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

Abstract

The present invention provides 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. 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 the NMR spectrum measured by 27Al-MAS-NMR, the ratio of the area intensity of the peak with a peak top at a chemical shift of 55±5 ppm to the area intensity of the peak with a peak top at a chemical shift of 0±5 ppm is 13 to less than 30.

Description

[Technical Field]

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

[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. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2011-206649 [Overview of the Initiative] [Problems that the invention aims to solve]

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

[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. [Means for solving the problem]

[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 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 the peak with a peak top at a chemical shift of 55±5 ppm to the area intensity of the peak with a peak top at a chemical shift of 0±5 ppm is 13 to less than 30. [2] The TON-type zeolite described in [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 [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] 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 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 as described in 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 100m 2 / g or more 500m 2 A TON-type zeolite described in any one of [1] to [5], which is less than or equal to / g. [7] External surface area is 10m 2 / g or more 200m 2 A TON-type zeolite described in any one of [1] to [6], which is less than or equal to / g. [8] A TON-type zeolite according to any one of [1] to [7], wherein the particle size 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 FER-type zeolite.

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

[11] A method for producing TON-type zeolite according to [9] or

[10] , wherein the raw material composition substantially contains no organic compounds other than the structure-directing agent source. [Effects of the Invention]

[0009] This disclosure provides 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. [Modes for carrying out the invention]

[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 either metallic atoms or metalloid atoms. 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 materials refers to zeolites that have a skeletal structure specified by the structural code (hereinafter also simply referred to as the "structural code") established by the Structure Commission of the International Zeolite Association (hereinafter also referred to as the "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 Association's website (http: / / www.iza-structure.org / databases / ). Note that, with respect 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 (for example, instrument name: Ultima IV, manufactured by Rigaku). Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.54178Å) Measurement mode: Continuous scan Scanning conditions: 10° / min Measurement range: 2θ = 5° to 40° Scattering slit: 1 / 3° Divergent slit: 1 / 3° Light-receiving slit: 0.3mm 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," while 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, manufactured by 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 given. The following conditions can be used for XRD pattern analysis. Fitting conditions: Automatic, background refinement Distributed 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 "crystallization step"). The raw material composition used in the method of production of this embodiment has an SiO2 / Al2O3 molar ratio of 70 to 110, and a molar ratio of water to silica (molar ratio of water to silica (hereinafter also referred to as "H2O / SiO2 molar ratio")) of 8 to 15. The seed crystal used in the method of production of this embodiment is FER-type zeolite. According to the method of production of this embodiment, a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm can be produced.

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

[0022] To measure the average maximum particle size, first, arbitrarily select 50 ± 10 primary particles whose contours are observed without interruption in the SEM observation image. Measure the distance between the two parallel lines that are tangent to the contour of each selected primary particle, and measure the distance between the parallel lines that yields the longest distance (maximum particle size). The average value of these distances is then taken as the average maximum particle size. The number of SEM observation images should be sufficient, as long as the number of primary particles observed is as described above; one or more SEM observation images may be used.

[0023] In addition, in the present embodiment, the single-phase TON-type zeolite is a zeolite substantially composed of only the TON-type zeolite. Being substantially composed of only the TON-type zeolite does not only mean being composed of only the TON-type zeolite, but also allows for containing a trace amount of at least one of the MFI-type zeolite and cristobalite that are likely to be by-produced together with the TON-type zeolite.

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

[0025] Also, the trace amount of cristobalite refers to the amount of cristobalite such that the cristobalite intensity ratio is 0.05 or less. The cristobalite intensity ratio is the ratio (p (2θ=20.4°) ) of the height intensity (hereinafter also referred to as "p (2θ=21.4°) ") of the XRD peak having a peak top at a diffraction angle 2θ = 21.4 ± 0.3°, which is the main XRD peak of cristobalite, with respect to the height intensity p (2θ=21.4°) of the main XRD peak of the TON-type zeolite. The ratio (p (2θ=20.4°) ) functions as a parameter indicating the mass ratio of cristobalite to the 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 crystallized in the crystallization process includes a silica source. The silica source included in the raw material composition is a compound containing silica (SiO2) or silicon, which is a precursor thereof, and includes, 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-product formation of cristobalite and MFI type zeolite, it is preferable that the silica source included in the raw material composition is 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 crystallized in the crystallization process includes an alumina source. The alumina source included in the raw material composition is a compound containing alumina (Al2O3) or aluminum, which is a precursor thereto, and includes, 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-product formation of cristobalite and MFI type zeolite, it is preferable that the alumina source included in the raw material composition is 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 includes an alkali source. The alkali source included 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 included 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 crystallized in the crystallization process has an SiO2 / Al2O3 molar ratio of 70 to 110. This ratio allows for the production of single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm. Conversely, if the SiO2 / Al2O3 molar ratio of the raw material composition is less than 70 or greater 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 produce single-phase TON-type zeolite.

[0036] The SiO2 / Al2O3 molar ratio of the raw material composition may be 70 or more and 110 or less, but from the viewpoint of further suppressing the by-product formation of cristobalite and MFI-type zeolite, it is preferable that it be 80 or more, 85 or more, or 90 or more, and preferably 105 or less, 100 or less, or 95 or less. The combination of the upper and lower limits of the SiO2 / Al2O3 molar ratio described above is arbitrary, but from the viewpoint of further suppressing the by-product formation of cristobalite and MFI-type zeolite, the SiO2 / Al2O3 molar ratio of the raw material composition 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.

[0037] The raw material composition crystallized in the crystallization process has an H2O / SiO2 molar ratio of 8 to 15. A H2O / SiO2 molar ratio of 8 to 15 in the raw material composition allows for the production of single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm. On the other hand, if the H2O / SiO2 molar ratio of the raw material composition is less than 8, at least one of cristobalite or MFI-type zeolite is more likely to be produced as a by-product, making it impossible to produce single-phase TON-type zeolite. Furthermore, if the H2O / SiO2 molar ratio of the raw material composition exceeds 15, the crystal growth rate becomes dominant over the nucleation rate in the crystallization of TON-type zeolite, resulting in a larger average maximum particle size of the produced TON-type zeolite. Additionally, if the H2O / SiO2 molar ratio of the raw material composition exceeds 15, at least one of cristobalite or MFI-type zeolite is more likely to be produced as a by-product.

[0038] The H2O / SiO2 molar ratio of the raw material composition may be 8 or more and 15 or less, 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 more, or 10 or more, and from the viewpoint of further reducing the average maximum particle size, it is preferable to have a ratio of 13 or less, or 12 or less. The combination of the upper and lower limits of the H2O / SiO2 molar ratio as described above 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 H2O / SiO2 molar ratio of the raw material composition is preferably 9 or more and 13 or less, and more preferably 10 or more and 12 or less.

[0039] The raw material composition to be crystallized in the crystallization process is not particularly limited in terms of the molar ratio of SDA to silica-equivalent silicon (hereinafter also referred to as the "SDA / SiO2 molar ratio"). From the viewpoint of reducing the average maximum particle size of the TON type produced and further suppressing the by-product formation of cristobalite and MFI type zeolite, the SDA / SiO2 molar ratio of the raw material composition is preferably 0.010 or more, 0.020 or more, or 0.040 or more, and preferably 0.500 or less, 0.300 or less, or 0.100 or less. The combination of the upper and lower limits of the SDA / SiO2 molar ratio described above is arbitrary, but from the viewpoint of reducing the average maximum particle size of the TON type produced and further suppressing the by-product formation of cristobalite and MFI type zeolite, the SDA / SiO2 molar ratio of the raw material composition 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 crystallized in the crystallization process is not particularly limited in terms of the molar ratio of alkali metal to silica-based silicon (hereinafter also referred to as the "M / SiO2 molar ratio"). From the viewpoint of reducing the average maximum particle size of the TON type produced and further suppressing the by-product formation of cristobalite and MFI type zeolite, the M / SiO2 molar ratio of the raw material composition is preferably 0.010 or more, 0.050 or more, or 0.100 or more, and preferably 0.500 or less, 0.200 or less, or 0.150 or less. The combination of the upper and lower limits of the M / SiO2 molar ratio described above is arbitrary, but from the viewpoint of reducing the average maximum particle size of the TON type produced and further suppressing the by-product formation of cristobalite and MFI type zeolite, the M / SiO2 molar ratio of the raw material composition 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. In the M / SiO2 ratio, M represents the total amount of alkali metals. When the alkali metal is potassium, or when the alkali metals are sodium and potassium, the M / SiO2 ratio becomes the K / SiO2 molar ratio or the (Na+K) / SiO2 molar ratio, respectively.

[0041] The raw material composition to be crystallized in the crystallization process is not particularly limited in terms of the molar ratio of hydroxide ions to silicon in silica terms (hereinafter also referred to as the "OH / SiO2 molar ratio"). From the viewpoint of reducing the average maximum particle size of the TON type produced and further suppressing the by-product formation of cristobalite and MFI type zeolite, the OH / SiO2 molar ratio of the raw material composition is preferably 0.010 or more, 0.050 or more, or 0.100 or more, and preferably 0.500 or less, 0.200 or less, or 0.150 or less. The combination of the upper and lower limits of the OH / SiO2 molar ratio described above is arbitrary, but from the viewpoint of reducing the average maximum particle size of the TON type produced and further suppressing the by-product formation of cristobalite and MFI type zeolite, the OH / SiO2 molar ratio of the raw material composition 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. SiO2 / Al2O3 molar ratio = 80 to 105 More preferably 90 to 95 SDA / SiO2 molar ratio = 0.010 or higher and 0.500 or lower More preferably 0.040 or more and 0.100 or less M / SiO2 molar ratio = 0.010 or higher and 0.500 or lower More preferably 0.100 or more and 0.150 or less OH / SiO2 molar ratio = 0.010 or greater and 0.500 or less More preferably 0.100 or more and 0.150 or less H2O / SiO2 molar ratio = 9 to 13 More preferably 10 to 12

[0043] In the crystallization process, the raw material composition is crystallized in the presence of a seed crystal, which is an 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 with 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 ratio of the total mass of silicon and aluminum in the seed crystal (FER-type zeolite) converted to silica (SiO2) and alumina (Al2O3), respectively, to 100% by mass of the total mass of silicon and aluminum in the raw material composition (excluding seed crystal) converted to silica (SiO2) and alumina (Al2O3), respectively (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. While the combination of the upper and lower limits for the seed crystal content mentioned above is arbitrary, from the viewpoint of making the average maximum particle size of the TON type produced 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 produced and further suppressing the by-product formation of cristobalite and MFI-type zeolite, it is preferable that it be a crystalline aluminosilicate with an SiO2 / Al2O3 molar ratio of 10 to 200, and more preferably a crystalline aluminosilicate with an SiO2 / Al2O3 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 vessel and heating it. Examples of hydrothermal treatment conditions include the following: Processing temperature: 80°C or higher or 140°C or higher, Below 190°C or below 180°C Processing time: 2 hours or more, 500 hours or less Processing pressure: Self-generating 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] Acid treatment to remove SDA is a process of contacting TON-type zeolite with an acid. Acid treatment can remove not only SDA contained in TON-type zeolite but also alkali metal elements. The method of contacting TON-type zeolite with acid is not particularly limited, but one example is mixing TON-type zeolite with the acid. For the acid to be contacted with TON-type zeolite, hydrochloric acid can be used, and it is preferable to use hydrochloric acid with a concentration of 0.1 ml / L to 6.0 ml / 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 "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 "acid contact time"), the easier it is to remove SDA from TON-type zeolite; and the higher the contact temperature between TON-type zeolite and acid (hereinafter also referred to as "acid contact temperature"), the easier it is to remove SDA from TON-type zeolite. Therefore, it is preferable to appropriately adjust the acid / zeolite mass ratio, acid contact time, and acid contact temperature, taking into consideration the aforementioned characteristics, in order to achieve 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 a desired cation type. For example, converting the cation type of TON-type zeolite to an ammonium type (hereinafter referred to as "NH4")+ To convert the cation type of the TON-type zeolite to the proton type (H), 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 solution. + To make it a type, for example, NH4 + A treatment can be used in which the TON-type zeolite is heated in an air atmosphere at a temperature of 500°C to 600°C for 1 to 2 hours.

[0055] In the manufacturing method of this embodiment, the post-treatment steps described above (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 manufacturing method of this embodiment described above, a single-phase TON-type zeolite with an average maximum particle size of less than 1.5 μm can be produced. Furthermore, since the TON-type zeolite produced by the manufacturing method of this embodiment has an average maximum particle size of less than 1.5 μm and is a TON-type zeolite with a small particle size, it can have a larger contact area with the reactants compared to TON-type zeolites with a larger particle size of 1.5 μm or more, making it suitable as a substrate for isomerization reaction catalysts.

[0057] The following describes the TON-type zeolite that can be manufactured by the manufacturing method of this embodiment (hereinafter also referred to as "TON-type zeolite of this embodiment").

[0058] The TON-type zeolite of this embodiment (hereinafter also referred to as "TON-type zeolite of this embodiment") has an average maximum particle size of less than 1.5 μm, a molar ratio of silica to alumina (hereinafter also referred to as "SiO2 / Al2O3 molar ratio") of 70 to 110, and in the NMR spectrum measured by 27Al-MAS-NMR, the area intensity of the peak having a peak top at a chemical shift of 0 ± 5 ppm (hereinafter referred to as "s") (0ppm)The area intensity of the peak with a peak top at a chemical shift of 55±5 ppm (hereinafter referred to as "s") (55ppm) The ratio of (also called "s") (hereinafter referred to as "s") (55ppm) / s (0ppm) It is characterized by having a value of 13 or more but less than 30 (also known as "...").

[0059] The TON-type zeolite of this embodiment has an average maximum particle size of less than 1.5 μm. Because the TON-type zeolite of this embodiment has an average maximum particle size of less than 1.5 μm, it can have a larger contact area with the reactants compared to TON-type zeolites with larger particle sizes, such as those with an average maximum particle size of 1.5 μm or more, making it suitable as a substrate for isomerization reaction catalysts. From the viewpoint of making it a more suitable substrate for isomerization reaction catalysts, the average maximum particle size of the TON-type zeolite of this embodiment is preferably 1.2 μm or less, or 1.0 μm or less, and preferably 0.1 μm or more, or 0.3 μm or more. The above-mentioned combination of upper and lower limits for the average maximum particle size is arbitrary, but from the viewpoint of making it a more suitable substrate for isomerization reaction catalysts, the average maximum particle size of the TON-type zeolite of this 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 this embodiment has an SiO2 / Al2O3 molar ratio of 70 to 110. From the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the SiO2 / Al2O3 molar ratio of the TON-type zeolite of this embodiment is preferably 80 or more, 85 or more, or 90 or more, and preferably 105 or less, 100 or less, or 95 or less. The combination of the upper and lower limits of the SiO2 / Al2O3 molar ratio described above is arbitrary, but from the viewpoint of providing a substrate more suitable as a catalyst for isomerization reactions, the SiO2 / Al2O3 molar ratio of the TON-type zeolite of this embodiment is preferably 80 to 105, more preferably 85 to 100, and even more preferably 90 to 95.

[0061] The TON-type zeolite of this embodiment may contain T atoms other than aluminum (Al) and silicon (Si) as T atoms constituting the skeletal structure, provided that the SiO2 / Al2O3 molar ratio is 70 or more and 110 or less. 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 ratio is 13 or more and less than 30. 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 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, 4-coordinate aluminum (hereinafter referred to as "4-coordinate Al") belongs to a peak with a peak top at a chemical shift of 55±5 ppm, and 6-coordinate aluminum (hereinafter referred to as "6-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 standard 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 sample. The following conditions can be used for 27Al-MAS-NMR measurements. Observed nucleus: 27Al (182.4MHz) Rotation frequency: 24kHz Pulse width: 2.1 μs Waiting time: 2 seconds Total number of times: 3500

[0065] s (55ppm) / s (0ppm) From the NMR spectrum measured with 27Al-MAS-NMR, a peak with a peak top at a chemical shift of 0±5 ppm (hereinafter referred to as "P") is found. 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] From the NMR spectrum measured by 27Al-MAS-NMR, P 0ppm and P 55ppm To separate them, conventionally known waveform separation methods (peak fitting) can be used. Specifically, from the NMR spectrum measured with 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, the experimental NMR spectrum contains one P0 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% compared 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 integral intensity of can be used. Note that P 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 of this embodiment is not particularly limited, but from the viewpoint of making it a more suitable base material 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 making it a more suitable base material as a catalyst for isomerization reactions, the acid content of the TON-type zeolite of 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: BELCATII, manufactured by Microtrac-Bel 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 of zeolite used for ammonia adsorption [g]. 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, examples of inert gases include at least one of helium and argon, with helium being preferred.

[0069] Acid amount [mmol / g] =W NH3 / W Z ... (1) In the above equation (1), W NH3 This indicates the amount of ammonia released [mmol], 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 (before ammonia adsorption) after treatment at 600°C in an air atmosphere for 1 hour.

[0070] 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 BET specific surface area is 100 m². 2 / g or more, 150m 2 / g or more, or 200m 2 It is preferable that it be 1 / g or more, and 500m 2 / g or less, 400m 2 / g or less, or 300m 2 It is preferable that the amount is 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 100m². 2 / g or more 500m 2 It is preferable that it be less than or equal to / g, and 150m 2 / g or more 400m 2 It is more preferable that it be less than or equal to / g, and 200m 2 / g or more 300m 2 It is even more preferable that the value be 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℃ 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 external surface area is 10 m². 2 / g or more, 15m 2 / g or more, or 20m 2 It is preferable that it be 200m or more per gram. 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 mentioned 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 10m². 2 / g or more 200m 2 It is preferable that the amount 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 / g, 20m 2 / g or more 50m 2 It is even more preferable that the value be 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 that used to determine the BET specific surface area, with the t-plot method.

[0074] For the analysis of adsorption isotherms to determine the BET specific surface area and outer surface area, general analysis software (e.g., BELMaster) is used. TM Standard isotherms (manufactured by Microtrac-Bell) 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.

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

[0078] In the TON-type zeolite of the present 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 being a more suitable base material as a catalyst for the isomerization reaction, it is preferably less than 0.05. In the TON-type zeolite of the present embodiment, the lower limit value of the MFI-type zeolite intensity ratio is not particularly limited, and it may be 0 or more. That is, in the TON-type zeolite of the present embodiment, the MFI-type zeolite intensity ratio may be 0 or more and 0.05 or less, but from the viewpoint of being a more suitable base material as a catalyst for the isomerization reaction, it is preferably 0 or more and less than 0.05.

[0079] In the TON-type zeolite of the present embodiment, the cristobalite intensity ratio (p (2θ=21.4°) / p (2θ=20.4°)The cristobalite intensity ratio 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 more. 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. Since the TON-type zeolite of this embodiment has an average maximum particle size of less than 1.5 μm and 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 larger 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 between 13 and 30, the isomerization reaction catalyst that uses it as a base material is s (55ppm) / s (0ppm) Compared to isomerization catalysts using TON-type zeolite with a ratio of less than 13, the isomerization reaction of linear paraffins to branched paraffins can proceed more efficiently. For this reason, the isomerization catalyst using TON-type zeolite 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. In addition, the preferred isomerization catalyst using TON-type zeolite 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 generated 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 generated 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 it may be used as a catalyst on its own, or as a carrier for supporting a predetermined component.

[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 be 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass or more, and 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 isomerization reaction catalyst.

[0090] The drying of the TON-type zeolite impregnated with a metal aqueous solution in this embodiment can be any method that removes water from the TON-type zeolite in this embodiment, and is not particularly limited. 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 mentioned.

[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 filling a fixed-bed flow-type reaction tube with the isomerization catalyst according to this embodiment and flowing the linear paraffin-containing fluid through it (flow method), or filling the inside of a reaction vessel containing the isomerization catalyst according to this embodiment with the linear paraffin-containing fluid (batch reaction method).

[0094] The linear paraffin-containing fluid 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 contact atmosphere pressure (gauge pressure) 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] The weight hourly space velocity (WHSV) of the linear paraffin in the linear paraffin-containing fluid contacted with the catalyst for isomerization reaction according to this embodiment is, from the viewpoint of further improving the branched paraffin yield, 0.10 h -1 or more, 0.50 h -1 or more, or 1.00 h -1 or more, and preferably 5.00 h -1 or less, 3.00 h -1 or less, or 2.00 h -1 or less. The combination of the upper and lower limits of the WHSV of the above-mentioned linear paraffin is arbitrary, but from the viewpoint of further improving the branched paraffin yield, 0.10 h -1 or more and 5.00 h -1 or less is preferable, 0.50 h -1 or more and 3.00 h -1 or less is more preferable, and 1.00 h -1 or more and 2.00 h -1 or less is even more preferable. Note that the WHSV of the linear paraffin is a parameter representing the supply amount of the linear paraffin per unit mass of the catalyst for isomerization reaction in one hour ([g (catalyst for isomerization reaction)] / [g (linear paraffin) / h] (= [h -1 ))

[0101] The volume ratio of hydrogen to the linear paraffin in the linear paraffin-containing fluid contacted with the catalyst for isomerization reaction according to this embodiment (hereinafter, also referred to as "hydrogen / linear paraffin volume ratio") is, from the viewpoint of further improving the branched paraffin yield, preferably 100 or more, 200 or more, or 500 or more, and preferably 1000 or less, 900 or less, or 800 or less. The combination of the upper and lower limits of the above-mentioned hydrogen / linear paraffin volume ratio 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] Regarding the contact time between the catalyst for isomerization reaction according to this embodiment and the linear paraffin-containing fluid, it may be appropriately set according to the production amount of the 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. [Examples]

[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] (composition 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, PerkinElmer). From the obtained Si and Al measurements, the SiO2 / Al2O3 molar ratio of the sample was determined.

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

[0107] (Evaluation of crystallinity) From the XRD pattern obtained by the above measurement, the height intensity p of the XRD peak having a peak top at the diffraction angle 2θ = 20.4 ± 0.3° (2θ=20.4°) The height and intensity of the XRD peak p has its peak top at the diffraction angle 2θ = 21.4 ± 0.3°. (2θ=21.4°) , and the height intensity p of the XRD peak having a peak top at the diffraction angle 2θ = 23.1 ± 0.3° (2θ=23.1°) We calculated p. (2θ=20.4°) and p (2θ=23.1°) From the intensity ratio of MFI type zeolite (p (2θ=23.1°) / p (2θ=20.4°) ) calculates the obtained p (2θ=20.4°) and p (2θ=21.4°) From the cristobalite intensity ratio (p (2θ=21.4°) / p (2θ=20.4°) ) was calculated.

[0108] Note, p (2θ=20.4°) , p (2θ=21.4°) and p (2θ=23.1°) The detection and height intensity were calculated by analyzing the obtained XRD patterns using analysis software (software name: SmartLab StudioII, manufactured by Rigaku Corporation). The following conditions were used for the analysis. Fitting conditions: Automatic, background refinement Distributed pseudo-Voigt function (peak shape) Background removal method: Fitting method Kα2 removal method: Kα1 / Kα2 ratio=0.497 Smoothing method: Smoothing using 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 they substantially did not contain MFI-type zeolite, 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 they substantially did not contain cristobalite, 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 (182.4MHz) Rotation frequency: 24kHz Pulse width: 2.1 μs Waiting time: 2 seconds Total number of times: 3500

[0111] From the NMR spectrum (experimental NMR spectrum) obtained by 27Al-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 P0ppm 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 55ppm Waveform separation was performed assuming a full width at half maximum (FMAX) 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). For baseline correction, the points at -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 observations were performed using a standard 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 was measured using a standard gas adsorption apparatus (device name: BELSORP-MAXII, manufactured by Microtrac-Bel) via the constant volume method. The measurement conditions are as follows: Adsorbate gas: Nitrogen Measurement temperature: -196℃ 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 This is also called ). The BET method analysis was performed by plotting data with a relative pressure (P / P0) between 0.001 and 0.990 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 using the t-plot method) The adsorption isotherm of nitrogen gas obtained from the above measurements was analyzed using the t-plot method to determine the outer 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-BEL) 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 (instrument name: Microtrac MT3300EXII, manufactured by Microtrac-Bell Co., Ltd.). The measurement conditions were as follows. Measurement range: 0.02~2000μm Particle refractive index: 1.66 Particle permeability: transparent Particle shape: non-spherical Solvent refractive index: 1.333 Ultrasonic pretreatment: None

[0119] (Measurement of acid content) The acid content was measured using the Temperature Programmed Desorption (TPD) method with an online gas analyzer (BELCAT II, ​​Microtrac-Bel). First, 0.05 g of the sample was pre-treated by heating it 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 and 1% ammonia by volume. This mixture was flowed 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 flowed for 0.5 hours to remove any remaining ammonia in the atmosphere (ammonia not adsorbed on the zeolite).

[0120] After removing ammonia, the ammonia temperature-controlled desorption spectrum was obtained by increasing the temperature under the following conditions. Atmosphere: Helium flow atmosphere (flow rate 30 mL / min) Heating rate: 10°C / min Processing temperature: 100℃~700℃

[0121] After the temperature was raised from 100°C to 700°C, a mixed gas of ammonia and helium with a known ammonia content (hereinafter also referred to as "NH3-He mixed gas") was passed to the detector via a route that did not pass through the sample being measured (a separate line), and spectra for sensitivity correction of the detector were obtained. Spectra for sensitivity correction were obtained by passing four types of gases: a first NH3-He mixed gas with an ammonia concentration of 0.206 vol%; a second NH3-He mixed gas with an ammonia concentration of 0.137 vol%; a third NH3-He mixed gas with an ammonia concentration of 0.069 vol%; and helium gas alone. These NH3-He mixed gases and helium gases were passed at a flow rate of 30 mL / min, a flow time of 15 minutes, and a temperature of 100°C, respectively.

[0122] Background correction was performed on the obtained ammonia temperature-induced desorption spectrum. The background correction was carried out using multi-point correction. Specifically, the correction was performed by connecting a total of four points: the point just 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), the point just before the start of the flow of NH3-He mixed gas to correct the detector sensitivity, and the point just before the end of the flow of helium gas alone.

[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, "w (200℃) It is also called ", and P 420℃ The integral value of (hereinafter, "w (420℃) Also called ''. The total value of ) was calculated. From the integral value of the peak intensity of the peaks included in the spectrum for sensitivity correction and the amount of ammonia contained in the NH3-He mixed gas that was passed through to obtain the spectrum for sensitivity correction, the relationship between the integral value of the peak intensity and the amount of ammonia was 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] released 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 equation (1) above. Note that W in equation (1) above Z The mass of zeolite used for ammonia adsorption [g] was calculated using the dry mass [g] of the sample after treatment at 600°C in an air atmosphere for 1 hour.

[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. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar ratio = 0.050

[0127] To the obtained raw material composition, FER-type zeolite (product name: HSZ(registered trademark)-720NHA, SiO2 / Al2O3 molar ratio = 18) was added as a seed crystal so that the seed crystal content was 1% by mass. Then, 3600 g of the raw material composition was filled into a sealed container with a volume of 4000 mL and heated at 160°C for 36 hours while stirring at 400 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.

[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 has an SiO2 / Al2O3 molar ratio of 95.1 and an average maximum particle size of 0.9 μm. (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 The raw material composition was obtained in the same manner as in Example 1, except that the raw material composition had the following molar composition. SiO2 / Al2O3 molar ratio = 81.7 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar ratio = 0.050

[0130] To the obtained raw material composition, FER-type zeolite (product name: HSZ(registered trademark)-720NHA, SiO2 / Al2O3 molar ratio = 18) was added as a seed crystal so that the seed crystal content was 1% by mass. 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 has an SiO2 / Al2O3 molar ratio of 84.3 and an average maximum particle size of 0.6 μm. (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. SiO2 / Al2O3 molar ratio = 103.4 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 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 had an SiO2 / Al2O3 molar ratio of 97.5 and an average maximum particle size of 0.7 μm. (55ppm) / s (0ppm) The value was 15.6. The characteristics of the zeolite in this example are shown in Tables 1 to 3.

[0134] Comparative Example 1 The 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. SiO2 / Al2O3 molar ratio = 90.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 40 1,6-diaminohexane / SiO2 molar ratio = 0.300

[0135] TON-type zeolite (SiO2 / Al2O3 molar ratio = 90) was added as a seed crystal so that the seed crystal content was 1% by mass of the obtained raw material composition. The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition used 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 had an SiO2 / Al2O3 molar ratio of 93.6 and an average maximum particle size of 2.3 μm. (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 The 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. SiO2 / Al2O3 molar ratio = 90.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar ratio = 0.050

[0138] TON-type zeolite (SiO2 / Al2O3 molar ratio = 90) was added as a seed crystal so that the seed crystal content was 1% by mass of the obtained raw material composition. The zeolite of this comparative example was obtained in the same manner as in Example 2, except that the raw material composition used 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 had an SiO2 / Al2O3 molar ratio of 82.4 and an average maximum particle size of 6.3 μm. (55ppm) / s (0ppm) The value was 8.9. The characteristics of the zeolite in this comparative example are shown in Tables 1 to 3.

[0140] Comparative Example 3 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 TON-type zeolite (SiO2 / Al2O3 molar ratio = 90) was used as the seed crystal. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 40 1,6-diaminohexane / SiO2 molar 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 had an SiO2 / Al2O3 molar ratio of 89.4 and an average length of the longest side of the crystal of 2.7 μm. (55ppm) / s (0ppm) The value 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. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 40 1,6-diaminohexane / SiO2 molar ratio = 0.300

[0143] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI type and TON type, 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 set to the following molar composition. SiO2 / Al2O3 molar ratio = 90.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 40 1,6-diaminohexane / SiO2 molar 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. SiO2 / Al2O3 molar ratio = 62.2 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar 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. SiO2 / Al2O3 molar ratio = 111.3 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar 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. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar 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. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 40 1,6-diaminohexane / SiO2 molar ratio = 0.300

[0153] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI type and TON type, 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 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 FAU-type zeolite (product name: HSZ(registered trademark)-385HUA, SiO2 / Al2O3 molar ratio = 100) was used as the seed crystal. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar 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 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 FAU-type zeolite (product name: HSZ(registered trademark)-385HUA, SiO2 / Al2O3 molar ratio = 100) was used as the seed crystal. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 40 1,6-diaminohexane / SiO2 molar ratio = 0.050

[0157] The zeolite (crystalline aluminosilicate) in this comparative example exhibited XRD patterns characteristic of MFI type and TON type, 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 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 zeolite beta (product name: HSZ(registered trademark)-940NHA, SiO2 / Al2O3 molar ratio = 40) was used as the seed crystal. SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar ratio = 0.050

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

[0160] Comparative Example 13 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 the seed crystal was an MOR-type zeolite (product name: HSZ (registered trademark)-660HOA, SiO2 / Al2O3 molar ratio = 30). SiO2 / Al2O3 molar ratio = 92.0 OH / SiO2 molar ratio = 0.110 K / SiO2 molar ratio = 0.110 H2O / SiO2 molar ratio = 11 1,6-diaminohexane / SiO2 molar ratio = 0.050

[0161] The zeolite (crystalline aluminosilicate) of this comparative example exhibited XRD patterns characteristic of the MFI type and the TON type, and had a crystal structure of the MFI type and the TON type. The zeolite of 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 of the examples and comparative examples are shown in Tables 1 to 3 below. In the tables, "Cri" means cristobalite.

[0163]

Table 1

[0164]

Table 2

[0165]

Table 3

[0166] Measurement Example (Isomerization Reaction of n-Decane) In Example 1 and Comparative Example 1, the TON-type zeolite was contacted with an aqueous solution of H2PtCl6 (aqueous solution of hexachloroplatinate(IV) acid) to impregnate the TON-type zeolite with the aqueous solution of H2PtCl6. The TON-type zeolite impregnated with the aqueous solution of H2PtCl6 was 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. Using the TON-type zeolite supporting platinum elements as a catalyst for the isomerization reaction, the following isomerization reaction was carried out. The catalyst for the isomerization reaction contained 0.5% by mass of platinum elements with respect to 100% by mass of the catalyst for the isomerization reaction, respectively.

[0167] The catalysts for the isomerization reaction were each press-molded into agglomerated particles with an agglomeration diameter of 20 mesh to 30 mesh. 1 g of the sample in the form of agglomerated particles was filled into each atmospheric-pressure fixed-bed flow-through reaction tube and pretreated under the following conditions (pretreatment 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 the pretreatment, the temperature was decreased from 350°C to the following reaction temperature, and a fluid mixture of hydrogen and n-decane was introduced into the atmospheric-pressure fixed-bed flow-through reaction tube filled with the catalyst for the isomerization reaction, and the isomerization reaction was carried out under the following conditions. Flowing 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 from the fixed-bed flow-through reactor 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 reactor 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] [Table 4]

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

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

[0174] Furthermore, the single branch selectivity for C10 was calculated using the following formula (4). C10 Single Branch Selection Rate (%) =([monoC10BP]out / [C10BP]out)×100 ···(4) In equation (4) above, [C10BP]out represents the concentration (v / v%) of C10 branched paraffin in the outlet gas, and [monoC10BP]out represents the concentration (v / v%) of C10 single branched paraffin in the outlet gas.

[0175] As shown in Table 4 above, the isomerization catalyst based on TON-type zeolite in 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 in 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 in Example 1 is more suitable as a substrate for the isomerization catalyst than the TON-type zeolite in 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. The molar ratio of silica to alumina is between 70 and 110. The average maximum particle size is less than 1.5 μm. In an NMR spectrum measured by 27Al-MAS-NMR, the ratio of the area intensity of a peak with its peak top at a chemical shift of 55±5 ppm to the area intensity of a peak with its peak top at a chemical shift of 0±5 ppm is 13 or greater and less than 30. TON-type zeolite.

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 claim 1 or 2, wherein the cristobalite intensity ratio, which is the ratio of the height intensity of the XRD peak having its peak top at a diffraction angle 2θ = 21.4 ± 0.3° to the height intensity of the XRD peak having its peak top at a diffraction angle 2θ = 20.4 ± 0.3° in the powder X-ray diffraction pattern, is less than 0.

05.

5. The TON-type zeolite according to claim 1 or 2, 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 claim 1 or 2, 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 claim 1 or 2, wherein the amount is less than or equal to / g.

8. The TON-type zeolite according to claim 1 or 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.

9. The process includes 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. The aforementioned raw material composition has a molar ratio of silica to alumina of 70 to 110, and a molar ratio of water to silica of 8 to 15. The aforementioned seed crystal is a FER-type zeolite. A method for manufacturing TON-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 does not contain any organic compounds other than the structure-directing agent source.

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