composition was obtained in the same manner as in Example 1, except that the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 81.7 OH / SiO ２Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0130] To the obtained raw material composition, FER-type zeolite (product name: HSZ(registered trademark)-720NHA, SiO2) is added so that the seed crystal content is 1% by mass. ２ / Al ２ O ３ A seed crystal (molar ratio = 18) was added. Then, 55 g of the raw material composition was packed into an 80 mL sealed container and heated at 160°C for 36 hours while stirring at 55 rpm to crystallize. After crystallization, the recovered crystals were filtered, washed with pure water, and dried in an air atmosphere at 110°C for 12 hours or more to obtain a dry powder. The obtained dry powder was calcined in an air atmosphere at 600°C for 4 hours to obtain calcined powder. The calcined powder was dispersed in pure water and filtered to form a cake, which was washed with a 20% by mass aqueous solution of ammonium chloride. Then, it was washed again with pure water, dried in an air atmosphere at 120°C for 12 hours or more, and calcined at 550°C for 2 hours to obtain the zeolite of this example.

[0131] The zeolite in this embodiment, based on its XRD pattern, is a single-phase TON-type zeolite (crystalline aluminosilicate), with a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of <0.05. Furthermore, the zeolite in this embodiment is SiO ２ / Al ２ O ３ The molar ratio is 84.3, the average maximum particle size is 0.6 μm, s （５５ｐｐｍ） / s （０ｐｐｍ） The (4-coordinate Al / 6-coordinate Al intensity ratio) was 22.5. The characteristics of the zeolite in this example are shown in Tables 1 to 3.

[0132] Example 3 The zeolite of this example was obtained in the same manner as in Example 2, except that the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 103.4 OH / SiO２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Ratio=0.050

[0133] The zeolite in this embodiment, based on its XRD pattern, was a single-phase TON-type zeolite (crystalline aluminosilicate) with a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of <0.05. Furthermore, the zeolite in this embodiment is SiO ２ / Al ２ O ３ The molar ratio is 97.5, the average maximum particle size is 0.7 μm, s （５５ｐｐｍ） / s （０ｐｐｍ） The value was 15.6. The characteristics of the zeolite in this embodiment are shown in Tables 1 to 3.

[0134] Comparative Example 1 A raw material composition was obtained in the same manner as in Example 2, except that an aqueous aluminum sulfate solution and colloidal silica (LUDOX® AS-40: manufactured by Sigma-Aldrich) were used instead of amorphous aluminosilicate, and the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 90.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 40 1,6-diaminohexane / SiO ２ Mole ratio = 0.300

[0135] The resulting raw material composition contains 1% by mass of seed crystals, using TON-type zeolite (SiO₂). ２ / Al ２ O ３ A seed crystal (with a molar ratio of 90) was added. The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition used in this comparative example was replaced with the raw material composition used in Example 2 (the raw material composition with added seed crystal).

[0136] The zeolite in this comparative example was a single-phase TON-type zeolite (crystalline aluminosilicate) based on its XRD pattern, with a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of <0.05. Furthermore, the zeolite in this comparative example was SiO ２ / Al ２ O ３ The molar ratio is 93.6, the average maximum particle size is 2.3 μm, s （５５ｐｐｍ） / s （０ｐｐｍ） The value was 9.4. The characteristics of the zeolite in this comparative example are shown in Tables 1 to 3.

[0137] Comparative Example 2 A raw material composition was obtained in the same manner as in Example 2, except that an aqueous aluminum sulfate solution and colloidal silica (LUDOX® AS-40: manufactured by Sigma-Aldrich) were used instead of amorphous aluminosilicate, and the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 90.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0138] The resulting raw material composition contains 1% by mass of seed crystals, using TON-type zeolite (SiO₂). ２ / Al ２ O ３ A seed crystal (with a molar ratio of 90) was added. The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition used in this comparative example was replaced with the raw material composition used in Example 2 (the raw material composition with added seed crystal).

[0139] The zeolite in this comparative example was a single-phase TON-type zeolite (crystalline aluminosilicate) based on its XRD pattern, with a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of <0.05. Furthermore, the zeolite in this comparative example was SiO２ / Al ２ O ３ The molar ratio is 82.4, the average maximum particle size is 6.3 μm, s （５５ｐｐｍ） / s （０ｐｐｍ） The value was 8.9. The characteristics of the zeolite used in this comparative example are shown in Tables 1 to 3.

[0140] Comparative Example 3: The raw material composition had the following molar composition, and TON-type zeolite (SiO₂) was used as the seed crystal. ２ / Al ２ O ３ The zeolite of this comparative example was obtained in the same manner as in Example 2, except that a molar ratio of 90 was used. ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 40 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0141] The zeolite in this comparative example was a single-phase TON-type zeolite (crystalline aluminosilicate) based on its XRD pattern, with a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of <0.05. Furthermore, the zeolite in this comparative example was SiO ２ / Al ２ O ３ The molar ratio is 89.4, the average length of the crystal's longest side is 2.7 μm, s （５５ｐｐｍ） / s （０ｐｐｍ） The result was 12.7.

[0142] Comparative Example 4 The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２Molar ratio = 40 1,6-diaminohexane / SiO ２ Mole ratio = 0.300

[0143] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI-type and TON-type zeolites, and possessed MFI-type and TON-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 2.01.

[0144] Comparative Example 5 The zeolite of this comparative example was obtained in the same manner as in Example 2, except that an aqueous aluminum sulfate solution and colloidal silica (LUDOX® AS-40: manufactured by Sigma-Aldrich) were used instead of amorphous aluminosilicate, and the raw material composition was as follows (molar composition). SiO ２ / Al ２ O ３ Molar ratio = 90.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 40 1,6-diaminohexane / SiO ２ Mole ratio = 0.300

[0145] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of TON-type and MFI-type zeolites, and possessed TON-type and MFI-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 0.57.

[0146] Comparative Example 6 The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 62.2 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0147] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of TON-type and MFI-type zeolites, and possessed TON-type and MFI-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of 0.09 and an MFI-type zeolite intensity ratio of 0.30.

[0148] Comparative Example 7 The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition had the following molar composition: SiO ２ / Al ２ O ３ Molar ratio = 111.3 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0149] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of TON-type and cristobalite, and was a TON-type zeolite containing cristobalite. The zeolite in this comparative example had a cristobalite intensity ratio of 0.47 and an MFI-type zeolite intensity ratio of <0.05.

[0150] Comparative Example 8 The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition had the following molar composition and seed crystals were not mixed into the raw material composition. SiO ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0151] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of TON-type and MFI-type zeolites, and possessed TON-type and MFI-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 0.23.

[0152] Comparative Example 9 The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition had the following molar composition and seed crystals were not mixed into the raw material composition. SiO ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 40 1,6-diaminohexane / SiO ２ Mole ratio = 0.300

[0153] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI-type and TON-type zeolites, and possessed MFI-type and TON-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 2.68.

[0154] Comparative Example 10 The raw material composition had the following molar composition, and FAU-type zeolite (product name: HSZ(registered trademark)-385HUA, SiO) was used as the seed crystal. ２ / Al ２ O ３ The zeolite of this comparative example was obtained in the same manner as in Example 2, except that a molar ratio of 100 was used. ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0155] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of TON-type and MFI-type zeolites, and possessed TON-type and MFI-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 0.26.

[0156] Comparative Example 11 The raw material composition had the following molar composition, and FAU-type zeolite (product name: HSZ(registered trademark)-385HUA, SiO) was used as the seed crystal. ２ / Al ２ O ３ The zeolite of this comparative example was obtained in the same manner as in Example 2, except that a molar ratio of 100 was used. ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 40 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0157] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI-type and TON-type zeolites, and possessed MFI-type and TON-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 1.25.

[0158] Comparative Example 12 The raw material composition had the following molar composition, and the seed crystal was zeolite beta (product name: HSZ(registered trademark)-940NHA, SiO ２ / Al ２ O ３ The zeolite of this comparative example was obtained in the same manner as in Example 2, except that a molar ratio of 40 was used. ２ / Al ２ O ３Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0159] The zeolite (crystalline aluminosilicate) in this comparative example exhibited an XRD pattern characteristic of MFI type and cristobalite, and was an MFI type zeolite containing cristobalite.

[0160] Comparative Example 13 The raw material composition had the following molar composition, and the seed crystal was a MOR-type zeolite (product name: HSZ(registered trademark)-660HOA, SiO ２ / Al ２ O ３ The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the molar ratio was set to 30. SiO ２ / Al ２ O ３ Molar ratio = 92.0 OH / SiO ２ Molar ratio = 0.110 K / SiO ２ Molar ratio = 0.110 H ２ O / SiO ２ Molar ratio = 11 1,6-diaminohexane / SiO ２ Mole ratio = 0.050

[0161] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI-type and TON-type zeolites, and possessed MFI-type and TON-type crystal structures. The zeolite in this comparative example had a cristobalite intensity ratio of <0.05 and an MFI-type zeolite intensity ratio of 1.03.

[0162] The evaluation results for the examples and comparative examples are shown in Tables 1 to 3 below. In the tables, "Cri" refers to cristobalite.

[0163]

[0164]

[0165]

[0166] Measurement example (isomerization reaction of n-decane): TON-type zeolite and H of Example 1 and Comparative Example 1. ２ PtCl ６ By contacting the TON-type zeolite with an aqueous solution (hexachloride platinum(IV) acid aqueous solution), H ２ PtCl ６ The material was impregnated with an aqueous solution. ２ PtCl ６ TON-type zeolites impregnated with an aqueous solution were dried at 110°C for 5 hours, and then calcined in air at 450°C for 4 hours to support platinum elements on each TON-type zeolite. The platinum-supported TON-type zeolites were used as catalysts for the isomerization reaction, and the following isomerization reaction was carried out. Each isomerization catalyst contained 0.5% by mass of platinum elements per 100% by mass of the isomerization catalyst.

[0167] Each isomerization catalyst was press-molded to produce aggregated particles with an aggregation diameter of 20 to 30 mesh. One g of the aggregated sample was packed into each of the atmospheric pressure fixed-bed flow-through reaction tubes and pre-treated under the following conditions (pre-treatment conditions): Gas used: Hydrogen gas Flow rate: 25 ml / min Pressure: 0.2 MPaG Temperature: 350°C Time: 3 hours

[0168] Immediately after the completion of pretreatment, the temperature was lowered from 350°C to the reaction temperature below. A fluid mixture of hydrogen and n-decane was introduced into a fixed-bed flow-through reaction tube filled with the isomerization catalyst at atmospheric pressure, and the isomerization reaction was carried out under the following conditions: Flow fluid: Mixture of hydrogen and n-decane Reaction temperature: 260°C Pressure: 0.2 MPaG WHSV of n-decane: 1.67 h －１ (n-decane flow rate 1.67 g / h) Hydrogen / n-decane volume ratio: 656 vol / vol (hydrogen flow rate 1.5 L / h)

[0169] Ten hours after a fluid mixture of hydrogen and n-decane was passed through the system, the outlet gas of the fixed-bed flow-through reaction tube was sampled using an autosampler (product name: GHS-343A, manufactured by J-Science Co., Ltd.), and the components of the outlet gas were analyzed using gas chromatography (product name: GC-7100, manufactured by J-Science Co., Ltd.). The outlet gas was sampled while maintaining a temperature of 220°C between the outlet of the fixed-bed flow-through reaction tube and the autosampler. A capillary column (product name: Supelco® SPB-Octy, manufactured by Sigma-Aldrich) was used as the gas chromatography separation column.

[0170] The conversion rate of n-decane, the yield of the isomer of n-decane, a C10 branched paraffin (hereinafter also referred to as "C10 branched paraffin"), and the selectivity of a C10 single branched paraffin (hereinafter also referred to as "C10 single branch selectivity") are shown in Table 4 below.

[0171]

[0172] The conversion rate of n-decane was calculated using the following formula (2): Conversion rate of n-decane (%) = {([C10SP]in - [C10SP]out) / [C10SP]in} × 100 ... (2) In the above formula (2), [C10SP]in represents the concentration of n-decane (v / v%) in the gas introduced into the fixed-bed flow-through reactor, and [C10SP]out represents the concentration of n-decane (v / v%) in the outlet gas.

[0173] The C10 branched paraffin yield was determined from the following formula (3): C10 branched paraffin yield (%) = ([C10BP]out / [All]out) × [C10SP]cvt ... (3) In the above formula (3), [C10BP]out represents the concentration of C10 branched paraffin in the outlet gas (v / v%), [All]out represents the total concentration of all products (components other than n-decane) contained in the outlet gas (v / v%), and [C10SP]cvt is the conversion rate of n-decane (%) obtained from the above formula (2).

[0174] Furthermore, the C10 single branch selectivity was calculated from the following formula (4): C10 single branch selectivity (%) = ([monoC10BP]out / [C10BP]out) × 100 ... (4) In the above formula (4), [C10BP]out represents the concentration of C10 branched paraffin in the outlet gas (v / v%), and [monoC10BP]out represents the concentration of C10 single branched paraffin in the outlet gas (v / v%).

[0175] As shown in Table 4 above, the isomerization catalyst based on TON-type zeolite of Example 1 (hereinafter also referred to as "the isomerization catalyst of Example 1") showed a higher yield of C10 branched paraffin and a higher selectivity for single branching of C10 compared to the isomerization catalyst based on TON-type zeolite of Comparative Example 1 (hereinafter also referred to as "the isomerization catalyst of Comparative Example 1"). From these results, it was found that the TON-type zeolite of Example 1 is more suitable as a substrate for the isomerization catalyst than the TON-type zeolite of Comparative Example 1.

[0176] The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2025-41440, filed on March 14, 2025, are incorporated herein by reference as part of the disclosure of the specification.

Claims

1. A TON-type zeolite having a molar ratio of silica to alumina of 70 to 110, an average maximum particle size of less than 1.5 μm, and in an NMR spectrum measured by 27Al-MAS-NMR, the ratio of the area intensity of a peak with a peak top at a chemical shift of 55 ± 5 ppm to the area intensity of a peak with a peak top at a chemical shift of 0 ± 5 ppm is 13 to less than 30.

2. The TON-type zeolite according to claim 1, wherein the average maximum particle size is 0.1 μm or more and less than 1.5 μm.

3. The TON-type zeolite according to claim 1 or 2, wherein the MFI-type zeolite intensity ratio, which is the ratio of the height intensity of the XRD peak having a peak top at a diffraction angle 2θ = 23.1 ± 0.3° to the height intensity of the XRD peak having a peak top at a diffraction angle 2θ = 20.4 ± 0.3° in the powder X-ray diffraction pattern, is less than 0.

05.

4. The TON-type zeolite according to any one of claims 1 to 3, wherein the cristobalite intensity ratio, which is the ratio of the height intensity of the XRD peak having a peak top at a diffraction angle of 21.4 ± 0.3° (2θ) to the height intensity of the XRD peak having a peak top at a diffraction angle of 20.4 ± 0.3° (2θ) in the powder X-ray diffraction pattern, is less than 0.

05.

5. A TON-type zeolite according to any one of claims 1 to 4, wherein the acid content is 0,200 mmol / g or more and 1,000 mmol / g or less.

6. BET specific surface area is 100 m² ２ / g or more 500m ２ A TON-type zeolite according to any one of claims 1 to 5, wherein the amount is less than or equal to / g.

7. External surface area is 10m ２ / g or more 200m ２ A TON-type zeolite according to any one of claims 1 to 6, wherein the amount is less than or equal to / g.

8. The TON-type zeolite according to any one of claims 1 to 7, wherein the particle diameter D50 at which the cumulative volume from the small particle side in the volume particle size distribution accounts for 50% is 20 μm or more and 150 μm or less.

9. A method for producing TON-type zeolite, comprising the step of crystallizing a raw material composition containing a silica source, an alumina source, an alkali source, a structure-directing agent source, and water in the presence of a seed crystal, wherein the raw material composition has a molar ratio of silica to alumina of 70 or more and 110 or less, and a molar ratio of water to silica of 8 or more and 15 or less, and the seed crystal is a FER-type zeolite.

10. The method for producing a TON-type zeolite according to claim 9, wherein the structure-directing agent source is 1,6-diaminohexane.

11. The method for producing a TON-type zeolite according to claim 9 or 10, wherein the raw material composition substantially contains no organic compounds other than the structure-directing agent source.

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