Zeolite zts-8 and production method thereof

Abstract

To provide: a novel zeolite belonging to an SSZ-33 family and a production method thereof; a hydrocarbon absorbent including the zeolite; and a hydrocarbon absorption method using the same.SOLUTION: A zeolite has at least the following powder X-ray diffraction peaks. A powder X-ray diffraction peak with a peak top at a lattice plane spacing d=3.85±0.06 Å as CuKα radiation is used as a light source has a half-value width of 0.20° or more and 0.80° or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to zeolite ZTS-8 and methods for producing the same. [Background technology]

[0002] Zeolite-containing compositions have been commonly used as hydrocarbon adsorbents, and an example of a suitable zeolite for hydrocarbon adsorbents is an aluminosilicate zeolite belonging to the SSZ-33 family.

[0003] Patent Document 1 reports a method for producing an aluminosilicate zeolite (SSZ-26) that is a zeolite belonging to the SSZ-33 family and is characterized in that only FAU-type zeolite is used as a silica-alumina source, 1,4-bis(N-cyclohexylpyrrolidinium)butane dication is used as Q, and the Q / SiO2 ratio of the reaction mixture is less than 0.05. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2019-529296 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide at least one of a novel zeolite belonging to the SSZ-33 family and a method for producing the same, a hydrocarbon adsorbent containing the zeolite, and a hydrocarbon adsorption method using the same. [Means for solving the problem]

[0006] The present inventors have investigated zeolites that can be used as hydrocarbon adsorbents and their manufacturing methods, and as a result have discovered a novel zeolite belonging to the SSZ-33 family that exhibits hydrocarbon adsorption performance.

[0007] That is, the present invention is as described in the claims, and the gist of the present disclosure is as follows. [1] A zeolite characterized by having at least the following powder X-ray diffraction peaks, and the half-width of the powder X-ray diffraction peak having a peak top at a lattice spacing d = 3.85 ± 0.06 Å when CuKα radiation is used as a light source is 0.20° or more and 0.80° or less.

[0008] [Table 1]

[0009] [2] The zeolite according to [1], wherein the ratio of the intensity of the powder X-ray diffraction peak having a peak top at d = 10.46 ± 0.55 Å to the intensity of the powder X-ray diffraction peak having a peak top at d = 11.33 ± 0.23 Å ​​when CuKα radiation is used as a light source is 0.155 or more. [3] The zeolite according to [1] or [2] above, having a pore volume of 0.10 mL / g or more and 0.50 mL / g or less. [4] The zeolite according to any one of [1] to [3], wherein the molar ratio of silica to alumina is 10 or more and 10,000 or less. [5] The zeolite according to any one of [1] to [4] above, having an average crystal size of 0.05 μm or more and 5.0 μm or less. [6] The zeolite according to any one of [1] to [5], wherein the cation type is at least one of the group consisting of a proton type, a sodium type, a potassium type, an ammonium type, a quaternary ammonium type, and a cesium type. [7] A method for producing the zeolite according to any one of [1] to [6] above, characterized by comprising a step of crystallizing a composition containing a silica source, an alumina source, an alkali source, a quaternary ammonium cation, and water, but not containing FAU zeolite. [8] The method for producing a zeolite according to [7], wherein the alkali source contains at least a potassium compound. [9] The method according to [7] or [8] above, wherein the quaternary ammonium cation is 1,4-bis(N-cyclohexylpiperidinium)butane dication.

[10] The method according to any one of [7] to [9] above, wherein the molar ratio of OH to silica in the composition is greater than 0 and not greater than 0.30.

[11] The method according to any one of [7] to

[10] above, wherein the molar ratio of quaternary ammonium cation to silica in the composition is greater than 0 and not greater than 0.10.

[12] A hydrocarbon adsorbent containing the zeolite according to any one of [1] to [6].

[13] A method for adsorbing hydrocarbons, using the zeolite according to any one of [1] to [6] above. [Effects of the Invention]

[0010] The present disclosure can provide at least one of a novel zeolite belonging to the SSZ-33 family, a method for producing the same, a hydrocarbon adsorbent containing the zeolite, and a hydrocarbon adsorption method using the same. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present disclosure will be described below by showing an example of an embodiment. Note that the terms used in this embodiment are as follows.

[0012] An "aluminosilicate" is a composite oxide having a structure consisting of a repeating network of aluminum (Al) and silicon (Si) via oxygen (O). Among aluminosilicates, those that have a crystalline XRD peak in their powder X-ray diffraction (hereinafter also referred to as "XRD") pattern are called "crystalline aluminosilicates," and those that do not have a crystalline XRD peak are called "amorphous aluminosilicates."

[0013] In this embodiment, the XRD pattern can be obtained by XRD measurement under the following conditions.

[0014] Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Step scan Scan condition: 40° / min Measurement time: 3 seconds Measurement range: 2θ=3° to 43° Divergence vertical limit slit: 10mm Divergence / entrance slit: 1° Receiving slit: open Receiving solar slit: 5° Detector: Semiconductor detector (D / teX Ultra) Filter: Ni filter The XRD pattern can be measured using a general powder X-ray diffractometer (e.g., D8 Advance, manufactured by Bruker). The crystalline XRD peak is a peak detected by identifying the 2θ of the peak top in an XRD pattern analysis using general analysis software, and an example of such a peak is an XRD peak with a half-width of 2θ = 0.50° or less.

[0015] "Zeolite" is a compound having a regular structure in which skeleton atoms (hereinafter also referred to as "T atoms") are connected by oxygen (O), and the T atoms are at least one of metal atoms and / or metalloid atoms. Examples of metalloid atoms include at least one selected from the group consisting of boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), and tellurium (Te).

[0016] A "zeolite-like substance" is a compound having a regular structure in which T atoms are oxygen-mediated, and the T atoms contain at least one atom other than a metal or metalloid. Examples of zeolite-like substances include complex phosphorus compounds containing phosphorus (P) as the T atom, such as aluminophosphate (AlPO) and silicoaluminophosphate (SAPO).

[0017] The zeolite framework structure (hereinafter also referred to as "zeolite structure") is a framework structure specified by the framework code (hereinafter also referred to as "framework code") established by the Structure Commission of the International Zeolite Association (hereinafter also referred to as "IZA"). The zeolite framework structure can be identified by comparing the XRD pattern of the target zeolite with the XRD pattern of each zeolite structure (hereinafter also referred to as "reference pattern") listed in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007). With regard to the zeolite structure, framework structure, crystalline structure, and crystalline phase are used interchangeably.

[0018] "Zeolite belonging to the SSZ-33 family" refers to a zeolite containing at least a CON structure, and further refers to an intergrowth zeolite consisting of a zeolite structure other than the CON structure and a CON structure. For example, the former (CON-type zeolite) includes CIT-1, and the latter (intergrowth zeolite containing a CON structure) includes SSZ-26 and SSZ-33.

[0019] The zeolite of this embodiment will be described below.

[0020] The zeolite of this embodiment (hereinafter also referred to as "ZTS-8") has at least the following powder X-ray diffraction peaks (hereinafter also referred to as "XRD peaks").

[0021] [Table 2]

[0022] These XRD peaks have peak tops at each lattice spacing d and are characteristic of ZTS-8. In this embodiment, the XRD pattern may include each of the XRD peaks in the table above, and may also include other XRD peaks that belong to the SSZ-33 family.

[0023] ZTS-8 preferably has at least the following XRD peaks in its XRD pattern:

[0024] [Table 3]

[0025] A more preferred XRD pattern of ZTS-8 is the following XRD pattern.

[0026] [Table 4]

[0027] In addition to the above peaks, ZTS-8 may contain XRD peaks with relative intensities of less than 5. However, these low-intensity XRD peaks do not need to be taken into consideration when identifying the crystal structure.

[0028] The XRD pattern of ZTS-8 preferably does not have an XRD peak having a peak top at a lattice spacing d=9.60±0.30 Å, and more preferably does not have XRD peaks having peak tops at lattice spacings d=14.30±1.00 Å, 9.60±0.30 Å, and 4.26±0.04 Å.

[0029] ZTS-8 is a zeolite that has the XRD peaks shown in the table above, and the half-width of the XRD peak (hereinafter also referred to as the "main peak"), which has a peak top at a lattice spacing d=3.85±0.06 (Å) when CuKα radiation is used as a radiation source, is 0.20° or more and 0.80° or less. The half-width of the main peak is preferably 0.30° or more and 0.70° or less.

[0030] In the XRD pattern of ZTS-8, the ratio of the intensity of the XRD peak having a peak top at d=10.46±0.55Å (lattice spacing d=11.33±0.23Å) to the intensity of the XRD peak having a peak top at d=10.46±0.55Å (when CuKα radiation is used as a light source) is preferably 0.155 or more, more preferably 0.160 or more. Furthermore, the ratio of the XRD peak intensities is preferably 0.700 or less, more preferably 0.500 or less.

[0031] ZTS-8 preferably has a pore volume (hereinafter also referred to as "pore volume") of 0.10 mL / g or more or 0.13 mL / g or more, and preferably 0.50 mL / g or less or 0.35 mL / g or less.

[0032] The pore volume can be determined by t-plot analysis of the nitrogen adsorption isotherm obtained using a general nitrogen adsorption apparatus (e.g., BELSORP-mini II, manufactured by Microtrack-Bell). The t-plot analysis can be performed under the following conditions, using the analysis software (e.g., BELMASTER, manufactured by Microtrack-Bell) that comes with the nitrogen adsorption apparatus.

[0033] Adsorbate cross section: 0.162nm 2 Saturated water vapor pressure: 103.72kPa First line: A line connecting the points t=0 nm and t=0.27±0.03 nm Second straight line: A tangent line passing through the inflection point of a sigmoid t-plot curve, for example, a line joining the points t=0.70±0.15 nm and t=1.00±0.10 nm The average crystal size of ZTS-8 is 0.05 μm or more and 5.0 μm or less, preferably 0.05 μm or more and 3.0 μm or less, and more preferably 0.1 μm or more and 2.0 μm or less.

[0034] In this embodiment, the average crystal size refers to the average particle size of primary particles. The particle size of primary particles is the particle size of primary particles confirmed in an SEM observation image obtained by observation with a scanning electron microscope (hereinafter also referred to as "SEM"), and the average crystal size is the average value of the particle sizes of the primary particles. One method for measuring the average crystal size is to extract 80 to 150 primary particles observed at a magnification of 3,000 to 50,000 times, measure the average of the longest and shortest diameters of the primary particles to obtain the crystal size of the primary particles, and use the average value of the crystal sizes as the average crystal size. When extracting primary particles for particle size measurement, it is sufficient that the number of SEM observation images is 1 or more.

[0035] In this embodiment, the primary particles of ZTS-8 are particles that are observed as independent particles when observed with an SEM at a magnification of 10,000 to 20,000 times.

[0036] ZTS-8 has a molar ratio of silica to alumina (hereinafter also referred to as "SiO2 / Al2O3 ratio") of 10 or more and 10,000 or less, preferably 20 or more and 500 or less, and more preferably 25 or more and 60 or less.

[0037] ZTS-8 may contain T atoms other than Si and Al. Examples of T atoms constituting ZTS-8 include one or more selected from the group consisting of boron (B), gallium (Ga), germanium (Ge), iron (Fe), titanium (Ti), and tin (Sn).

[0038] The ions (M) contained in ZTS-8 include protons (H + ), sodium (Na + ), potassium (K + ), ammonium (NH4 + ), and cesium (Cs + ) The ions in ZTS-8 can be replaced with other ions by ion exchange.

[0039] ZTS-8 is a material with a molar ratio of cation (M) converted to oxide to alumina (hereinafter referred to as "M 2 / nAlso referred to as the "O / Al2O3 ratio." Where n is the average valence of M. When the ratio (n) exceeds 0.1, the cation type is the ion (M) type. Also, when ZTS-8 contains multiple types of cations, the ZTS-8 may be considered to be a cation type consisting of multiple cations (e.g., sodium-potassium type).

[0040] The cation type of ZTS-8 is proton (H + ) type, ammonium (NH4 + ) type and cesium (Cs + ) type group, preferably ammonium (NH4 + ) type and cesium (Cs + ) type, more preferably cesium (Cs + ) type.

[0041] ZTS-8 may contain a quaternary ammonium cation, and may further contain a quaternary ammonium cation that functions as an organic structure directing agent (hereinafter also referred to as "SDA") for directing zeolites belonging to the SSZ-33 family. Examples of such quaternary ammonium cations include N,N,N,N',N',N'-hexamethyl[4.3.3.0]propellane-8,11-diammonium cation, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]propellane-8,11-diammonium cation, and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]propellane-8,11-diammonium cation. 2,6)decane cation, (1-adamantyl)trimethylammonium cation, (2-adamantyl)trimethylammonium cation, N,N,N,N',N',N'-hexamethyl-1,5-dimethylbicyclo[3.3.0]octane-3,7-diammonium cation, N,N-dimethyl-endo-bicyclo[2.2.2]oct-5-ene-2,3-pyrrolidinium cation, N,N-dimethyl-endo-bicyclo[3.2.2]non-5-ene-2,3-pyrrolidinium cation, N,N,N-trimethyl((-)-cis-myrtanyl)ammonium cation, N,N,N-trimethyl((+)-cis-myrtanyl)ammonium cation, N,N,N-trimethyl-(1S,2S,3S,5R)-isopinocampheylammonium cation, cis-N,N-die and at least one selected from the group consisting of ethyldecahydroquinolinium cation, cis-N,N-diethyldecahydroquinolinium cation, trans-N,N-diethyldecahydroquinolinium cation, 1,4-bis(N-cyclohexylpyrrolidinium)butane dication, 1,5-bis(N-cyclohexylpyrrolidinium)pentane dication, 1,5-bis(N,N-dimethylcyclohexylammonium)pentane dication, 1,4-bis(N-cyclohexylpiperidinium)butane dication, 1,4-bis(N-cyclopentylpiperidinium)butane dication, 1,4-bis(N-isopentylpyrrolidinium)butane dication, tetraethylammonium cation, and 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane cation.

[0042] ZTS-8 may contain SDA, but it is preferable that it does not contain SDA, as this facilitates improving the hydrocarbon adsorption capacity. A realistic example of the SDA content of ZTS-8 is an SDA / SiO2 ratio of more than 0 and less than 0.005.

[0043] Next, the manufacturing method of ZTS-8 will be described.

[0044] The production method of this embodiment includes a step of crystallizing a composition (hereinafter also referred to as a "raw material composition") that contains a silica source, an alumina source, an alkali source, a quaternary ammonium cation, and water, but does not contain FAU zeolite (hereinafter also referred to as a "crystallization step"). By the crystallization step, ZTS-8 is obtained as a zeolite product from the raw material composition.

[0045] The alumina source is an aluminum-containing compound or aluminum (Al), and examples thereof include at least one selected from the group consisting of aluminum hydroxide, sodium aluminate, potassium aluminate, aluminum oxide, aluminum sulfate, aluminum chloride, aluminum nitrate, amorphous aluminosilicates, metallic aluminum, pseudoboehmite, alumina sol, and aluminum alkoxides. Aluminum hydroxide, sodium aluminate, potassium aluminate, aluminum oxide, aluminum sulfate, aluminum chloride, aluminum nitrate, crystalline aluminosilicates, amorphous aluminosilicates, alumina sol, and aluminum alkoxides are preferred. From an industrial viewpoint, the alumina source is preferably at least one selected from the group consisting of aluminum hydroxide, sodium aluminate, potassium aluminate, aluminum oxide, aluminum sulfate, aluminum chloride, and amorphous aluminosilicates, more preferably at least one selected from the group consisting of sodium aluminate, potassium aluminate, aluminum oxide, aluminum sulfate, aluminum chloride, and amorphous aluminosilicates, and even more preferably amorphous aluminosilicates.

[0046] The silica source is a silicon-containing compound or silicon (Si), and examples thereof include one or more selected from the group consisting of silica sol, fumed silica, colloidal silica, precipitated silica, amorphous silicic acid, crystalline aluminosilicate, and amorphous aluminosilicate, and is preferably at least one of amorphous silicic acid and amorphous aluminosilicate.

[0047] Particularly preferred alumina and silica sources include amorphous aluminosilicates, and further include amorphous aluminosilicates having an SiO / AlO ratio of 10 or more, 15 or more, or 20 or more, and 10,000 or less, 1,000 or less, or 80 or less. In addition, the alumina and silica sources do not include FAU-type zeolite.

[0048] The quaternary ammonium cation may be any quaternary ammonium cation that functions as an organic structure directing agent (hereinafter also referred to as "SDA") for zeolites belonging to the SSZ-33 family. Examples of such quaternary ammonium cations include N,N,N,N',N',N'-hexamethyl[4.3.3.0]propellane-8,11-diammonium cation, N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]propellane-8,11-diammonium cation, and N,N,N-trimethyl-8-ammonium tricyclo[5.2.1.0]propellane-8,11-diammonium cation. 2,6)decane cation, (1-adamantyl)trimethylammonium cation, (2-adamantyl)trimethylammonium cation, N,N,N,N',N',N'-hexamethyl-1,5-dimethylbicyclo[3.3.0]octane-3,7-diammonium cation, N,N-dimethyl-endo-bicyclo[2.2.2]oct-5-ene-2,3-pyrrolidinium cation, N,N-dimethyl-endo-bicyclo[3.2.2]non-5-ene-2,3-pyrrolidinium cation, N,N,N-trimethyl((-)-cis-myrtanyl)ammonium cation, N,N,N-trimethyl((+)-cis-myrtanyl)ammonium cation, N,N,N-trimethyl-(1S,2S,3S,5R)-isopinocampheylammonium cation, cis-N,N-die and at least one selected from the group consisting of ethyldecahydroquinolinium cation, cis-N,N-diethyldecahydroquinolinium cation, trans-N,N-diethyldecahydroquinolinium cation, 1,4-bis(N-cyclohexylpyrrolidinium)butane dication, 1,5-bis(N-cyclohexylpyrrolidinium)pentane dication, 1,5-bis(N,N-dimethylcyclohexylammonium)pentane dication, 1,4-bis(N-cyclohexylpiperidinium)butane dication, 1,4-bis(N-cyclopentylpiperidinium)butane dication, 1,4-bis(N-isopentylpyrrolidinium)butane dication, tetraethylammonium cation, and 1-benzyl-4-aza-1-azoniabicyclo[2.2.2]octane cation.

[0049] SDA may be contained in the raw material composition in the form of a salt, and examples of the salt of SDA include at least one selected from the group consisting of hydroxide, fluoride, chloride, bromide, iodide, carbonate, and sulfate of SDA, and preferably at least one selected from the group consisting of hydroxide, chloride, and bromide of SDA.

[0050] Particularly preferred salts of SDA include one or more selected from the group consisting of 1,4-bis(N-cyclohexylpiperidinium)butane dication hydroxide, 1,4-bis(N-cyclohexylpiperidinium)butane dication bromide, and 1,4-bis(N-cyclohexylpiperidinium)butane dication chloride, because they can reduce production costs.

[0051] The alkali source is an alkali metal or a compound containing an alkali metal element, and examples thereof include at least one selected from the group consisting of hydroxides, carbonates, sulfates, chlorides, bromides, and iodides of alkali metals. At least one selected from the group consisting of hydroxides, chlorides, bromides, and iodides is preferred, and hydroxides are more preferred.

[0052] The alkali metal (element) may be at least one selected from the group consisting of sodium, potassium, rubidium, and cesium, with at least one of sodium and potassium being preferred, and potassium being more preferred.

[0053] The alkali source preferably contains at least a potassium compound, more preferably only a potassium compound, and more preferably potassium hydroxide as the potassium compound.

[0054] The water may be distilled water, deionized water, or pure water, and furthermore, water derived from other components contained in the amorphous composition, such as hydrated compounds, can also be considered as water in the raw material composition.

[0055] The raw material composition may contain seed crystals in a sufficiently small amount relative to the alumina and silica sources to promote the crystallization of ZTS-8.

[0056] The seed crystals have a total mass ratio (hereinafter also referred to as "seed crystal content") of aluminum and silicon in the seed crystals converted into Al2O3 and SiO2, respectively, relative to the total mass of aluminum and silicon in the raw material composition converted into Al2O3 and SiO2, of 0% by mass or more and 10% by mass or less, and further preferably 0.5% by mass or less and 6% by mass or less.

[0057] The seed crystals may be any zeolite other than FAU type zeolite, and may be any of AEI type zeolite, AFI type zeolite, AFT type zeolite, AFV type zeolite, AFX type zeolite, * Examples of the zeolite include at least one selected from the group consisting of BEA type zeolite, CHA type zeolite, EAB type zeolite, EMT type zeolite, ERI type zeolite, FAU type zeolite, FER type zeolite, GIS type zeolite, GME type zeolite, HEU type zeolite, KFI type zeolite, LEV type zeolite, LTL type zeolite, MAZ type zeolite, MER type zeolite, MFI type zeolite, MOR type zeolite, MSE type zeolite, OFF type zeolite, and zeolites belonging to the SSZ-33 family; * At least one selected from the group consisting of BEA type zeolite and zeolite belonging to the SSZ-33 family is preferred.

[0058] Preferred compositions of the raw material composition include the following molar compositions: In the following, M is an alkali metal other than potassium, and when the raw material composition contains two or more alkali metals other than potassium (for example, sodium and cesium), the M / SiO2 ratio can be considered to be the (Na+Cs) / SiO2 ratio, etc.

[0059] SiO2 / Al2O3 ratio = 10 or more, 15 or more, or 20 or more, and 10,000 or less, 1,000 or less, or 80 or less SDA / SiO2 ratio = 0.005 or more, 0.010 or more, 0.020 or more Or 0.030 or more and 0.500 or less, 0.400 or less, 0.300 or less or 0.150 or less K / SiO2 ratio = 0.00 or more, 0.05 or more, or 0.10 or more, and 1.00 or less, 0.70 or less, or 0.30 or less M / SiO2 ratio = 0.00 or more, 0.05 or more, or 0.10 or more, and 1.00 or less, 0.70 or less, or 0.30 or less OH / SiO2 ratio = 0.10 or more or 0.15 or more, and 1.00 or less, 0.60 or less, or 0.50 or less H2O / SiO2 ratio = 3 or more, 8 or more, or 10 or more, and 200 or less, 100 or less, or 60 or less In the crystallization step, the raw material composition is crystallized. Crystallization is preferably carried out by hydrothermal synthesis. The crystallization temperature is 100°C or higher, preferably 130°C or higher, and more preferably 150°C or higher. The crystallization temperature does not need to be higher than necessary, and is, for example, 200°C or lower, preferably 180°C or lower. During crystallization, the raw material composition may be stirred or left to stand.

[0060] The time for the crystallization step is optional, but is preferably 5 hours or more, more preferably 10 hours or more, and more preferably 200 hours or less, and even more preferably 100 hours or less.

[0061] The manufacturing method of this embodiment may include, after the crystallization step, at least one of a washing step, a drying step, an SDA removal step, an alkali removal step, a metal-containing step, a washing step after the metal-containing step, a drying step after the metal-containing step, and an activation step.

[0062] In the washing step, solid-liquid separation is performed to separate ZTS-8 from a liquid phase by a known method, and the ZTS-8 obtained as a solid phase may be washed with pure water.

[0063] The drying step removes moisture physically adsorbed on ZTS-8. Drying conditions are optional, and examples include leaving ZTS-8 in the air at 50°C to 250°C for 1 hour to 120 hours, or drying with a spray dryer.

[0064] The SDA removal step removes SDA contained in ZTS-8. While ZTS-8 of this embodiment may contain SDA, it is preferable that it does not contain SDA, as this facilitates improving the hydrocarbon adsorption capacity. Therefore, ZTS-8 containing SDA is preferably subjected to the SDA removal step. Examples of methods for removing SDA include one or more methods selected from the group consisting of a liquid-phase treatment using an acidic aqueous solution, an exchange treatment using a resin, a pyrolysis treatment, and a calcination treatment. From the viewpoint of production efficiency, the SDA removal step is preferably at least one of a pyrolysis treatment and a calcination treatment. In the case of a calcination treatment, examples of calcination conditions include a temperature of 400°C to 700°C in the atmosphere for 1 hour to 24 hours.

[0065] The alkali removal step removes alkali metals contained in ZTS-8 after the drying step, or in ZTS-8 after the SDA removal step if SDA was used in the crystallization step, to change the cation type. The alkali metals are derived from components contained in the raw material composition in the crystallization step. The cation type of ZTS-8 after alkali removal can be at least one of ammonium type and proton type. Examples of alkali removal methods include one or more selected from the group consisting of liquid-phase treatment with an electrolyte solution, exchange treatment with a resin, thermal decomposition treatment, and calcination treatment. For example, to obtain ZTS-8 with a proton cation type, a method of treating zeolite from which SDA has been removed with an acid, or a method of treating zeolite from which SDA has been removed with ammonium (NH4 + ) type and then heat treatment to convert it to the proton type. + type zeolite (hereinafter referred to as "NH4 + To obtain ZTS-8, which is a type zeolite, a liquid phase treatment using an electrolyte solution (for example, an aqueous ammonium chloride solution) can be carried out.

[0066] The metal-containing step involves contacting a metal with ZTS-8 from which the alkali has been removed and the cation type has been changed, with the aim of containing the metal in the ZTS-8. The metal to be contained is not particularly limited. For example, when the ZTS-8 of this embodiment contains at least one metal selected from the group consisting of sodium, potassium, rubidium, and cesium, it is preferable to use a compound containing the metal, and more preferably an inorganic acid salt containing the metal. Furthermore, it is preferable to use at least one inorganic acid salt containing the metal selected from the group consisting of sulfates, nitrates, acetates, hydroxides, and chlorides.

[0067] The metal-containing step may be any method that allows the metal to be contained in the pores of ZTS-8 after alkali removal and cation type change. Specific methods include one or more selected from the group consisting of ion exchange, evaporation to dryness, and impregnation. The impregnation method, or a method in which an aqueous solution containing the metal compound is mixed with ZTS-8, is preferred. This allows the metal to be contained in the pores of ZTS-8.

[0068] The washing step after the metal-containing step is intended to remove impurities contained in the ZTS-8 after the metal-containing step, and any washing method can be used. For example, the ZTS-8 after the metal-containing step can be washed with a sufficient amount of pure water.

[0069] The drying step after the metal-containing step is intended to remove moisture remaining on the surface and in the pores of the zeolite, and can be carried out, for example, in air at 100°C or higher and 200°C or lower, preferably 110°C or higher and 190°C or lower, for 1 hour or higher and 24 hours or lower.

[0070] The activation process is intended to remove organic matter or moisture from the ZTS-8 obtained in the drying process after the metal-containing process, and can be performed, for example, by treating the ZTS-8 in the atmosphere at 200°C or higher and 600°C or lower for 1 hour to 10 hours, and preferably at 300°C or higher and 600°C or lower for 1 hour to 5 hours.

[0071] When used as a catalyst, adsorbent, or the like, ZTS-8 of this embodiment may contain a transition metal. Preferred transition metals contained in ZTS-8 of this embodiment include at least one metal selected from Groups 8, 9, 10, and 11 of the periodic table, as well as one or more metals selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), silver (Ag), iron (Fe), copper (Cu), cobalt (Co), manganese (Mn), and indium (In). The method for incorporating a transition metal into ZTS-8 is not particularly limited, but examples include ion exchange and impregnation.

[0072] The ZTS-8 of this embodiment can be used as a solid acid catalyst, a metal catalyst support, or a hydrocarbon adsorbent.

[0073] The ZTS-8 of this embodiment is used as a hydrocarbon adsorbent containing it, and may further be a hydrocarbon adsorbent consisting solely of the ZTS-8 of this embodiment.

[0074] The hydrocarbon adsorbent of this embodiment can be used in any shape depending on the application, and is not particularly limited, and can be used in the form of, for example, a powder, a molded body, an adsorption member, etc. Specific molded body shapes include one or more selected from the group consisting of spherical, approximately spherical, elliptical, disk-like, cylindrical, polyhedral, irregular, and petal-like.

[0075] When the hydrocarbon adsorbent of this embodiment is formed into a molded body, the hydrocarbon adsorbent made of ZTS-8 can be molded, but in terms of excellent operability and durability, it is preferable to mold the hydrocarbon adsorbent containing the above-mentioned zeolite in addition to the above-mentioned zeolite. The molding method can be, for example, one or more selected from the group consisting of rolling granulation molding, press molding, extrusion molding, injection molding, slip casting, and sheet molding.

[0076] When the hydrocarbon adsorbent of this embodiment is used as an adsorption member, the adsorption member can be manufactured by mixing the above-mentioned hydrocarbon adsorbent, together with additives such as a binder as necessary, with a solvent such as water or alcohol to prepare a slurry, and then coating the slurry on a substrate.

[0077] The hydrocarbon adsorbent of this embodiment can be used in a method for adsorbing hydrocarbons.

[0078] The hydrocarbon adsorbent of this embodiment can adsorb hydrocarbons by a method including a step of contacting a hydrocarbon-containing fluid with the hydrocarbon adsorbent of this embodiment.

[0079] The hydrocarbon-containing fluid may be, for example, at least one of a hydrocarbon-containing gas and a hydrocarbon-containing liquid.

[0080] The hydrocarbon-containing gas is a gas containing at least one type of hydrocarbon, and preferably a gas containing two or more types of hydrocarbons. Examples of hydrocarbons contained in the hydrocarbon-containing gas include at least one selected from the group consisting of paraffins, olefins, and aromatic hydrocarbons. The number of carbon atoms in the hydrocarbon may be one or more, preferably from one to 15. Preferably, the hydrocarbons contained in the hydrocarbon-containing gas are at least one or two or more selected from the group consisting of methane, ethane, ethylene, propylene, butane, linear paraffins having 5 or more carbon atoms, linear olefins having 5 or more carbon atoms, benzene, toluene, and xylene. More preferably, the hydrocarbons contained in the hydrocarbon-containing gas are at least one or two or more selected from the group consisting of methane, ethane, ethylene, propylene, butane, benzene, toluene, and xylene. More preferably, the hydrocarbons contained in the hydrocarbon-containing gas are at least one or two or more selected from the group consisting of methane, ethane, ethylene, and propylene, and at least one selected from the group consisting of benzene, toluene, and xylene. The hydrocarbon-containing gas may contain at least one selected from the group consisting of carbon monoxide, carbon dioxide, hydrogen, oxygen, nitrogen, nitrogen oxides, sulfur oxides, and water. Specific examples of hydrocarbon-containing gases include combustion gases such as exhaust gas from an internal combustion engine.

[0081] The hydrocarbon-containing gas in the hydrocarbon adsorption method preferably contains one or more hydrocarbons selected from the group consisting of meta-xylene, ortho-xylene and branched paraffins.

[0082] Preferably, the contact temperature in this step is from room temperature to 200°C.

[0083] The hydrocarbon adsorbent of this embodiment has the effect of having a higher hydrocarbon desorption start temperature than hydrocarbon adsorbents other than those of this embodiment. It is generally known that the hydrocarbon desorption start temperature is correlated with the SiO2 / Al2O3 ratio, but the hydrocarbon adsorbent of this embodiment exhibits an unprecedentedly high hydrocarbon desorption start temperature under the same SiO2 / Al2O3 ratio conditions. [Example]

[0084] The manufacturing method of this embodiment will be described below with reference to examples, but this embodiment is not limited to these examples. (Identification of crystalline phases) The samples were subjected to XRD measurement using a general powder X-ray diffractometer (device name: Ultima IV Protectus, manufactured by Rigaku Corporation) under the following measurement conditions:

[0085] Acceleration current / voltage: 40mA / 40kV Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Continuous scan Scan condition: 40° / min Measurement range: 2θ=3° to 43° Divergence vertical limit slit: 10mm Divergence / entrance slit: 1° Receiving slit: open Detector: D / teX Ultra Ni filter used The structure of the sample was identified by comparing the obtained XRD pattern with the XRD pattern described in Collection of simulated XRD powder patterns for zeolites, Fifth revised edition (2007).

[0086] The XRD measurements were carried out at room temperature (10°C to 35°C) in humid air (relative humidity 30% to 90%). The samples were exposed to humid air at room temperature for at least 5 minutes before the measurements were carried out. (composition 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 device (device name: OPTIMA5300DV, manufactured by PerkinElmer). The SiO2 / Al2O3 ratio of the sample was calculated from the measured values ​​of Si and Al. (pore volume) The amount of nitrogen gas adsorbed onto the sample was measured using a standard nitrogen adsorption apparatus (apparatus name: BELSORP-mini II, manufactured by Microtrac-Bell Co., Ltd.). The pore volume was calculated by applying the t-plot method to the nitrogen gas adsorption results. The t-plot method was performed using the analysis software (product name: BELMaster, manufactured by Microtrac-Bell Co., Ltd.) that came with the nitrogen adsorption apparatus. The standard constant volume method was used for nitrogen gas adsorption. The measurement conditions are as follows:

[0087] Measurement temperature: -196℃ Pretreatment: 350℃, vacuum drying for 2 hours (Hydrocarbon adsorption measurement) The hydrocarbon desorption initiation temperature of the hydrocarbon adsorbent was measured. The obtained hydrocarbon adsorbents were each pressure-molded and pulverized to form irregularly shaped bodies with an aggregate size of 20 to 30 mesh, and the resulting bodies were used as measurement samples. 0.1 g of each measurement sample was packed into an atmospheric pressure fixed-bed flow-type reactor and treated at 500°C for 1 hour under a nitrogen flow, followed by cooling to 50°C as a pretreatment.

[0088] A hydrocarbon-containing gas was passed through each of the hydrocarbon adsorbents that had been pretreated as described above. The hydrocarbon concentration (methane equivalent concentration; hereinafter also referred to as "inlet concentration") of the hydrocarbon-containing gas at the inlet side of the atmospheric pressure fixed-bed flow reactor and the hydrocarbon concentration (methane equivalent concentration; hereinafter also referred to as "outlet concentration") of the hydrocarbon-containing gas at the outlet side of the atmospheric pressure fixed-bed flow reactor were measured using a hydrogen ionization detector (FID). The time-integrated value of the inlet concentration was taken as the amount of hydrocarbons before flow [μmol C], and the time-integrated value of the outlet concentration was taken as the amount of hydrocarbons after flow [μmol C]. The 50-200°C purification efficiency was calculated using the following formula from the amount of hydrocarbons before flow and the amount of hydrocarbons after flow in the measurement temperature range from 50°C to 200°C.

[0089] 50~200℃ Purification rate [%] = {(amount of hydrocarbons before distribution - amount of hydrocarbons after distribution) / amount of hydrocarbons before distribution} x 100 The composition of the hydrocarbon-containing gas and the measurement conditions are shown below.

[0090] Hydrocarbon-containing gas: Toluene 3000 ppmC by volume (methane equivalent concentration) Water 3% by volume Nitrogen Remainder Gas flow rate: 200 mL / min Measurement temperature: 50~600℃ Heating rate: 10°C / min (Measurement of hydrocarbon desorption onset temperature) Pretreatment was carried out in the same manner as in the hydrocarbon adsorption measurement.

[0091] A hydrogen ionization detector (FID) was used to continuously quantitatively analyze hydrocarbons in the gas after passing through the hydrocarbon adsorbent.

[0092] The time integral value of the inlet concentration was taken as the amount of hydrocarbons passing through the hydrocarbon adsorbent, and the time integral value of the outlet concentration (methane equivalent concentration) was subtracted from this amount of hydrocarbons to determine the amount of hydrocarbons adsorbed by each adsorbent as the amount of hydrocarbons adsorbed per mass of the hydrocarbon adsorbent (μmolC / g).Then, the temperature at which the amount of hydrocarbons adsorbed most quickly reached 0 μmolC / g as the temperature of the measurement sample increased was taken as the hydrocarbon desorption start temperature.

[0093] Example 1 1,4-bis(N-cyclohexylpiperidinium) butane dication hydroxide (hereinafter (also known as "BCBP(OH)2"). "), pure water, potassium hydroxide, and SiO2 / A Amorphous aluminosilicate with an l2O3 ratio of 35.8 was mixed to produce a raw material with the following molar composition: A composition was obtained.

[0094] SiO2 / Al2O3 ratio =35.8 K / SiO2 ratio =0.15 BCBP / SiO2 ratio =0.05 H2O / SiO2 ratio =50 OH / SiO2 ratio =0.25 The raw material composition was filled into an 80 mL sealed container and subjected to hydrothermal synthesis at 160°C for 7 days while being rotary stirred at 50 rpm to obtain a crystallized product. The obtained crystallized product was subjected to solid-liquid separation, washed with pure water, and then dried in air at 110°C for 20 hours to obtain a zeolite product, which was used as the zeolite of this example.

[0095] The zeolite used in this example was ZTS-8, with an average crystal size of 1.8 μm, a SiO / AlO ratio of 35.0, and a KO / AlO ratio of 0.04. The XRD pattern of the zeolite product is shown in the table below. The half-width of the main peak was 0.48°.

[0096] [Table 5]

[0097] Example 2 The zeolite obtained in Example 1 was calcined in air at 550°C for 2 hours to obtain a calcined zeolite, which was used as the zeolite of this example.

[0098] The zeolite used in this example was ZTS-8, with an average crystal size of 1.8 μm and an SDA / SiO ratio below the detection limit (<0.001). The XRD pattern of the calcined zeolite is shown in the table below. The half-width of the main peak was 0.51°.

[0099] [Table 6]

[0100] Example 3 The zeolite obtained in Example 2 was mixed with water, and then filtered to obtain a cake of zeolite. A 20% by mass aqueous solution of ammonium chloride was poured into the cake. Next, the zeolite was washed by pouring in warm water in an amount 10 times the volume of the zeolite. After washing, the zeolite was dried at 110°C in the air for 20 hours, and the cation type was determined to be NH4 + Type of zeolite (NH4 + type zeolite) was obtained, and the zeolite of this example was obtained.

[0101] The obtained NH4 + The type zeolite was ZTS-8, with an average crystal size of 1.8 μm, an SiO2 / Al2O3 ratio of 35, and a K2O / Al2O3 ratio of 0.001 or less (below the detection limit). + The XRD pattern of the zeolite is shown in the table below. The half-width of the main peak was 0.50°.

[0102] [Table 7]

[0103] Example 4 The zeolite obtained in Example 3 was cesium-exchanged in the following manner.

[0104] A 2% by mass aqueous solution of cesium chloride was prepared using cesium chloride (special grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). + The amount of liquid used was such that the molar mass of Cs was 2 equivalents to the molar mass of Al of the zeolite. + After mixing the zeolite with water and filtering, the resulting cake was poured with the cesium chloride aqueous solution. Then, the zeolite was washed by pouring in warm water with a volume 10 times the volume of the zeolite. After washing, the zeolite was dried at 110°C in the air to support Cs, and the cation type was Cs. + type zeolite (hereinafter referred to as "Cs + This was used as the zeolite of this example.

[0105] The obtained Cs + The type zeolite was ZTS-8, with a pore volume of 0.15 mL / g, an average crystal size of 1.8 μm, an SiO2 / Al2O3 ratio of 35, and a Cs2O / Al2O3 ratio of 0.89. + The XRD pattern of the zeolite is shown in the table below. The half-width of the main peak was 0.49°.

[0106] [Table 8]

[0107] Example 5 The zeolite of this example was obtained in the same manner as in Example 1, except that an amorphous aluminosilicate with a SiO / AlO ratio of 28.9 was used, a raw material composition having the following molar composition was used, a zeolite obtained in the same manner as in Example 1 was used as the seed crystals, and the seed crystals were added so that the seed crystal content was 1.0 mass%.

[0108] SiO2 / Al2O3 ratio =28.9 K / SiO2 ratio =0.20 BCBP / SiO2 ratio =0.05 H2O / SiO2 ratio =50 OH / SiO2 ratio =0.30 The resulting zeolite product was ZTS-8, with an average crystal size of 1.1 μm, a SiO / AlO ratio of 26, and a KO / AlO ratio of 0.11. The XRD pattern of the zeolite product is shown in the table below. The half-width of the main peak was 0.42°.

[0109] [Table 9]

[0110] Example 6 A calcined zeolite body was obtained in the same manner as in Example 2, except that the zeolite of Example 5 was used, and this was used as the zeolite of this example.

[0111] The zeolite used in this example was ZTS-8, with an average crystal size of 1.1 μm and an SDA / SiO ratio below the detection limit (<0.001). The XRD pattern of the zeolite used in this example is shown in the table below. The half-width of the main peak was 0.49°.

[0112] [Table 10]

[0113] Example 7 The alkali removal step was carried out in the same manner as in Example 3, except that the zeolite of Example 6 was used, and NH4 + This type zeolite was used as the zeolite of this example.

[0114] The zeolite used in this example was ZTS-8, with an average crystal size of 1.1 μm, a SiO / AlO ratio of 26, and a KO / AlO ratio of 0.001. The XRD pattern of the zeolite used in this example is shown in the table below. The half-width of the main peak was 0.48°.

[0115] [Table 11]

[0116] Example 8 The metal loading step was carried out in the same manner as in Example 4, except that the zeolite of Example 7 was used. + This type zeolite was used as the zeolite of this example.

[0117] The zeolite used in this example was ZTS-8, with an average crystal size of 1.1 μm, a pore volume of 0.15 mL / g, an SiO2 / Al2O3 ratio of 26, and a Cs2O / Al2O3 ratio of 0.84. + The XRD pattern of the zeolite is shown in the table below. The half-width of the main peak was 0.49°.

[0118] [Table 12]

[0119] Example 9 1,4-bis(N-cyclohexylpiperidinium)butane dication bromide (hereinafter also referred to as "BCBPBr2"), pure water, potassium hydroxide, and amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 36.8 were mixed to obtain a raw material composition having the following molar composition:

[0120] SiO2 / Al2O3 ratio =36.8 K / SiO2 ratio =0.20 BCBP / SiO2 ratio =0.04 H2O / SiO2 ratio =34 OH / SiO2 ratio =0.20 The zeolite of Example 1 was used as seed crystals, and the seed crystals were mixed with the raw material composition so that the seed crystal content was 1.0 mass% relative to the raw material composition. The raw material composition was then filled into a 4 L sealed container and subjected to hydrothermal synthesis at 160°C for 120 hours while being rotary stirred at 251 rpm. The resulting crystallized product was separated into solid and liquid, washed with pure water, and then dried in air at 110°C to obtain a zeolite product.

[0121] The zeolite used in this example was ZTS-8, with a SiO / AlO ratio of 35.0 and a KO / AlO ratio of 0.18. The XRD pattern of the zeolite used in this example is shown in the table below. The half-width of the main peak was 0.46°.

[0122] [Table 13]

[0123] The zeolites obtained in Examples 1 and 2, and Examples 5 and 6, regardless of the presence or absence of SDA, satisfied the XRD patterns in Table 1, and the half-width of the main peak was found to be ZTS-8, which is 0.20° or more and 0.80° or less.

[0124] The zeolites obtained in Examples 1 to 8 were found to be ZTS-8, which satisfied the XRD patterns in Table 1 regardless of the cation type, and had a main peak half-width of 0.20° or more and 0.80° or less.

[0125] Comparative Example 1 The cation type is the proton type. * Using BEA-type zeolite (product name: HSZ-931HOA, manufactured by Tosoh Corporation; SiO2 / Al2O3=30), a metal loading step was carried out in the same manner as in Example 1 to obtain the zeolite of this comparative example.

[0126] The obtained zeolite had a SiO2 / Al2O3 ratio of 30, a Cs2O / Al2O3 ratio of 0.72, and a cation type of Cs + Is a type * It was a BEA type zeolite.

[0127] Comparative Example 2 A 15.9 mass% aqueous solution of N,N,N-trimethyl((-)-cis-mirtanyl)ammonium cation hydroxide (hereinafter also referred to as "TMMAOH"), aluminum isopropoxide, and tetraethoxysilane were mixed and heated at 90°C for 20 hours to evaporate the water. The TMAAOH was obtained by methylating (-)-cis-mirtanylamine with iodomethane and then ion-exchanging with an ion-exchange resin (product name: SA10AOH, manufactured by Mitsubishi Chemical Corporation). The obtained TMAAOH (solid) was pulverized in a mortar, and then 48 mass% hydrofluoric acid and 5 mass% CON-type zeolite as seed crystals were added and mixed to obtain a raw material composition having the following molar composition:

[0128] SiO2 / Al2O3 ratio = 50.0 TMMAOH / SiO2 ratio = 0.50 HF / SiO2 ratio = 0.50 H2O / SiO2 ratio = 5.0 The resulting composition was sealed in an autoclave with a Teflon (registered trademark) inner tube, and the autoclave was heated at 170°C under autogenous pressure for 7 days while standing to obtain a zeolite product. The zeolite product was filtered, washed, and dried overnight in air at 110°C. It was then heated at 450°C for 1 hour in a nitrogen atmosphere, followed by 600°C for 2 hours in air. This yielded a calcined zeolite with an SiO2 / Al2O3 ratio of 53. The XRD pattern of the calcined zeolite is shown in the table below. When CuKα radiation was used as a light source, the half-width of the peak at lattice spacing d = 3.843 (Å) was 0.13°, and the calcined zeolite was a CON-type zeolite (CIT-1) with a proton-type cation type.

[0129] [Table 14]

[0130] Next, a metal-containing step was carried out in the same manner as in Example 1, except that the calcined zeolite was used, to obtain the zeolite of this comparative example. The zeolite of this comparative example was CIT-1, with a Cs2O / Al2O3 ratio of 0.64 and a cation type of Cs + It was the type.

[0131] The zeolites of Examples 4 and 8 and Comparative Examples 1 and 2 were used as hydrocarbon adsorbents and their hydrocarbon adsorption measurements were carried out. The results are shown in the table below.

[0132] [Table 15]

[0133] ZTS-8 has a higher desorption starting temperature and purification rate than *BEA-type zeolite (Comparative Example 1), which is used as a hydrocarbon adsorbent, and an existing zeolite belonging to the SSZ-33 family (Comparative Example 2). This confirmed that ZTS-8 has a higher hydrocarbon adsorption capacity than existing substances belonging to the SSZ-33 family and zeolites with other structures.

Claims

1. A zeolite having at least the following powder X-ray diffraction peaks, wherein the full width at half maximum of the powder X-ray diffraction peak having a peak top at a lattice spacing d = 3.85 ± 0.06 Å when CuKα radiation is used as a light source is 0.20° or more and 0.80° or less, and wherein the ratio of the intensity of the powder X-ray diffraction peak having a peak top at a lattice spacing d = 10.46 ± 0.55 Å when CuKα radiation is used as a light source to the intensity of the powder X-ray diffraction peak having a peak top at a lattice spacing d = 11.33 ± 0.23 Å ​​when CuKα radiation is used as a light source is 0.155 or more. Table 1

2. 2. The zeolite according to claim 1, wherein the molar ratio of silica to alumina is 20 or more and 500 or less.

3. 3. The zeolite according to claim 1, wherein the pore volume is from 0.10 mL / g to 0.50 mL / g.

4. 4. The zeolite according to claim 1, which does not have an XRD peak having a peak top at a lattice spacing d=9.60±0.30 Å.

5. 5. The zeolite according to claim 1, wherein the average crystal size is 0.05 μm or more and 5.0 μm or less.

6. 6. The zeolite according to claim 1, wherein the cation type is at least one of the group consisting of a proton type, a sodium type, a potassium type, an ammonium type, a quaternary ammonium type, and a cesium type.

7. 7. A method for producing a zeolite according to claim 1, comprising: a step of crystallizing a composition containing a silica source, an alumina source, an alkali source, a quaternary ammonium cation, and water, but not containing FAU zeolite, wherein the quaternary ammonium cation is 1,4-bis(N-cyclohexylpiperidinium)butane dication.

8. The method for producing a zeolite according to claim 7, wherein the alkali source contains at least a potassium compound.

9. The method according to claim 7 or 8, wherein the quaternary ammonium cation is at least one selected from the group consisting of 1,4-bis(N-cyclohexylpiperidinium)butane dication hydroxide, 1,4-bis(N-cyclohexylpiperidinium)butane dication bromide, and 1,4-bis(N-cyclohexylpiperidinium)butane dication chloride.

10. 10. The method of claim 7, wherein the composition has a molar ratio of OH to silica of greater than 0 and not greater than 0.

30.

11. 11. The method of claim 7, wherein the molar ratio of quaternary ammonium cation to silica in the composition is greater than 0 and less than or equal to 0.

10.

12. A hydrocarbon adsorbent comprising the zeolite according to any one of claims 1 to 6.

13. A method for adsorbing hydrocarbons, using a zeolite according to any one of claims 1 to 6.

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