Aluminosilicate for zeolite production

Abstract

To provide at least one of aluminosilicate for promotion of crystallization of AEI-type zeolite and a manufacturing method thereof, and a manufacturing method of AEI-type zeolite using the same.SOLUTION: An additive for manufacturing zeolite comprises aluminosilicate characterized by: having a powder X-ray diffraction peak with peak tops at least at lattice spacing of d=3.50±0.07Å, d=6.90±0.20Å, and d=10.40±1.50Å, a half-value width of a powder X-ray diffraction peak having peak a top at d=3.50±0.07Å of 0.8 or over and 4.5 or under, and a diffraction intensity to a diffraction intensity of an XRD peak with a peak top at d=3.50±0.07Å of 10% or over; and not having an XRD peak of a half-value width of 0.25 or under.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to aluminosilicates, and in particular to aluminosilicates for the production of zeolites. [Background technology]

[0002] AEI zeolite has been studied for use as a catalyst for olefin production and selective catalytic reduction catalyst (so-called SCR catalyst), and has conventionally been produced by a method involving structural transformation of Y zeolite (Patent Document 1).

[0003] However, because Y-type zeolite is expensive, studies have been conducted on methods for producing AEI-type zeolite that do not use Y-type zeolite as a starting material. To date, methods for producing AEI-type zeolite have been reported that use, as starting materials other than Y-type zeolite, zeolites other than Y-type zeolite (Patent Document 2), amorphous aluminosilicates (Patent Documents 3 and 4, Non-Patent Document 1), and amorphous compounds such as silica, such as fumed silica, and aluminum hydroxide (Patent Document 5). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 5,958,370 [Patent Document 2] JP 2017-48105 A [Patent Document 3] Japanese Patent Application Laid-Open No. 2017-36204 [Patent Document 4] Japanese Patent Application Laid-Open No. 2017-39638 [Patent Document 5] Patent No. 6572751 [Non-patent literature]

[0005] [Non-Patent Document 1] 33rd Zeolite Research Symposium, A12 (2017) Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present disclosure is to provide at least one of an aluminosilicate that promotes the crystallization of AEI zeolite, a method for producing the same, and a method for producing AEI zeolite using the same. [Means for solving the problem]

[0007] In the present disclosure, the crystallization of AEI zeolite was investigated, and as a result, it was found that the crystallization of AEI zeolite was promoted by using an aluminosilicate as an additive.

[0008] That is, the gist of the present disclosure is as follows. [1] An aluminosilicate characterized by having a powder X-ray diffraction peak with a peak top at at least the following lattice spacing d, and the half-width of the powder X-ray diffraction peak with a peak top at d = 3.50 ± 0.07 Å is 0.8 or more and 4.5 or less.

[0009] [Table 1]

[0010] [2] The aluminosilicate according to the above [1], wherein the half-width of the powder X-ray diffraction peak having a peak top at d=10.40±1.50 Å is 2.0 or more and 5.5 or less. [3] The aluminosilicate according to [1] or [2] above, wherein the half-value width of the powder X-ray diffraction peak having a peak top at d=6.90±0.20 Å is 0.4 or more and 2.5 or less. [4] The aluminosilicate according to any one of [1] to [3] above, which has a powder X-ray diffraction peak with a peak top at d=3.99±0.10 Å. [5] BET specific surface area is 50m 2 / g or more. [6] A method for producing an AEI zeolite, comprising: a step of crystallizing a composition containing a silica source, an alumina source, an alumina source, a structure-directing agent source, water, and the aluminosilicate described in any one of [1] to [5] above. [7] The method according to the above [6], wherein the silica source and the alumina source are amorphous substances containing at least one of silicon and aluminum. [8] The method for producing AEI zeolite according to [6] or [7] above, wherein the composition does not contain Y zeolite. [9] The method for producing an AEI zeolite according to any one of [6] to [8] above, wherein the composition contains sodium and an alkali metal other than sodium.

[10] A method for producing an AEI zeolite according to any one of [6] to [9] above, wherein the molar ratio of hydroxide ions to silica in the composition is less than 0.45.

[11] The method for producing an AEI zeolite according to any one of [6] to

[10] above, wherein the composition has the following molar composition: M is an alkali metal other than sodium, and SDA is an organic structure-directing agent. SiO2 / Al2O3 ratio = 20 or more, 50 or less Na / SiO2 ratio = 0.05 or more, 0.3 or less M / SiO2 ratio = 0.05 or more, 0.5 or less SDA / SiO2 ratio = 0.1 or more, 0.3 or less OH / SiO2 ratio = 0.1 or more, less than 0.45 H2O / SiO2 ratio = 8 or more, less than 20

[0011]

[12] The method for producing an AEI zeolite according to any one of [6] to

[11] above, wherein the fluorine content of the composition is 100 ppm by mass or less. [Effects of the Invention]

[0012] The present disclosure can provide at least one of an aluminosilicate that promotes the crystallization of AEI zeolite, a method for producing the same, and a method for producing AEI zeolite using the same. [Brief explanation of the drawings]

[0013] [Figure 1] XRD pattern of low-crystalline aluminosilicate of Example 2 [Figure 2] XRD pattern of the low-crystalline aluminosilicate of Example 4 [Figure 3] XRD pattern of AEI zeolite of Example 7 DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, the aluminosilicate according to the present disclosure will be described with reference to an example embodiment.

[0015] This embodiment is an aluminosilicate having a powder X-ray diffraction peak with a peak top at at least the following lattice spacing d, and the half-width of the powder X-ray diffraction peak with a peak top at d=3.50±0.07 Å is 0.8 to 4.5. The aluminosilicate of this embodiment promotes the crystallization of AEI zeolite, and in particular, enables AEI zeolite to be crystallized in a shorter time in a method for producing AEI zeolite that uses an alumina source and a silica source other than zeolite as starting materials.

[0016] [Table 2]

[0017] In this embodiment, the term "aluminosilicate" refers to a composite compound of silica and alumina having a skeletal structure consisting of a repetition of a network of aluminum (Al) and silicon (Si) via oxygen (O).

[0018] The aluminosilicate of this embodiment has a powder X-ray diffraction peak having a peak top at at least the following lattice spacing d:

[0019] [Table 3]

[0020] The aluminosilicate of this embodiment can be considered to be a crystalline aluminosilicate because its powder X-ray diffraction (hereinafter also referred to as "XRD") pattern includes an XRD peak having a peak top at d = 3.50 ± 0.07 Å (hereinafter also referred to as "main XRD peak"), an XRD peak having a peak top at d = 6.90 ± 0.20 Å, and an XRD peak having a peak top at d = 10.40 ± 1.50 Å.

[0021] Preferably, the aluminosilicate of this embodiment has at least the following XRD peaks:

[0022] [Table 4]

[0023] In addition to the above-described XRD peaks, the aluminosilicate of this embodiment preferably has an XRD peak having a peak top at d=3.99±0.10 Å. In addition to these XRD peaks, the aluminosilicate of this embodiment may have an XRD peak whose diffraction intensity (hereinafter also referred to as "relative intensity") relative to the diffraction intensity of the main XRD peak is less than 10%.

[0024] The aluminosilicate of this embodiment has a main XRD peak half width of 0.8 to 4.5, preferably 1.0 to 4.0, and more preferably 1.1 to 3.5. Because the XRD peak with the highest diffraction intensity is a broad peak with a large half width, the aluminosilicate of this embodiment can also be considered a low-crystalline aluminosilicate, i.e., a crystalline aminosilicate having a degree of crystallinity that does not allow for the structure to be specified.

[0025] The aluminosilicate of this embodiment preferably has an XRD peak having a top at d = 10.40 ± 1.50 Å with a half-width of 2.0 or more and 5.5 or less, and more preferably has an X-ray powder diffraction peak having a top at d = 6.90 ± 0.20 Å with a half-width of 0.4 or more and 2.5 or less.

[0026] The aluminosilicate of this embodiment preferably does not have an XRD peak in its XRD pattern with a relative intensity of 10% or more and a half-value width of 0.25 or less, and more preferably does not have an XRD peak with a relative intensity of 10% or more and a half-value width of 0.2 or less.

[0027] In this embodiment, the values ​​of the lattice spacing d and half-width of the XRD peak are values ​​of the aluminosilicate in a dried state, that is, in a state containing a structure-directing agent.

[0028] The conditions for the XRD measurement in this embodiment are as follows. Radiation source: CuKα radiation (λ=1.5405Å) Measurement mode: Step scan Measurement range: 2θ=3°~43° Scan condition: 32° / min Measurement time: 3 seconds

[0029] XRD measurement can be performed using a general X-ray diffractometer (e.g., Ultima IV, manufactured by Rigaku Corporation) with a measurement sample being an aluminosilicate dried at 100 to 120°C in the air (i.e., an aluminosilicate that has not been subjected to heat treatment at 300°C or higher).

[0030] In the XRD pattern obtained in the above measurement, each XRD peak is observed as a peak having a peak top at the following 2θ. 2θ=8.5±1.2° of the XRD peak with lattice spacing d=10.40±1.50Å 2θ=12.5±0.7° of the XRD peak with lattice spacing d=6.90±0.20Å 2θ=25.5±0.5° of the XRD peak with lattice spacing d=3.50±0.07Å Lattice spacing d=3.99±0.10Å, XRD peak 2θ=22.3±0.5°

[0031] In this embodiment, the detection of each XRD peak and the measurement of the half-width can be performed by peak searching the obtained XRD pattern to detect each XRD peak and determine the half-width of the detected XRD peak. The peak search can be performed by second-order differential calculus on an XRD pattern that has been smoothed using convolution of a Gaussian function with a smoothing parameter of 10.00, background processing using the Sonneveld-Visser method with a peak width threshold of 1.00 and an intensity threshold of 10.00, and removal of the Kα2 line with an intensity ratio of 0.4970. The half-width is the full width at half maximum (FWHM) that corresponds to half the width of the peak (peak width) measured for each detected XRD peak, which is half the maximum peak intensity.

[0032] XRD pattern analysis, such as smoothing, background processing, profile fitting, and calculation of half-width, can be performed using an analysis program attached to the X-ray diffractometer (for example, integrated powder X-ray analysis software PDXL2 Ver. 2.3.1.0, manufactured by RIGAKU Corporation).

[0033] The aluminosilicate of this embodiment has a BET specific surface area of ​​50 m when impurities in the pores, such as organic structure-directing agents, are removed. 2 / g or more is preferable, and 2 It is more preferable that the BET specific surface area is high, for example, 500 m 2 / g or less, and even 400m 2 / g or less.

[0034] In this embodiment, the BET specific surface area may be measured by a BET single-point method using nitrogen as the carrier gas and a relative pressure (p / p) of 0.30. Specific measurement conditions for the BET specific surface area include the following: Adsorption medium: N2 Adsorption temperature: -196℃ Pretreatment conditions: Treatment in air at 350°C for 30 minutes

[0035] The BET specific surface area can be measured for an aluminosilicate after treatment at 400 to 600° C. in air using a common device (for example, Bellsorp Mini II, manufactured by Microtrackbell).

[0036] The molar ratio of silica to alumina in the aluminosilicate of this embodiment (hereinafter also referred to as "SiO2 / Al2O3 ratio") is arbitrary, but may be, for example, 10 or more and 80 or less, preferably 15 or more and 30 or less.

[0037] In this embodiment, the composition such as the SiO2 / Al2O3 ratio can be measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES), which can be performed using a general ICP device (device name: OPTIMA5300DV, manufactured by PerkinElmer).

[0038] The aluminosilicate of this embodiment is preferably used as an aluminosilicate for producing zeolite, an additive for producing zeolite, etc., but can also be used for known applications of aluminosilicates, such as a catalyst, adsorbent, catalyst support, adsorbent support, etc. When the aluminosilicate of this embodiment is used as an aluminosilicate for producing zeolite or an additive for producing zeolite, it may be in a state in which organic cations are contained in the pores or in a state in which the organic cations have been removed.

[0039] The aluminosilicate of this embodiment can be synthesized by any method, including, for example, a synthesis method comprising a step of crystallizing a composition containing a silica source, an alumina source, an alkali source, an OSDA source, and water and having the following molar composition at 130°C or higher and 180°C or lower for 5 hours or longer and shorter than 30 hours.

[0040] SiO2 / Al2O3 ratio =20 or more and 30 or less Alkali / SiO2 ratio = 0.15 or more and 0.25 or less OSDA / SiO2 ratio = 0.01 or more and 1.00 or less H2O / SiO2 ratio =5 or more and 20 or less OH / SiO2 ratio = 0.30 or more and less than 0.45 In the above composition, alkali is one or more alkali metal cations selected from the group consisting of sodium, potassium, cesium and rubidium, preferably sodium and potassium, and OSDA is an organic cation capable of directing zeolite.

[0041] The alumina source, silica source, and alkali source may each be any compound containing aluminum (Al), silicon (Si), and one or more alkali metals. Examples of the alumina source include an amorphous compound containing aluminum, examples of the silica source include an amorphous compound containing silicon, and examples of the alkali source include alkali metal hydroxides.

[0042] The OSDA source may be any compound containing an organic cation capable of directing zeolite, or further, a compound containing an organic cation that serves as a template for zeolite. Examples of the OSDA source include compounds containing one or more cations selected from the group consisting of 1,1,3,5-tetramethylpiperidinium cation, 1,1,2,6-tetramethylpiperidinium cation, tetramethylammonium cation, and choline cation. Examples include one or more hydroxides, chlorides, bromides, and iodides containing one or more cations selected from the group consisting of 1,1,3,5-tetramethylpiperidinium cation (hereinafter also referred to as "TMP"), tetramethylammonium cation (hereinafter also referred to as "TMA"), and choline cation (hereinafter also referred to as "Cholin").

[0043] The crystallization may be carried out under conditions that allow the crystallization to proceed appropriately, such as hydrothermal treatment at 130°C or higher and 180°C or lower for 5 hours or longer but less than 30 hours, preferably 10 hours or longer but 25 hours or shorter.

[0044] Hereinafter, an example of a method for producing AEI zeolite using the aluminosilicate of this embodiment as an additive for producing zeolite will be described.

[0045] The method for producing AEI zeolite of the present embodiment includes the steps of: Alkaline source and crystallizing a composition containing a silica source, an alumina source, a structure-directing agent source, water, and the aluminosilicate of the present embodiment. Alkaline source By crystallizing a composition containing a structure-directing agent source, water, and the aluminosilicate of this embodiment (hereinafter also referred to as a "raw material composition"), AEI zeolite is crystallized in a shorter time than when a composition not containing the aluminosilicate of this embodiment is crystallized. Furthermore, crystallization of AEI zeolite having an SiO / AlO ratio of 15 or more, and further 17 or more, is more likely to be promoted.

[0046] AEI zeolite is a zeolite having an AEI structure, and in particular, a crystalline aluminosilicate having an AEI structure.

[0047] The zeolite structure in this embodiment is a structure defined by the IZA Structure Committee, and the "AEI structure" is a structure that corresponds to the AEI type in structure code. The AEI structure can be identified by comparing it with either the XRD pattern described in "Collection of simulated XRD powder patterns for zeolites," Fifth revised edition, p. 23 (2007) or the XRD pattern described in the AEI section of Zeolite Framework Types on the IZA Structure Committee's website http: / / www.iza-struture.org / databases / .

[0048] "Crystalline aluminosilicate" is a composite compound of crystalline silica and alumina having a skeletal structure consisting of a repeating network of aluminum (Al) and silicon (Si) via oxygen (O), and does not include zeolite-related substances that have metal elements other than aluminum (Al) and silicon (Si) in their skeletons, such as crystalline silicoaluminophosphates and crystalline aluminophosphates that contain phosphorus (P) in their skeletons.

[0049] The AEI zeolite obtained by the production method of this embodiment can be, for example, a crystalline aluminosilicate having an XRD pattern equivalent to that of SSZ-39.

[0050] The alumina source is aluminum (Al) or a compound containing aluminum, and examples thereof include one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum chloride, aluminum nitrate, crystalline aluminosilicate, amorphous aluminosilicate, metallic aluminum, pseudoboehmite, alumina sol, and aluminum alkoxide. Since this makes it easier to obtain the crystallization-promoting effect of the aluminosilicate of this embodiment, the alumina source is preferably an amorphous aluminum compound, and specific examples of the compound include one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum chloride, aluminum nitrate, amorphous aluminosilicate, alumina sol, and aluminum alkoxide. From an industrial viewpoint, the alumina source is preferably one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum chloride, and amorphous aluminosilicates, more preferably one or more selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum sulfate, aluminum chloride, and amorphous aluminosilicates, even more preferably one or more selected from the group consisting of aluminum oxide, aluminum sulfate, aluminum chloride, and amorphous aluminosilicates, and still more preferably an amorphous aluminosilicate.

[0051] The silica source is silicon (Si) or a compound containing silicon, and examples thereof include at least one selected from the group consisting of silica sol, fumed silica, colloidal silica, precipitated silica, amorphous silicic acid, crystalline aluminosilicate, and amorphous aluminosilicate. Preferably, the silica source is an amorphous silicon compound, and specific examples thereof include at least one of amorphous silicic acid and amorphous aluminosilicate.

[0052] Particularly preferred alumina sources and silica sources include amorphous aluminosilicates, and further, amorphous aluminosilicates having a molar ratio of silica to alumina (hereinafter also referred to as "SiO2 / Al2O3 ratio") of more than 10 and not more than 100 (silica content of more than 78 mass% and not more than 97 mass%), 15 or more and not more than 50 (silica content of 84 mass% or more and not more than 94 mass%), or even 15 or more and not more than 40 (silica content of 84 mass% or more and not more than 93 mass%).

[0053] The alkali source is an alkali metal or a compound containing an alkali metal element, and examples thereof include one or more selected from the group consisting of hydroxides, carbonates, sulfates, chlorides, bromides, and iodides of alkali metals. One or more selected from the group consisting of hydroxides, chlorides, bromides, and iodides is preferred, and hydroxide is more preferred.

[0054] Examples of the alkali metal contained in the alkali source include one or more elements selected from the group consisting of sodium, potassium, rubidium, and cesium, with at least one of sodium and potassium being preferred, and sodium being more preferred. Because structural units capable of deriving AEI zeolite tend to be more easily produced, the alkali metal is preferably sodium and one or more selected from the group consisting of potassium, rubidium, and cesium, and more preferably potassium and sodium.

[0055] The organic structure directing agent source (hereinafter also referred to as "SDA source") may be a compound containing a cation that directs AEI zeolite. Examples of the cation that directs AEI zeolite include a compound containing one or more selected from the group consisting of a 1,1,3,5-tetramethylpiperidinium cation, a 1,1-diethyl-2,6-dimethylpiperidinium cation, a 1,1,2,6-tetramethylpiperidinium cation, a 1-ethyl-1,2,6-trimethylpiperidinium cation, and a 1,1,2-triethylpiperidinium cation. A compound containing one or more of a 1,1,3,5-tetramethylpiperidinium cation (TMP) and a 1,1-diethyl-2,6-dimethylpiperidinium cation (hereinafter also referred to as "DEDMP") is preferred, and TMP + is more preferred.

[0056] The SDA source may be at least one selected from the group consisting of hydroxide, chloride, bromide and iodide of SDA, and is preferably at least one selected from the group consisting of hydroxide, chloride and bromide of SDA.

[0057] Particularly preferred sources of SDA include one or more selected from the group consisting of 1,1,3,5-tetramethylpiperidinium hydroxide, 1,1,3,5-tetramethylpiperidinium bromide, and 1,1,3,5-tetramethylpiperidinium chloride.

[0058] The water may be distilled water, deionized water, or pure water, and further, 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.

[0059] The raw material composition may contain seed crystals. The seed crystals may be zeolite crystals having sufficient crystallinity to allow their structure to be identified by their XRD patterns. YoSpecific examples of the seed crystals include one or more selected from the group consisting of AEI zeolite, CHA zeolite, OFF zeolite, ERI zeolite, KFI zeolite, AFX zeolite, AFT zeolite, EAB zeolite, GME zeolite, and LEV zeolite. At least one of AEI zeolite and CHA zeolite is preferred, and AEI zeolite is more preferred.

[0060] In this embodiment, the mass ratio of the total of Al in Al2O3 conversion and Si in SiO2 conversion of the seed crystals to the total of Al in Al2O3 conversion and Si in SiO2 conversion of the raw material composition (excluding the seed crystals and additives) (hereinafter also referred to as the "seed crystal content") is preferably from 0% by mass to 30% by mass, more preferably from 1% by mass to 10% by mass.

[0061] The aluminosilicate of this embodiment contained in the raw material composition preferably has a mass ratio (hereinafter also referred to as "additive content") of the total of Al as calculated as Al2O3 and Si as calculated as SiO2 of the aluminosilicate of this embodiment to the total of Al as calculated as Al2O3 and Si as calculated as SiO2 of the raw material composition (excluding seed crystals and additives) of 1.0 mass% or more and 10 mass% or less, more preferably 1.2 mass% or more and 5 mass% or less. Ze In a method for producing AEI zeolite using an alumina source and a silica source other than zeolite as starting materials, the crystallization time of AEI zeolite tends to be shorter.

[0062] The method for mixing the raw materials such as the alumina source with the aluminosilicate of this embodiment is arbitrary, and examples thereof include mixing the aluminosilicate of this embodiment together with the alumina source etc. to prepare a raw material composition, dissolving the raw materials such as the alumina source and then mixing the aluminosilicate of this embodiment to prepare a raw material composition, etc. When mixing with the raw materials, the aluminosilicate of this embodiment may be pulverized and then mixed with these.

[0063] Examples of preferable compositions of the raw material composition of this embodiment before mixing with the aluminosilicate and seed crystals include, in molar proportions, an SiO / AlO ratio of 10 to 100, preferably 15 to 50, and more preferably 15 to 40; an SDA to silica molar ratio (hereinafter also referred to as the "SDA / SiO ratio") of 0.05 to 0.5, preferably 0.10 to 0.40, more preferably 0.10 to 0.30, and even more preferably 0.10 to 0.20; an M / SiO ratio of 0.1 to 0.6, preferably 0.1 to less than 0.3, and more preferably 0.1 to 0.25; and an HO / SiO ratio of 3 to 50, preferably 5 to 50, and more preferably 5 to 25.

[0064] By including the aluminosilicate of this embodiment, the AEI zeolite is likely to crystallize, especially even when the OH / SiO2 ratio is in a low range. Therefore, the OH / SiO2 ratio of the raw material composition is set to 0.1 or more and 0.5 or less, preferably 0.2 or more and less than 0.45, and more preferably 0.2 or more and 0.4 or less.

[0065] In this embodiment, the OH / SiO ratio is the molar ratio of hydroxide ions (OH) in the raw material composition to the molar ratio of silica in the raw material composition. - The hydroxide ions in the raw material composition include hydroxide ions derived from the alumina source, silica source, alkali source, and SDA source.

[0066] When the raw material composition contains sodium and one or more elements selected from the group consisting of potassium, rubidium, and cesium, the (K+Rb+Cs) / SiO2 ratio is, for example, 0 or more and 0.5 or less, preferably 0 or more and 0.3 or less, and more preferably 0 or more and 0.1 or less, and the Na / SiO2 ratio is, for example, 0.01 or more and 1.0 or less, preferably 0.05 or more and 0.4 or less, and more preferably 0.05 or more and 0.3 or less.

[0067] The following compositions are preferred as molar compositions of the raw material composition before mixing of the aluminosilicate and seed crystals in this embodiment.

[0068] SiO2 / Al2O3 ratio = 20 or more, 50 or less Na / SiO2 ratio = 0.05 or more, 0.3 or less M / SiO2 ratio = 0.05 or more, 0.5 or less SDA / SiO2 ratio = 0.1 or more, 0.3 or less OH / SiO2 ratio = 0.1 or more, less than 0.45 H2O / SiO2 ratio = 8 or more, less than 20 Here, SDA is a structure directing agent, and M is an alkali metal other than sodium.

[0069] 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 160°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.

[0070] The time for the crystallization step is optional, but may be 30 hours or more and 150 hours or less. By including the aluminosilicate of this embodiment, even if the time for the crystallization step is 72 hours or less, or even 48 hours, the yield of the AEI zeolite (hereinafter also simply referred to as "yield") can be 55% or more and 80% or less.

[0071] The yield in this embodiment is calculated using the following formula.

[0072] Yield (mass%) = W Cry / W Raw ×100 W in the above equation Cry and W Raw are the total masses of Al in terms of Al2O3 and Si in terms of SiO2 in the AEI zeolite and the raw material composition, respectively.

[0073] In order to facilitate the application of manufacturing equipment made of general-purpose materials, the amorphous composition and raw material composition preferably do not contain fluorine (F) and phosphorus (P). The fluorine content and phosphorus content of the amorphous composition and raw material composition, as measured by general composition analysis such as ICP measurement, are preferably 100 mass ppm or less, more preferably 10 mass ppm or less, and even more preferably below the measurement limit.

[0074] The manufacturing method of this embodiment may include at least one of a washing step, a drying step, an SDA removal step, and an ion exchange step.

[0075] The washing step involves solid-liquid separation into AEI zeolite and a liquid phase, and the solid-liquid separation is carried out by a known method, and the AEI zeolite obtained as a solid phase may be washed with pure water.

[0076] The drying step removes moisture physically adsorbed on the AEI zeolite. Drying conditions are arbitrary, and examples include drying the AEI zeolite in the air at 50°C or higher and 150°C or lower for 2 hours or longer by leaving it to stand or by using a spray dryer.

[0077] The SDA removal step removes SDA contained in the AEI zeolite. Examples of methods for removing SDA include one or more methods selected from the group consisting of a liquid-phase treatment with an acidic aqueous solution, an exchange treatment with 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.

[0078] The ion exchange process converts the AEI zeolite into any cation type. For example, the cation type can be ammonium (NH4 + ) type, AEI type zeolite can be mixed with an ammonium chloride solution and stirred for ion exchange. + ) type, ammonium (NH4 + ) type AEI zeolite is calcined in air.

[0079] Examples of AEI zeolite obtained by the production method of this embodiment (hereinafter also referred to as "AEI zeolite of this embodiment") include AEI zeolites that satisfy at least one of the following: an SiO2 / Al2O3 ratio of 12.2 to 100, preferably 15 to 50, and more preferably 17 to 30; an average crystal size of 0.3 to 5.0 μm, preferably 0.4 to 3.0 μm, and more preferably 0.5 to 3.0 μm; and an acid amount of 0.5 mmol / g to 3 mmol / g, and preferably 1 mmol / g to 2 mmol / g.

[0080] In this embodiment, the "crystal size" refers to the particle size of primary particles, which is the long diameter of the smallest independent particle observed under an electron microscope. The "average crystal size" refers to the arithmetic mean of the crystal sizes of 30 or more primary particles randomly sampled under an electron microscope. Therefore, the secondary particle size and average secondary particle size, which are the diameters of secondary particles formed by agglomeration of multiple primary particles, are different from the crystal size and average crystal size. The shape of the primary particles may be at least one of the following: a cubic crystal shape, a tetragonal crystal shape, and a twin crystal shape formed by combining a cubic crystal shape and a tetragonal crystal shape.

[0081] The "acid amount" can be determined by ammonia TPD measurement of proton-type AEI zeolite from which organic matter has been removed.

[0082] The AEI zeolite of this embodiment has high heat resistance and exhibits little decrease in crystallinity before and after exposure to a hydrothermal atmosphere, and preferably exhibits less decrease in crystallinity before and after exposure to a hydrothermal atmosphere than conventional AEI zeolites obtained using Y zeolite as a raw material. The degree of decrease in crystallinity due to exposure to a hydrothermal atmosphere can be measured using the ratio of the crystallinity after exposure to a hydrothermal atmosphere to the crystallinity before exposure to a hydrothermal atmosphere (hereinafter also referred to as the "crystallization retention rate") as an indicator, which can be determined by comparing the XRD peak intensities before and after exposure to a hydrothermal atmosphere.

[0083] The AEI zeolite of the present embodiment can be used as a catalyst support or an adsorbent. Furthermore, by modifying the AEI zeolite of the present embodiment with at least one of copper and iron, it is expected to be used as a catalyst, and further as a nitrogen oxide reduction catalyst. [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) XRD measurements of the samples were performed using a standard X-ray diffractometer (Ultima IV, manufactured by Rigaku Corporation). The source used was CuKα radiation (λ = 1.5405 Å), and the measurement range was 2θ from 3° to 43°. The structure of the sample was identified by comparing the obtained XRD pattern with the XRD pattern in Table 1 of Patent Document 1. (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. (BET specific surface area) The specific surface area of ​​the sample was determined by BET measurement. A common specific surface area measuring device (device name: Bellsorp Mini II, manufactured by Microtrack Bell) was used for the measurement. As a pretreatment, the sample was kept at 350°C for 2 hours. After that, the BET specific surface area was measured using nitrogen gas. The BET specific surface area was measured using the one-point method with p / p0 = 0.30.

[0085] <Synthesis of aluminosilicate> Reference example 1 Amorphous aluminosilicate with an SiO2 / Al2O3 ratio of 27, 1,1,3,5-tetramethylpiperidinium hydroxide, tetramethylammonium chloride, sodium oxide, potassium hydroxide, and pure water were mixed to obtain the following composition.

[0086] SiO2 / Al2O3 ratio = 27 Alkali / SiO2 ratio = 0.21 (Na / SiO2 ratio =0.18) (K / SiO2 ratio =0.03) OSDA / SiO2 ratio = 0.155 (TMP / SiO2 ratio =0.15) (TMA / SiO2 ratio =0.005) H2O / SiO2 ratio =12 OH / SiO2 ratio =0.36 AEI zeolite was mixed into the mixed composition so that the seed crystal content was 1.0 mass %, and the mixture was then filled into a sealed container and subjected to hydrothermal treatment at 170°C for 48 hours while stirring.

[0087] After the hydrothermal treatment, the resulting product was recovered by solid-liquid separation, washed with pure water, and dried in air at 110°C to obtain the aluminosilicate of this example. In the XRD pattern of the aluminosilicate of this example (before OSDA removal) after drying at 110°C, XRD peaks with a relative intensity of 10% or more are shown in the table below.

[0088] [Table 5]

[0089] This reference example The aluminosilicate of XR is a low-crystalline aluminosilicate. D The structure could not be identified from the pattern.

[0090] Example 2 Amorphous aluminosilicate with an SiO2 / Al2O3 ratio of 27, TMPOH, TMACl, sodium oxide, potassium hydroxide, and pure water were mixed to obtain the following composition.

[0091] SiO2 / Al2O3 ratio =27 Alkali / SiO2 ratio = 0.22 (Na / SiO2 ratio =0.20) (K / SiO2 ratio =0.02) OSDA / SiO2 ratio = 0.1825 (TMP / SiO2 ratio =0.18) (TMA / SiO2 ratio =0.0025) H2O / SiO2 ratio =12 OH / SiO2 ratio =0.40 After mixing, the pulverized aluminosilicate of Example 1 was mixed in so that the additive content was 0.5% by mass, and then AEI zeolite was mixed in so that the seed crystal content was 0.5% by mass, thereby obtaining a composition.

[0092] The aluminosilicate of this example was obtained in the same manner as in Example 1, except that the obtained composition was used. In the XRD pattern of the aluminosilicate of this example, XRD peaks with a relative intensity of 10% or more are shown in the table below. The obtained XRD pattern is also shown in Figure 1.

[0093] [Table 6]

[0094] The aluminosilicate of this example is a low-crystalline aluminosilicate, and its structure could not be identified from the obtained XRD pattern. In addition, after calcining the aluminosilicate of this example at 600°C in air, the BET specific surface area was 343 m 2 / g.

[0095] Example 3 Pure water, sodium hydroxide, potassium hydroxide, choline hydroxide, and amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 23 were mixed to obtain the following composition.

[0096] SiO2 / Al2O3 ratio =23 Alkali / SiO2 ratio = 0.22 (Na / SiO2 ratio =0.20) (K / SiO2 ratio =0.02) OSDA / SiO2 ratio = 0.08 (Cholin / SiO2 ratio =0.08) H2O / SiO2 ratio =15 OH / SiO2 ratio =0.30 After mixing, the pulverized aluminosilicate of Example 2 was mixed in so that the additive content was 0.5 mass %, to obtain a composition.

[0097] The aluminosilicate of this example was obtained in the same manner as in Example 1, except that the obtained composition was used and the hydrothermal treatment time was 18 hours. In the XRD pattern of the aluminosilicate of this example, XRD peaks with a relative intensity of 10% or more are shown in the table below. No XRD peaks other than those in the table below were detected in the XRD pattern.

[0098] [Table 7]

[0099] The aluminosilicate of this example is a low-crystalline aluminosilicate, and its structure could not be identified from the obtained XRD pattern. In addition, the BET specific surface area of ​​the aluminosilicate of this example after calcination at 600°C in air was 87 m 2 / g.

[0100] Example 4 The aluminosilicate of this example was obtained in the same manner as in Example 1, except that the additive used was an aluminosilicate obtained in the same manner as in Example 3, and the hydrothermal treatment time was 20 hours. In the XRD pattern of the aluminosilicate of this example, XRD peaks with a relative intensity of 10% or more are shown in the table below. The obtained XRD pattern is also shown in Figure 2.

[0101] [Table 8]

[0102] The aluminosilicate of this example is a low-crystalline aluminosilicate, and its structure could not be specified from the obtained XRD pattern. Also, the BET specific surface area of the aluminosilicate of this example after firing at 600 °C in the atmosphere was 180 m 2 / g.

[0103] <Production of AEI-type zeolite> Example 5 Pure water, sodium hydroxide, potassium hydroxide, TMPOH, and an amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 30 were mixed to have the following composition. SiO2 / Al2O3 ratio = 30 Na / SiO2 ratio = 0.22 K / SiO2 ratio = 0.02 TMPOH / SiO2 ratio = 0.17 H2O / SiO2 ratio = 11 OH / SiO2 ratio = 0.41 After mixing, the aluminosilicate of Example 2 pulverized so that the additive content became 1.5 mass% was mixed, and then AEI-type zeolite was mixed so that the seed crystal content became 0.5 mass% to obtain a raw material composition.

[0104] The obtained raw material composition was filled in a sealed container and hydrothermally treated at 170 °C for 48 hours while stirring. After the crystallized product after the hydrothermal treatment was separated by solid-liquid separation and recovered, it was washed with pure water and dried at 110 °C in the atmosphere to obtain the AEI-type zeolite of this example. The SiO2 / Al2O

[0105] Example 6 Pure water, sodium hydroxide, potassium hydroxide, TMPOH, and an amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 30 were mixed to have the following composition, and the aluminosilicate obtained in Example 3 was used as an additive. Otherwise, the AEI-type zeolite of this example was obtained in the same manner as in Example 5 and the same method as Example SiO2 / Al2O3 ratio = 30 Na / SiO2 ratio =0.22 K / SiO2 ratio =0.02 TMPOH / SiO2 ratio =0.15 H2O / SiO2 ratio =11 OH / SiO2 ratio =0.39

[0106] The SiO2 / Al2O3 ratio of the obtained AEI zeolite was 18.3, and the yield was 63 mass%.

[0107] Example 7 The AEI zeolite of this example was obtained in the same manner as in Example 6, except that pure water, sodium hydroxide, potassium hydroxide, TMPOH, and an amorphous aluminosilicate having a SiO / AlO ratio of 30 were mixed to obtain the following composition, and that the aluminosilicate obtained in Example 4 was used as the additive. SiO2 / Al2O3 ratio =30 Na / SiO2 ratio =0.22 K / SiO2 ratio =0.02 TMPOH / SiO2 ratio =0.16 H2O / SiO2 ratio =11 OH / SiO2 ratio =0.40

[0108] The SiO2 / Al2O3 ratio of the obtained AEI zeolite was 18.7, and the yield was 64% by mass. The XRD pattern of the obtained AEI zeolite is shown in Figure 3. Figure 3 confirms that the XRD peaks themselves are different between the aluminosilicate used as the additive and the AEI zeolite obtained in this example, and that the AEI zeolite obtained in this example has high crystallinity.

[0109] Comparative Example 1 Pure water, sodium hydroxide, potassium hydroxide, TMPOH, and amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 30 were mixed to obtain the following composition. SiO2 / Al2O3 ratio =30 Na / SiO2 ratio =0.22 K / SiO2 ratio =0.02 TMPOH / SiO2 ratio =0.15 H2O / SiO2 ratio =11 OH / SiO2 ratio =0.39

[0110] After mixing, AEI zeolite was added so that the seed crystal content was 0.5% by mass, thereby obtaining a raw material composition.

[0111] The obtained raw material composition was filled into a sealed container and subjected to hydrothermal treatment at 170°C for 48 hours while stirring. The product after the hydrothermal treatment was amorphous, and crystallization of AEI zeolite was not confirmed in the raw material composition containing no additives.

[0112] Comparative Example 2 A hydrothermal treatment was performed in the same manner as in Comparative Example 1, except that FER zeolite was mixed so that the additive content was 1.5% by mass before mixing with AEI zeolite, and a product was obtained. The product after the hydrothermal treatment was amorphous, and crystallization of AEI zeolite was not confirmed.

[0113] In the XRD pattern of the FER-type zeolite used as the additive, the peak with the highest diffraction intensity was an XRD peak having a peak top at a lattice spacing d=3.53 Å, and its half-value width was 0.17.

[0114] From this comparative example, it was confirmed that the crystallization of AEI zeolite was not promoted even when an aluminosilicate with a small half-width was used as an additive.

[0115] Comparative Example 3 Pure water, sodium hydroxide, potassium hydroxide, amorphous aluminosilicate with a SiO2 / Al2O3 ratio of 27, and TMPOH were mixed to obtain a raw material composition having the following composition. SiO2 / Al2O3 ratio =27 Na / SiO2 ratio =0.13 K / SiO2 ratio =0.03 TMPOH / SiO2 ratio =0.20 H2O / SiO2 ratio =9.8 OH / SiO2 ratio =0.36

[0116] After mixing 4.3% by mass of AEI zeolite into the raw material composition, the raw material composition was filled into a sealed container and subjected to hydrothermal synthesis for 75 hours at 170°C while stirring. The obtained product was amorphous, and AEI zeolite was not obtained.

[0117] Comparative Example 4 With reference to the examples in U.S. Patent No. 5,958,370, AEI zeolite was produced using Y zeolite as a starting material. That is, pure water, sodium hydroxide, an aqueous sodium silicate solution, Y zeolite with a SiO2 / Al2O3 ratio of 6, and 1,1-diethyl-cis-2,6-dimethylpiperidinium hydroxide (hereinafter also referred to as "DEDMPOH") were mixed to obtain a raw material composition having the following composition: SiO2 / Al2O3 ratio =50 Na / SiO2 ratio =0.56 DEDMPOH / SiO2 ratio =0.16 H2O / SiO2 ratio =44.8 OH / SiO2 ratio =0.72

[0118] The content of zeolite in the raw material composition was 13.9% by mass. The raw material composition was filled into a sealed container and subjected to hydrothermal treatment at 135°C while stirring until AEI zeolite was crystallized. As a result, the crystals of AEI zeolite were transformation It was confirmed that it takes 168 hours to complete the process.

Claims

1. An additive for producing AEI zeolite, which is an aluminosilicate, characterized in that it has a powder X-ray diffraction peak having a peak top at at least the following lattice spacing d, the powder X-ray diffraction peak having a peak top at d = 3.50 ± 0.07 Å has a half-width of 0.8 or more and 4.5 or less, and the diffraction intensity relative to the diffraction intensity of the XRD peak having a peak top at d = 3.50 ± 0.07 Å is 10% or more, and it does not have an XRD peak with a half-width of 0.25 or less. 【Table 1】

2. 2. The additive for producing AEI zeolite, which is an aluminosilicate according to claim 1, wherein the half-width of a powder X-ray diffraction peak having a peak top at d=10.40±1.50 Å is 2.0 or more and 5.5 or less.

3. 3. The additive for producing AEI zeolite, which is an aluminosilicate according to claim 1 or 2, wherein the half-width of a powder X-ray diffraction peak having a peak top at d=6.90±0.20 Å is 0.4 or more and 2.5 or less.

4. 4. An additive for producing AEI zeolite, which is the aluminosilicate according to any one of claims 1 to 3, having a powder X-ray diffraction peak with a peak top at d = 3.99 ± 0.10 Å.

5. BET specific surface area is 50m ２ 5. An additive for producing AEI zeolite, which is the aluminosilicate according to claim 1, having a SiO2 content of 0.1g / g or more.

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