JP2022156977A - Faujasite type zeolite with high packing density and method for producing the same - Google Patents
Faujasite type zeolite with high packing density and method for producing the same Download PDFInfo
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- 239000010457 zeolite Substances 0.000 title claims abstract description 131
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 121
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000012856 packing Methods 0.000 title abstract description 18
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000010191 image analysis Methods 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
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- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 abstract description 31
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- 238000000034 method Methods 0.000 abstract description 19
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- 238000004458 analytical method Methods 0.000 abstract description 2
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- 239000011734 sodium Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 8
- 238000000635 electron micrograph Methods 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 description 8
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- 239000007864 aqueous solution Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
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- 238000002441 X-ray diffraction Methods 0.000 description 6
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- 239000002994 raw material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- -1 Na and K Chemical class 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
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- 239000003513 alkali Substances 0.000 description 3
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- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は充填密度が高いフォージャサイト型ゼオライトおよびその製造方法に関する。 The present invention relates to a faujasite-type zeolite with a high packing density and a method for producing the same.
ゼオライトという物質名は結晶性の多孔質アルミノシリケートの総称である。ゼオライトは、石油精製や石油化学をはじめとする多くの工業プロセスにおいて、触媒、吸着剤、および分離膜などの用途に幅広く使用されてきた。例えば、流動接触分解プロセスは、触媒を用いて石油中の重油分を分解し、付加価値の高いガソリンなどの留分を得る重要なプロセスである。このプロセスの触媒として、強い固体酸を有する多孔性材料であるフォージャサイト型ゼオライトが古くから使用されてきた。また、フォージャサイト型ゼオライトは吸着剤としても、古くから使用されている。 The substance name zeolite is a general term for crystalline porous aluminosilicates. Zeolites have been used extensively in applications such as catalysts, adsorbents, and separation membranes in many industrial processes, including petroleum refining and petrochemicals. For example, the fluid catalytic cracking process is an important process that uses a catalyst to crack heavy oil in petroleum to obtain fractions such as gasoline with high added value. Faujasite-type zeolites, which are porous materials with strong solid acids, have long been used as catalysts for this process. Faujasite-type zeolites have also been used as adsorbents for a long time.
一般的に、ゼオライトは、触媒や吸着剤用途で用いる場合、単位容積当たりの充填密度を上げ、単位容積当たりの接触面積を最大にすることが望ましいとされている（特許文献１）。また、これを解決する方法として、ゼオライトの一次粒子を凝集させて球状の二次粒子を形成する方法が知られている（特許文献２）。この方法では、バインダー成分を添加して噴霧乾燥することで、球状の二次粒子が形成される。二次粒子の形状を球状にすることにより、単位容積あたりの充填密度を上げることができるとされている（特許文献１）。これは、不定形粒子を充填した場合には隙間が多くなるのに対し、球状粒子を充填した場合には無駄な空隙が生じにくく、流動性にも優れていることから充填密度を高めることができるためである。 In general, when zeolites are used as catalysts or adsorbents, it is desirable to increase the packing density per unit volume and maximize the contact area per unit volume (Patent Document 1). In addition, as a method for solving this problem, a method is known in which primary particles of zeolite are aggregated to form spherical secondary particles (Patent Document 2). In this method, spherical secondary particles are formed by adding a binder component and spray drying. It is said that the packing density per unit volume can be increased by making the shape of the secondary particles spherical (Patent Document 1). This is because when irregularly shaped particles are filled, the gaps increase, whereas when spherical particles are filled, useless gaps are less likely to occur, and the fluidity is excellent, so the packing density can be increased. Because we can.
このように、噴霧乾燥することで球状の二次粒子を形成する方法では、ゼオライトのみでは球状の二次粒子が形成されないので、バインダー成分が添加される。しかしながら、ゼオライト以外の成分が含まれるので、ゼオライトの含有量が少なくなるという課題があった。 Thus, in the method of forming spherical secondary particles by spray drying, since spherical secondary particles cannot be formed with zeolite alone, a binder component is added. However, since it contains components other than zeolite, there is a problem that the content of zeolite is reduced.
本発明のフォージャサイト型ゼオライト（以下、ＦＡＵ型ゼオライトと云う）は、従来のように二次粒子を球状にしたものではなく、一次粒子の形状を球状に近づけて充填密度を高めたものである。本発明は該ＦＡＵ型ゼオライトとその製造方法を提供する。 The faujasite-type zeolite of the present invention (hereinafter referred to as FAU-type zeolite) does not have spherical secondary particles as in the prior art, but has primary particles with a spherical shape to increase the packing density. be. The present invention provides the FAU-type zeolite and a method for producing the same.
本発明は、以下の構成によって前記課題を解決した、ＦＡＵ型ゼオライトとその製造方法に関する。
〔１〕次式[１]によって示される一次粒子の球形度が０.６０以上であるＦＡＵ型ゼオライト。（式[１]において、Ｘは球形度、Ａは画像解析による測定面積、Ｂは画像機解析によって測定した長径を直径とした真円の面積）
Ｘ＝Ａ／Ｂ ・・・[１]
〔２〕ＦＡＵ型ゼオライトの製造方法であって、Ｓｉ源、Ａｌ源、および種結晶を含む水性混合液を調製する前駆体調製工程と、前記水性混合液を水熱処理してＦＡＵ型ゼオライト結晶を成長させる水熱処理工程を備え、上記種結晶を含む水性混合溶液のＳｉ源として遅溶解性シリカ粒子を用いることを特徴とする製造方法。
〔３〕上記遅溶解性シリカ粒子として、比表面積が１００m２/g以下のシリカ粒子を用いる上記[２]に記載する製造方法。
The present invention relates to an FAU-type zeolite and a method for producing the same, in which the above problems are solved by the following configurations.
[1] FAU-type zeolite whose primary particles have a sphericity of 0.60 or more, as represented by the following formula [1]. (In formula [1], X is sphericity, A is the area measured by image analysis, and B is the area of a perfect circle whose diameter is the major axis measured by image analysis)
X=A/B [1]
[2] A method for producing FAU-type zeolite, comprising a precursor preparation step of preparing an aqueous mixed solution containing a Si source, an Al source, and seed crystals, and a hydrothermal treatment of the aqueous mixed solution to produce FAU-type zeolite crystals. A production method comprising a step of growing hydrothermal treatment, and using slow-dissolving silica particles as the Si source of the aqueous mixed solution containing the seed crystals.
[3] The production method according to [2] above, wherein silica particles having a specific surface area of 100 m 2 /g or less are used as the slow-dissolving silica particles.
本発明のＦＡＵ型ゼオライトは、球に近い形状の一次粒子が多いので、単位容積あたりのゼオライト含有量が多い粉体を得ることができる。 Since the FAU-type zeolite of the present invention has many primary particles having a nearly spherical shape, it is possible to obtain a powder having a large zeolite content per unit volume.
〔ＦＡＵ型ゼオライト〕
本発明のＦＡＵ型ゼオライトは、画像解析により求めた一次粒子の球形度が０.６０以上の球に近い形状にしたＦＡＵ型ゼオライトである。ＦＡＵ型ゼオライトは、Ｓｉ、Ａｌ、Ｏを基本骨格元素とするフォージャサイト構造を有しており、このフォージャサイト構造はＸ線回析測定により得られた回折パターンから確認することができる。
[FAU-type zeolite]
The FAU-type zeolite of the present invention is a FAU-type zeolite having a sphericity of primary particles of 0.60 or more as determined by image analysis and having a shape close to a sphere. FAU-type zeolite has a faujasite structure with Si, Al, and O as basic skeleton elements, and this faujasite structure can be confirmed from a diffraction pattern obtained by X-ray diffraction measurement.
従来のＦＡＵ型ゼオライトは、結晶面がはっきりした八面体形状や六角板状の一次粒子を多く含むので、充填密度が低かった（比較例１、４）。これに対し、本発明のＦＡＵ型ゼオライトは、球形度が高い一次粒子を多く含むので、従来のＦＡＵ型ゼオライトに比較して充填密度が高い。球形度は、次式[１]に示すように、ゼオライト一次粒子の画像解析による測定面積Ａ、画像機解析によって測定した一次粒子の長径を直径とした真円の面積Ｂであるとき、真円の面積Ｂに対する測定面積Ａの比によって表される。
Ｘ＝Ａ／Ｂ ・・・[１]
（式[１]において、Ｘは球形度、Ａは画像解析による測定面積、Ｂは画像機解析によって測定した長径を直径とした真円の面積）
球形度の概念を図１に示す。球形度は１.０に近いほど真球に近い。
Conventional FAU-type zeolites contain many octahedral or hexagonal plate-shaped primary particles with clear crystal faces, and therefore have a low packing density (Comparative Examples 1 and 4). In contrast, the FAU-type zeolite of the present invention contains a large number of primary particles with a high degree of sphericity, and therefore has a higher packing density than conventional FAU-type zeolites. As shown in the following formula [1], the sphericity is the area A measured by image analysis of the zeolite primary particles, and the area B of the perfect circle whose diameter is the major axis of the primary particles measured by image analysis. is represented by the ratio of the measured area A to the area B of .
X=A/B [1]
(In formula [1], X is sphericity, A is the area measured by image analysis, and B is the area of a perfect circle whose diameter is the major axis measured by image analysis)
The concept of sphericity is shown in FIG. The closer the sphericity is to 1.0, the closer to a true sphere.
本発明のＦＡＵ型ゼオライトの一次粒子の球形度は平均値で０.６０以上であり、好ましくは０.６５以上、さらに好ましくは０.７０以上である。なお、本発明のＦＡＵ型ゼオライトは、その一次粒子の球形度を球に近くしたものであり、一次粒子の球形度の範囲は０.６０以上～１.０以下である。 The average sphericity of the primary particles of the FAU-type zeolite of the present invention is 0.60 or more, preferably 0.65 or more, and more preferably 0.70 or more. In the FAU-type zeolite of the present invention, the sphericity of the primary particles is made close to a sphere, and the sphericity of the primary particles ranges from 0.60 to 1.0.
本発明のＦＡＵ型ゼオライトの一次粒子径は、０.１μｍ～１０μｍ以下の範囲が好ましく、０.５μｍ～５μｍ以下の範囲がより好ましく、０．７μｍ～５μｍの範囲が特に好ましい。本発明のＦＡＵ型ゼオライトの一次粒子径がこれらの範囲にあると、充填密度がより高くなる。この一次粒子径は画像解析によって測定することができる。 The primary particle size of the FAU-type zeolite of the present invention is preferably 0.1 μm to 10 μm or less, more preferably 0.5 μm to 5 μm or less, and particularly preferably 0.7 μm to 5 μm. When the primary particle size of the FAU-type zeolite of the present invention is within these ranges, the packing density becomes higher. This primary particle size can be measured by image analysis.
本発明のＦＡＵ型ゼオライトの性状は、ＳｉとＡｌのモル比（ＳｉＯ２／Ａｌ２Ｏ３モル比：ＳＡＲ）によって大きく影響を受ける。例えば、ＳＡＲが低い（Ａｌの含有量が多い）ＦＡＵ型ゼオライトは、固体酸量が多くなる。また、耐水熱性はＳＡＲが高い（Ａｌの含有量が少ない）ほうが優れる。好ましいＳＡＲの範囲は、その用途によって異なる。例えば、洗剤のビルダー、水分吸着剤用途としては、ＳＡＲが低いＦＡＵ型ゼオライトが好ましく、具体的にはＳＡＲが５未満であることがより好ましく、ＳＡＲが２未満のＸ型ゼオライトであることが特に好ましい。ＶＯＣ吸着剤用途としては、ＳＡＲが３０以上のＦＡＵ型ゼオライトであることが好ましく、ＳＡＲが５０以上のＦＡＵ型ゼオライトであることがより好ましい。また、触媒用途としては、ＳＡＲが５以上のＦＡＵ型ゼオライト（Ｙ型ゼオライト）であることが好ましく、ＳＡＲが５～４００の範囲がより好ましく、５～２００の範囲が特に好ましい。 The properties of the FAU-type zeolite of the present invention are greatly affected by the molar ratio of Si to Al (SiO 2 /Al 2 O 3 molar ratio: SAR). For example, FAU-type zeolite with a low SAR (high Al content) has a large amount of solid acid. Moreover, the higher the SAR (the lower the Al content), the better the hydrothermal resistance. The preferred SAR range depends on the application. For example, for detergent builders and moisture adsorbent applications, FAU-type zeolite with a low SAR is preferable, specifically, an SAR of less than 5 is more preferable, and an X-type zeolite with an SAR of less than 2 is particularly preferable. preferable. For use as a VOC adsorbent, FAU-type zeolite with a SAR of 30 or more is preferable, and FAU-type zeolite with a SAR of 50 or more is more preferable. For catalytic applications, FAU-type zeolite (Y-type zeolite) having an SAR of 5 or more is preferable, an SAR of 5 to 400 is more preferable, and an SAR of 5 to 200 is particularly preferable.
本発明のＦＡＵ型ゼオライトは、陽イオン交換サイトを有しており、種々の陽イオンでイオン交換することができる。例えば、Ｎａ、Ｋ等のアルカリ金属、遷移金属、希土類、プロトン、アンモニウムイオン等の種々の陽イオンで交換することができ、交換する陽イオンによってＦＡＵ型ゼオライトの性状も変化する。例えば、洗剤や吸着剤用であれば、ＮａやＫ等のアルカリ金属でイオン交換されていることが好ましい。また、触媒用途であってその固体酸性質を利用する反応に用いる場合は、プロトンでイオン交換されていることが好ましく、固体酸性質の発現を阻害するアルカリの含有量は少ないほうがより好ましく、具体的にはＭ２Ｏ換算（Ｍはアルカリ金属）で２質量％以下であることが好ましく、１質量％以下であることがより好ましく、０.５質量％未満であることが特に好ましい。なお、陽イオン交換サイトの種類によってＦＡＵ型ゼオライトの充填密度も変化するので、本発明の効果を確認する際には、実施例および比較例において、陽イオン交換サイトの陽イオンを同一にして比較した。 The FAU-type zeolite of the present invention has cation exchange sites and can be ion-exchanged with various cations. For example, it can be exchanged with various cations such as alkali metals such as Na and K, transition metals, rare earth elements, protons and ammonium ions, and the properties of the FAU-type zeolite change depending on the cations to be exchanged. For example, for detergents and adsorbents, ion exchange with alkali metals such as Na and K is preferred. In addition, when used as a catalyst for a reaction that utilizes its solid acidity, it is preferably ion-exchanged with protons, and it is more preferable that the content of alkali that inhibits the expression of solid acidity is small. In terms of M 2 O (M is an alkali metal), the content is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably less than 0.5% by mass. Since the packing density of FAU-type zeolite varies depending on the type of cation exchange site, the effects of the present invention should be confirmed by comparing the cations of the cation exchange sites in the examples and comparative examples. did.
本発明のＦＡＵ型ゼオライトは、比表面積が６００ｍ２/ｇ以上であることが好ましい。ゼオライトは、一般的に、その骨格に由来する細孔構造によって極めて広い比表面積を有する。本発明のＦＡＵ型ゼオライトの比表面積が６００ｍ２/ｇより低い場合、骨格に由来する細孔構造が十分に発達していないおそれがあり、その固体酸量が低くなってしまうことがある。ＦＡＵ型ゼオライトの比表面積は高いほど好ましいが、その上限は９００ｍ２/ｇ以下であってもよい。より具体的には、本発明のＦＡＵ型ゼオライトの比表面積は６５０ｍ２/ｇ以上～７５０ｍ２/ｇ以下の範囲でもよい。 The FAU-type zeolite of the present invention preferably has a specific surface area of 600 m 2 /g or more. Zeolites generally have a very large specific surface area due to the pore structure derived from their framework. If the specific surface area of the FAU-type zeolite of the present invention is lower than 600 m 2 /g, the pore structure derived from the skeleton may not be sufficiently developed, and the solid acid content may become low. The higher the specific surface area of the FAU-type zeolite, the better, but the upper limit may be 900 m 2 /g or less. More specifically, the specific surface area of the FAU-type zeolite of the present invention may range from 650 m 2 /g to 750 m 2 /g.
本発明のＦＡＵ型ゼオライトは、その用途によって種々の形態に加工されて使用される。洗剤のビルダー用に使用される場合は、粉末のまま使用され、吸着剤用として使用される場合は、バインダー成分と共にペレット状、タブレット状に成型され、使用される。また、触媒用途として使用される場合は、活性金属成分、助触媒成分、担体成分、バインダー成分等と共に、球状、ペレット状、タブレット状に成型され、使用される。具体的な触媒用途としては、例えば、石油精製における流動接触分解用触媒や水素化分解用触媒として使用できる。 The FAU-type zeolite of the present invention is used after being processed into various forms depending on its use. When it is used as a detergent builder, it is used as a powder, and when it is used as an adsorbent, it is molded into pellets or tablets together with a binder component before use. When used as a catalyst, it is molded into a spherical, pellet, or tablet shape together with an active metal component, a cocatalyst component, a carrier component, a binder component, etc., and used. As a specific catalyst application, for example, it can be used as a fluid catalytic cracking catalyst or a hydrocracking catalyst in petroleum refining.
本発明のＦＡＵ型ゼオライトは球形度が高いので充填密度を高めることができる。具体的には、例えば、０.４g/cm３超～０.６g/cm３以下の充填密度を得ることができる。充填密度が高いＦＡＵ型ゼオライトは、単位容積当たりに充填されるＦＡＵ型ゼオライトの量が多くなるので、輸送コストの面で優れる。なお、本発明のＦＡＵ型ゼオライトには、バインダー成分が含まれないので、バインダー成分を添加して球状の二次粒子に成型されたものに比べて、単位容積当たりのＦＡＵ型ゼオライト量を多くすることができる。 Since the FAU-type zeolite of the present invention has a high sphericity, it is possible to increase the packing density. Specifically, for example, a packing density of more than 0.4 g/cm 3 to 0.6 g/cm 3 or less can be obtained. FAU-type zeolite with a high packing density is excellent in terms of transportation costs because the amount of FAU-type zeolite packed per unit volume is large. Since the FAU-type zeolite of the present invention does not contain a binder component, the amount of FAU-type zeolite per unit volume is increased compared to spherical secondary particles formed by adding a binder component. be able to.
〔ＦＡＵ型ゼオライトの製造方法〕
以下、本発明のＦＡＵ型ゼオライトの製造方法を具体的に説明する。
本発明の製造方法は、ＦＡＵ型ゼオライトの製造方法であって、Ｓｉ源、Ａｌ源、およびＦＡＵ型ゼオライト種結晶（以下、単に種結晶と云うことがある）を含む水性混合液を調製する前駆体調製工程と、前記水性混合液を水熱処理してＦＡＵ型ゼオライト結晶を成長させる水熱処理工程を備え、上記種結晶を含む水性混合溶液のＳｉ源として遅溶解性シリカ粒子を用いることを特徴とする製造方法である。
[Method for producing FAU-type zeolite]
Hereinafter, the method for producing the FAU-type zeolite of the present invention will be specifically described.
The production method of the present invention is a method for producing FAU-type zeolite, and is a precursor for preparing an aqueous mixed solution containing a Si source, an Al source, and FAU-type zeolite seed crystals (hereinafter sometimes simply referred to as seed crystals). and a hydrothermal treatment step of hydrothermally treating the aqueous mixed solution to grow FAU-type zeolite crystals, and slow-dissolving silica particles are used as the Si source of the aqueous mixed solution containing the seed crystals. It is a manufacturing method that
水性混合液は、例えば、種結晶を含むシード溶液に、Ｓｉ源である遅溶解性シリカ粒子と、Ａｌ源を加えて調製される。上記遅溶解性シリカ粒子とは溶解の遅いシリカ粒子を云い、例えば、比表面積１００m２/g以下のシリカ粒子が用いられる。因みに、例えば、比表面積４００m２/g以上のシリカ微粉末は溶解し易く（易溶解性）、シード溶液に加えるＳｉ源として適さない。 The aqueous mixed solution is prepared, for example, by adding slow-dissolving silica particles as a Si source and an Al source to a seed solution containing seed crystals. The slow-dissolving silica particles are slow-dissolving silica particles, and for example, silica particles having a specific surface area of 100 m 2 /g or less are used. Incidentally, for example, fine silica powder having a specific surface area of 400 m 2 /g or more is easily dissolved (easily soluble) and is not suitable as a Si source to be added to the seed solution.
ＦＡＵ型ゼオライトは、Ｓｉ、Ａｌ、Ｏを基本骨格元素とする結晶性アルミノシリケートの一種であり、その原料として骨格の構成元素であるＳｉを含む原料（Ｓｉ源）、Ａｌを含む原料（Ａｌ源）が用いられる。本発明の製造方法は、例えば、上記種結晶を含むシード溶液に、Ｓｉ源である遅溶解性シリカ粒子と、Ａｌ源を加えた水性混合液を調製し、該水性混合液を加熱処理してＦＡＵ型ゼオライト結晶を成長させる。ＦＡＵ型ゼオライトは、水溶液中でＳｉとＡｌとが溶解再析出を繰り返すことにより結晶成長することが知られている。本発明の製造方法は、該種結晶を成長させるＳｉ源として遅溶性シリカ粒子を用いることによって、ＳｉとＡｌの溶解再析出の速度を遅くし、従来のＦＡＵ型ゼオライトとは異なる球に近い形状の一次粒子を成長させる。 FAU-type zeolite is a type of crystalline aluminosilicate having Si, Al, and O as basic skeleton elements. ) is used. In the production method of the present invention, for example, an aqueous mixed solution is prepared by adding slowly soluble silica particles as a Si source and an Al source to the seed solution containing the seed crystals, and the aqueous mixed solution is heat-treated. FAU-type zeolite crystals are grown. FAU-type zeolite is known to undergo crystal growth through repeated dissolution and reprecipitation of Si and Al in an aqueous solution. The production method of the present invention slows the rate of dissolution and reprecipitation of Si and Al by using slowly soluble silica particles as the Si source for growing the seed crystals, and has a nearly spherical shape that is different from conventional FAU-type zeolites. to grow the primary particles of
〔前駆体調製工程〕
本発明の製造方法は、例えば、ＦＡＵ型ゼオライト種結晶を含むシード溶液に、Ｓｉ源である遅溶解性シリカ粒子と、Ａｌ源を加えた水性混合液を調製する前駆体調製工程を有する。該種結晶を含む溶液は、下記モル組成の水溶液を熟成して調製することができる。本発明の製造方法では該種結晶を含む水溶液をシード溶液と云う。
Ｎａ２Ｏ／Ａｌ２Ｏ３＝５～３２
ＳｉＯ２／Ａｌ２Ｏ３＝５～３０
Ｈ２Ｏ／Ａｌ２Ｏ３＝１００～２０００
[Precursor preparation step]
The production method of the present invention has, for example, a precursor preparation step of preparing an aqueous mixed solution by adding slow-dissolving silica particles as a Si source and an Al source to a seed solution containing FAU-type zeolite seed crystals. A solution containing the seed crystals can be prepared by aging an aqueous solution having the following molar composition. In the production method of the present invention, an aqueous solution containing the seed crystals is called a seed solution.
Na 2 O/Al 2 O 3 =5 to 32
SiO 2 /Al 2 O 3 =5 to 30
H 2 O/Al 2 O 3 =100-2000
シード溶液の調製に用いるＮａ源は、ＮａＯＨ、珪酸ナトリウム(水ガラス)、アルミン酸ナトリウム等である。 また、Ｓｉ源は、シリカゾル、シリカゲル、テトラアルコキシシランなどのアルコキシシラン、水ガラス等である。このシード溶液のＳｉ源は溶解し易い（易溶解性）ものを用いることができる。このＳi源は反応性の点から水ガラスが好ましい。なお、水ガラスのＮａ２Ｏ／ＳｉＯ２モル比は１～３.５のものが通常使用される。Ａｌ源は、アルミナゾル、アルミナゲル、アルミン酸ナトリウム、硫酸アルミニウム等である。これらのうちシリカとの反応性および結晶化の点からアルミン酸ナトリウムが好ましい。 The Na source used for preparing the seed solution is NaOH, sodium silicate (water glass), sodium aluminate and the like. Si sources include silica sol, silica gel, alkoxysilanes such as tetraalkoxysilane, and water glass. The Si source of this seed solution can be easily dissolved (easily soluble). This Si source is preferably water glass from the viewpoint of reactivity. Water glass having a Na 2 O/SiO 2 molar ratio of 1 to 3.5 is usually used. Al sources include alumina sol, alumina gel, sodium aluminate, aluminum sulfate, and the like. Among these, sodium aluminate is preferred from the viewpoint of reactivity with silica and crystallization.
アルミン酸ナトリウム、ＮａＯＨ、および水ガラス等の各原料を混合した後のＮａ２Ｏ／Ａｌ２Ｏ３モル比は、５～３２の範囲が好ましく、８～２４の範囲がより好ましい。Ｎａ２Ｏ／Ａｌ２Ｏ３モル比がこの範囲にあると、種結晶が生成しやすくなる。各原料を混合した後のＳｉＯ２／Ａｌ２Ｏ３モル比は、５～３０の範囲が好ましく、１０～２０の範囲がより好ましい。ＳｉＯ２／Ａｌ２Ｏ３モル比が５未満では、Ｐ型ゼオライトやグメリナイト等のＦＡＵ型ゼオライト以外の結晶が混在する場合があり、ＳｉＯ２／Ａｌ２Ｏ３モル比が３０を越えると、ＦＡＵ型ゼオライト結晶が得られ難くなる場合がある。 The Na 2 O/Al 2 O 3 molar ratio after mixing raw materials such as sodium aluminate, NaOH and water glass is preferably in the range of 5-32, more preferably in the range of 8-24. When the Na 2 O/Al 2 O 3 molar ratio is within this range, seed crystals are easily generated. The SiO 2 /Al 2 O 3 molar ratio after mixing the raw materials is preferably in the range of 5-30, more preferably in the range of 10-20. When the SiO 2 /Al 2 O 3 molar ratio is less than 5 , crystals other than FAU-type zeolite such as P-type zeolite and gmelinite may be mixed. type zeolite crystals may be difficult to obtain.
上記各原料を混合した後のＨ２Ｏ／Ａｌ２Ｏ３モル比は、１００～２０００の範囲が好ましく、１５０～１５００の範囲がより好ましい。Ｈ２Ｏ／Ａｌ２Ｏ３モル比が１００未満では、いびつな形状の一次粒子が得られやすくなる。Ｈ２Ｏ／Ａｌ２Ｏ３モル比が２０００を越えると、八面体や六角板状の一次粒子になりやすく、球状になり難くなる。 The H 2 O/Al 2 O 3 molar ratio after mixing the above raw materials is preferably in the range of 100-2000, more preferably in the range of 150-1500. If the H 2 O/Al 2 O 3 molar ratio is less than 100, primary particles with distorted shapes are likely to be obtained. If the H 2 O/Al 2 O 3 molar ratio exceeds 2,000, the primary particles are likely to be octahedral or hexagonal plate-like, and difficult to be spherical.
上記各原料を混合した水溶液を１０～７０℃、好ましくは２０～５０℃で熟成することによってシード溶液が得られる。熟成時間は熟成温度によっても異なるが、通常、１～２００時間である。 A seed solution is obtained by aging an aqueous solution obtained by mixing the above raw materials at 10 to 70°C, preferably 20 to 50°C. The aging time varies depending on the aging temperature, but is usually 1 to 200 hours.
上記シード溶液に、Ｓｉ源である遅溶解性シリカ粒子と、Ａｌ源、および水を加えて水性混合液を調製する。Ｓｉ源である遅溶解性シリカ粒子として、例えば、比表面積１００m２/g以下のシリカ粒子が用いられる。比表面積がこのように小さいシリカ粒子は溶解するのが遅い（遅溶解性）ので、次工程でのＳｉとＡｌの溶解再析出が緩やかに進み、球に近い一次粒子（ＦＡＵ型ゼオライト結晶の一次粒子）が得られる。Ａl源は前述の化合物を用いることができる。 Slowly soluble silica particles as a Si source, an Al source, and water are added to the above seed solution to prepare an aqueous mixed solution. Silica particles having a specific surface area of 100 m 2 /g or less, for example, are used as the slow-dissolving silica particles as the Si source. Silica particles with such a small specific surface area are slow to dissolve (slow solubility), so the dissolution and reprecipitation of Si and Al in the next step proceed slowly, resulting in primary particles close to spheres (primary particles of FAU-type zeolite crystals). particles) are obtained. Al source can use the above-mentioned compound.
上記Ｓｉ源、Ａｌ源、および種結晶を含む水性混合液のモル組成は以下の範囲が好ましい。水性混合液のモル組成がこの範囲にあると球に近い一次粒子が生成しやすくなる。
Ｎａ２Ｏ／Ａｌ２Ｏ３＝１～１０
ＳｉＯ２／Ａｌ２Ｏ３＝１～２０
Ｈ２Ｏ／Ａｌ２Ｏ３＝５０～６００
The molar composition of the aqueous mixture containing the Si source, Al source, and seed crystals is preferably in the following range. When the molar composition of the aqueous mixed solution is within this range, primary particles that are nearly spherical tend to form.
Na 2 O/Al 2 O 3 =1-10
SiO 2 /Al 2 O 3 =1 to 20
H 2 O/Al 2 O 3 =50-600
水性混合液のＮａ２Ｏ／Ａｌ２Ｏ３モル比は、１～１０の範囲が好ましく、１～５の範囲がより好ましい。また、水性混合液のＳｉＯ２／Ａｌ２Ｏ３モル比は、１～２０の範囲が好ましく、１～１０の範囲がより好ましい。更に、水性混合液のＨ２Ｏ／Ａｌ２Ｏ３モル比は、５０～６００の範囲が好ましく、８０～２００の範囲がより好ましい。水性混合液のモル組成がこれらの範囲にあると、球に近い形状の一次粒子が成長しやすい。 The Na 2 O/Al 2 O 3 molar ratio of the aqueous mixture is preferably in the range of 1-10, more preferably in the range of 1-5. The SiO 2 /Al 2 O 3 molar ratio of the aqueous mixture is preferably in the range of 1-20, more preferably in the range of 1-10. Furthermore, the H 2 O/Al 2 O 3 molar ratio of the aqueous mixture is preferably in the range of 50-600, more preferably in the range of 80-200. When the molar composition of the aqueous mixed solution is within these ranges, primary particles having a nearly spherical shape tend to grow.
前駆体調製工程として、ＦＡＵ型ゼオライト種結晶を含むシード溶液に、Ｓｉ源である遅溶解性シリカ粒子と、Ａｌ源を加えた水性混合液を調製する場合を示したが、該水性混合液の調製は種結晶を含むシード溶液にＳｉ源である遅溶解性シリカ粒子とＡｌ源を加える方法に限らない。 As the precursor preparation step, the case of preparing an aqueous mixed solution by adding slowly soluble silica particles as a Si source and an Al source to a seed solution containing FAU-type zeolite seed crystals was shown. The preparation is not limited to the method of adding slow-dissolving silica particles as a Si source and an Al source to a seed solution containing seed crystals.
〔水熱処理工程〕
この工程では、前述の前駆体調製工程で得られた水性混合液を加熱処理して、ＦＡＵ型ゼオライトの結晶化を進める。
[Hydrothermal treatment process]
In this step, the aqueous mixed solution obtained in the precursor preparation step described above is heat-treated to promote crystallization of the FAU-type zeolite.
加熱処理の方法は、オートクレーブ等を用いて加圧下で熱処理する方法、常圧下で熱処理する方法等の従来公知の方法を用いることができる。本発明の製造方法においては、Ｓｉ源の溶解速度を遅くするという観点から、常圧下で加熱処理する方法が好ましい。 As the heat treatment method, conventionally known methods such as heat treatment under pressure using an autoclave or the like and heat treatment under normal pressure can be used. In the production method of the present invention, the heat treatment under normal pressure is preferable from the viewpoint of slowing down the dissolution rate of the Si source.
加熱処理の温度は、ＦＡＵ型ゼオライトの結晶化を進める温度であればよく、５０℃～１００℃であることが好ましい。常圧下で加熱処理を行う場合は、８０℃～１００℃であることがより好ましい。加熱処理の時間は、加熱温度によっても左右されるが、２～２００時間であればよい。 The heat treatment temperature may be any temperature that promotes crystallization of the FAU-type zeolite, and is preferably 50°C to 100°C. When the heat treatment is performed under normal pressure, the temperature is more preferably 80°C to 100°C. The heat treatment time depends on the heating temperature, but may be 2 to 200 hours.
〔その他の工程〕
本発明の製造方法は、結晶化工程で得られたＦＡＵ型ゼオライトを含む溶液から溶媒を除去し、ＦＡＵ型ゼオライトを分離する工程を含むことができる。これは、乾燥、遠心分離、濾別等の従来公知の方法で容易に実施することができる。
[Other processes]
The production method of the present invention can include a step of removing the solvent from the solution containing the FAU-type zeolite obtained in the crystallization step to separate the FAU-type zeolite. This can be easily carried out by conventionally known methods such as drying, centrifugation, and filtering.
本発明の製造方法は、ＦＡＵ型ゼオライトをイオン交換する工程を含んでもよい。イオン交換したい陽イオンが溶解した水溶液にＦＡＵ型ゼオライトを懸濁し、適切な温度、時間で処理することによって容易にイオン交換することができる。陽イオンの種類にもよるが、イオン交換の温度は室温～９５℃の範囲が好ましく、イオン交換の時間は０.５～１０時間程度が好ましい。 The production method of the present invention may include a step of ion-exchanging the FAU-type zeolite. Ions can be easily exchanged by suspending FAU zeolite in an aqueous solution in which cations to be ion-exchanged are dissolved and treating the suspension at an appropriate temperature and time. Depending on the type of cation, the ion exchange temperature is preferably in the range of room temperature to 95° C., and the ion exchange time is preferably about 0.5 to 10 hours.
本発明の製造方法は、ＦＡＵ型ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比を高めるため、脱アルミニウム工程を含んでいてもよい。脱アルミニウムの方法は、従来公知の方法を用いることができる。例えば、酸処理、スチーム処理、ＥＤＴＡ処理等の方法でＦＡＵ型ゼオライトからアルミニウムを脱離させ、ＳｉＯ２／Ａｌ２Ｏ３モル比を２００程度まで高めることができる。 The production method of the present invention may include a dealumination step in order to increase the SiO 2 /Al 2 O 3 molar ratio of the FAU-type zeolite. A conventionally known method can be used for the dealumination method. For example, the SiO 2 /Al 2 O 3 molar ratio can be increased to about 200 by removing aluminum from the FAU-type zeolite by acid treatment, steam treatment, EDTA treatment, or the like.
以下、本発明の実施例を比較例と共に示す。なお、本発明は以下の実施例に限定されない。実施例および比較例では以下の方法によって比表面積、化学組成などの物性を測定した。 Examples of the present invention are shown below together with comparative examples. In addition, the present invention is not limited to the following examples. In Examples and Comparative Examples, physical properties such as specific surface area and chemical composition were measured by the following methods.
〔比表面積〕
不活性ガス雰囲気下において５００℃で１時間前処理を行った試料粉末を試料管に充填し、比表面積測定装置（日本ベル社製「MR-6」）を用いて、試料粉末の比表面積を測定した。具体的には、窒素ガス濃度３０vol％、ヘリウムガス濃度７０vol％の混合ガスを液体窒素で十分冷却した試料管に流通させて試料粉末に窒素を吸着させた後、試料管を２５℃にして試料粉末から脱離した窒素の量をＴＣＤ検出器で検出した。この脱離した窒素の量を窒素分子の断面積を用いて比表面積に換算することによって、試料粉末１ｇ当たりの比表面積を算出した。
〔Specific surface area〕
A sample tube is filled with the sample powder pretreated at 500°C for 1 hour in an inert gas atmosphere, and the specific surface area of the sample powder is measured using a specific surface area measuring device ("MR-6" manufactured by Bell Japan Co., Ltd.). It was measured. Specifically, a mixed gas with a nitrogen gas concentration of 30 vol% and a helium gas concentration of 70 vol% was passed through a sample tube sufficiently cooled with liquid nitrogen to adsorb nitrogen to the sample powder. The amount of nitrogen desorbed from the powder was detected with a TCD detector. The specific surface area per 1 g of sample powder was calculated by converting the amount of desorbed nitrogen into a specific surface area using the cross-sectional area of nitrogen molecules.
〔組成分析〕
蛍光Ｘ線装置(RIX-3000)を用いて、試料粉末のＳｉ、Ａｌおよびアルカリの各含有量を測定した。この測定結果から、ＳｉおよびＡｌの含有量を、それぞれＳｉＯ２、Ａｌ２Ｏ３モル量に換算し、ＳｉＯ２／Ａｌ２Ｏ３モル比を算出した。
[Composition analysis]
Using a fluorescent X-ray device (RIX-3000), each content of Si, Al and alkali in the sample powder was measured. From these measurement results, the contents of Si and Al were converted into SiO 2 and Al 2 O 3 molar amounts, respectively, and the SiO 2 /Al 2 O 3 molar ratio was calculated.
〔強熱減量〕
試料粉末を１０００℃で１時間加熱した際の重量減少から、以下の式で強熱減量を算出した。
強熱減量(％)＝〔（加熱前の試料粉末の重量(ｇ)－加熱後の試料粉末の重量(ｇ)〕／加熱前の試料粉末の重量(ｇ)
[Ignition loss]
From the weight loss when the sample powder was heated at 1000° C. for 1 hour, the ignition loss was calculated by the following formula.
Ignition loss (%) = [(weight of sample powder before heating (g) - weight of sample powder after heating (g)] / weight of sample powder before heating (g)
〔一次粒子の球形度〕
試料粉末を試料板に分散させた後、走査型電子顕微鏡（日本電子社製：JSM-7600S）を用いて一次粒子の形状を観察した（加速電圧１.０kV、倍率１万～５万倍）。得られた画像から無作為に５０個の一次粒子を選出し、画像解析によって測定した一次粒子の面積をＡ、画像解析によって測定した一次粒子の長径を直径とした真円の面積をＢとし、下記式[１]で球形度Ｘを算出した。また、一次粒子径はこの長径の平均値とした。
一次粒子の球形度(Ｘ)＝Ａ／Ｂ ・・・[１]
[Sphericality of primary particles]
After dispersing the sample powder on the sample plate, the shape of the primary particles was observed using a scanning electron microscope (manufactured by JEOL Ltd.: JSM-7600S) (accelerating voltage: 1.0 kV, magnification: 10,000 to 50,000 times). . 50 primary particles are randomly selected from the obtained image, the area of the primary particles measured by image analysis is A, the area of the perfect circle whose diameter is the major axis of the primary particles measured by image analysis is B, The sphericity X was calculated by the following formula [1]. In addition, the primary particle diameter was taken as the average value of the major diameters.
Sphericality of primary particles (X) = A/B [1]
〔充填密度〕
試料粉末を２００mlのメスシリンダーに１００mlの目盛になるまで充填し、その後約１cmの高さから上下に１００回タップした。該メスシリンダーに充填した試料粉末の重量をＴ(ｇ)、タップ後の体積をＶ１(cm３)とし、下記式[２]で充填密度(ρ)を算出した。
充填密度(ρ)＝Ｔ／Ｖ１ ・・・[２]
[Filling density]
The sample powder was filled into a graduated cylinder of 200 ml to the graduation of 100 ml, and then tapped up and down 100 times from a height of about 1 cm. Assuming that the weight of the sample powder filled in the graduated cylinder was T (g) and the volume after tapping was V1 (cm 3 ), the filling density (ρ) was calculated by the following formula [2].
Packing density (ρ) = T/V1 [2]
〔Ｘ線回折測定〕
試料粉末を乳鉢で粉砕し、試料板にセットした。これを以下の条件でＸ線回折測定し、得られたＸＲＤパターンからフォージャサイト構造の有無を確認した。
装置 ：株式会社リガク製MiniFlex
操作軸 ：２θ／θ
線源 ：ＣｕＫα
測定方法 ：連続式
電圧 ：４０ｋＶ
電流 ：１５ｍＡ
開始角度 ：２θ＝５°
終了角度 ：２θ＝５０°
サンプリング幅：０.０２０°
スキャン速度 ：１０.０００［°/min］
＜判断基準＞
上記測定により得られるＸ線回折パターンがフォージャサイト構造のミラー指数に帰属されるピークをすべて有している場合、フォージャサイト構造を有していると判断した。なお、各ピークのピーク位置は、それぞれ２θ＝±０.２°程度の誤差を含みうる。
[X-ray diffraction measurement]
The sample powder was pulverized in a mortar and set on a sample plate. This was subjected to X-ray diffraction measurement under the following conditions, and the presence or absence of a faujasite structure was confirmed from the obtained XRD pattern.
Equipment: MiniFlex manufactured by Rigaku Corporation
Operation axis: 2θ/θ
Radiation source: CuKα
Measurement method: Continuous type Voltage: 40 kV
Current: 15mA
Start angle: 2θ=5°
End angle: 2θ=50°
Sampling width: 0.020°
Scan speed: 10.000 [°/min]
<Judgment Criteria>
When the X-ray diffraction pattern obtained by the above measurement had all the peaks attributed to the Miller index of the faujasite structure, it was judged to have a faujasite structure. Note that the peak position of each peak may contain an error of about 2θ=±0.2°.
〔実施例１〕
＜前駆体調製工程＞
Ｎａ含有量(Na２O換算)１７質量％、Ａｌ含有量(Al２O３換算）２２質量％のアルミン酸ナトリウム水溶液０.２９kgを準備した。このアルミン酸ナトリウム水溶液を、２１.７質量％の水酸化ナトリウム水溶液２.４kgに加えた。この溶液を撹拌しながら、Ｓｉ濃度(SiO２換算)２４質量％の３号水ガラス２.３kgに加えて、１時間撹拌した後、３０℃で１２時間静置してシード溶液を調製した。シード溶液のモル組成は、１６Ｎａ２Ｏ：Ａｌ２Ｏ３：１５ＳｉＯ２：３３０Ｈ２Ｏであった。
[Example 1]
<Precursor preparation step>
0.29 kg of a sodium aluminate aqueous solution having a Na content (in terms of Na 2 O) of 17% by mass and an Al content (in terms of Al 2 O 3 ) of 22% by mass was prepared. This aqueous sodium aluminate solution was added to 2.4 kg of 21.7% by weight aqueous sodium hydroxide solution. While stirring, this solution was added to 2.3 kg of No. 3 water glass having a Si concentration of 24% by mass (in terms of SiO 2 ), stirred for 1 hour, and then allowed to stand at 30° C. for 12 hours to prepare a seed solution. The molar composition of the seed solution was 16Na2O : Al2O3 : 15SiO2 : 330H2O .
Ｓｉ源として、Ｓｉ濃度(SiO２換算)２４質量％の３号水ガラス１８ｋｇ、および遅溶解性シリカ粒子（デンカ株式会社製溶融シリカUFP-30、比表面積３７m２/g）４.５kgと水１６.８kgとを混合した。この溶液に上記シード溶液２.５kgを加えた後、Ａｌ源として、Ｎａ含有量(Na２O換算)７.７質量％およびＡｌ含有量(Al２O３換算)２２質量％のアルミン酸ナトリウム８.１kgを加えて、水性混合液を調製した。この水性混合液のモル組成は、２.８Ｎａ２Ｏ：Ａｌ２Ｏ３：８.６ＳｉＯ２：１１３Ｈ２Ｏであった。 As a Si source, 18 kg of No. 3 water glass with a Si concentration (in terms of SiO 2 ) of 24% by mass, and 4.5 kg of slowly soluble silica particles (Denka Co., Ltd. fused silica UFP-30, specific surface area 37 m 2 /g) and water. 16.8 kg were mixed. After adding 2.5 kg of the above seed solution to this solution, sodium aluminate having a Na content (in terms of Na2O ) of 7.7 mass% and an Al content ( in terms of Al2O3 ) of 22 mass% was used as an Al source. 8.1 kg was added to prepare an aqueous mixture. The molar composition of this aqueous mixture was 2.8 Na 2 O:Al 2 O 3 :8.6 SiO 2 :113 H 2 O.
＜水熱処理工程＞
上記水性混合液を室温で３時間熟成させた後、９５℃で３５時間加熱処理して、ゼオライト結晶を成長させた。その後、該ゼオライト結晶を濾別し、これを水で洗浄した後、１３０℃で２０時間乾燥した。得られたゼオライト結晶について、Ｘ線回折測定によってフォージャサイト構造を有していることを確認した。さらに前述の測定を行った。この結果を表１に示す。また、このＦＡＵ型ゼオライトの電子顕微鏡写真を図２に示す。
<Hydrothermal treatment process>
After the aqueous mixture was aged at room temperature for 3 hours, it was heat-treated at 95° C. for 35 hours to grow zeolite crystals. Thereafter, the zeolite crystals were separated by filtration, washed with water, and dried at 130° C. for 20 hours. The obtained zeolite crystal was confirmed to have a faujasite structure by X-ray diffraction measurement. In addition, the measurements described above were performed. The results are shown in Table 1. An electron micrograph of this FAU-type zeolite is shown in FIG.
〔実施例２〕
実施例１で得られたＦＡＵ型ゼオライト５kgを６０℃の水５０Ｌに加え、更に硫酸アンモニウムを１.４kg加えて懸濁液を調製した。この懸濁液を７０℃で１時間撹拌した後、ＦＡＵ型ゼオライトを濾別した。このＦＡＵ型ゼオライトを水で洗浄した後、６０℃の水５０Ｌに硫酸アンモニウム１.４kgを溶解した硫酸アンモニウム溶液で洗浄し、更に６０℃の水５０Ｌで洗浄した。洗浄後のＦＡＵ型ゼオライトを１３０℃で２０時間乾燥して、アンモニウムイオンでイオン交換されたＦＡＵ型ゼオライトを得た。このＦＡＵ型ゼオライトについて、前述の測定を行った。この結果を表１に示す。
[Example 2]
5 kg of the FAU-type zeolite obtained in Example 1 was added to 50 L of water at 60° C., and 1.4 kg of ammonium sulfate was further added to prepare a suspension. After this suspension was stirred at 70° C. for 1 hour, the FAU zeolite was filtered off. After washing the FAU-type zeolite with water, it was washed with an ammonium sulfate solution prepared by dissolving 1.4 kg of ammonium sulfate in 50 L of water at 60°C, and further washed with 50 L of water at 60°C. The washed FAU-type zeolite was dried at 130° C. for 20 hours to obtain an FAU-type zeolite ion-exchanged with ammonium ions. The above-described measurements were performed on this FAU-type zeolite. The results are shown in Table 1.
〔実施例３〕
実施例２で得られたＦＡＵ型ゼオライトを、飽和水蒸気雰囲気中にて６７０℃で１時間焼成して一回目の水蒸気処理を行った。このＦＡＵ型ゼオライト４.０kgを、温度６０℃の４００Ｌの水に加えた後、硫酸アンモニウム５.６kgを加えて懸濁液を調製した。この懸濁液を９０℃で１時間撹拌した後にＦＡＵ型ゼオライトを濾別した。これを温度６０℃の水２４０Ｌで洗浄し、１１０℃で２０時間乾燥して、ＳｉＯ２／Ａｌ２Ｏ３モル比を高めたＦＡＵ型ゼオライト結晶を得た。さらに、このＦＡＵ型ゼオライト結晶を飽和水蒸気雰囲気中にて６３０℃で２時間焼成して二回目の水蒸気処理を行った。このＦＡＵ型ゼオライト結晶１.０kgを室温の水１５Ｌに加え、２５質量％の硫酸１.４ｋｇを徐々に加えた。硫酸を全量加えた後に、７５℃に昇温して４時間撹拌し、ＦＡＵ型ゼオライトを濾別して、イオン交換水６０Ｌで洗浄した。洗浄後のＦＡＵ型ゼオライトを１１０℃で２０時間乾燥し、ＳｉＯ２／Ａｌ２Ｏ３モル比をさらに高めたＦＡＵ型ゼオライト結晶を得た。このＦＡＵ型ゼオライト結晶について、前述の測定を行った。この結果を表１に示す。
[Example 3]
The FAU-type zeolite obtained in Example 2 was calcined in a saturated steam atmosphere at 670° C. for 1 hour to perform the first steam treatment. After adding 4.0 kg of this FAU-type zeolite to 400 L of water at a temperature of 60° C., 5.6 kg of ammonium sulfate was added to prepare a suspension. After this suspension was stirred at 90° C. for 1 hour, the FAU zeolite was filtered off. This was washed with 240 L of water at a temperature of 60° C. and dried at 110° C. for 20 hours to obtain FAU-type zeolite crystals with an increased SiO 2 /Al 2 O 3 molar ratio. Further, the FAU-type zeolite crystals were calcined in a saturated steam atmosphere at 630° C. for 2 hours to perform a second steam treatment. 1.0 kg of this FAU-type zeolite crystal was added to 15 L of water at room temperature, and 1.4 kg of 25 mass % sulfuric acid was gradually added. After adding the entire amount of sulfuric acid, the mixture was heated to 75° C. and stirred for 4 hours, and the FAU zeolite was separated by filtration and washed with 60 L of ion-exchanged water. The washed FAU-type zeolite was dried at 110° C. for 20 hours to obtain FAU-type zeolite crystals with a further increased SiO 2 /Al 2 O 3 molar ratio. The above-described measurements were performed on this FAU-type zeolite crystal. The results are shown in Table 1.
〔比較例１：市販のＦＡＵ型ゼオライト〕
市販されているＦＡＵ型ゼオライト（ゼオリスト社製CBV100）を用いた。このＦＡＵ型ゼオライトについて、前述の測定を行った。結果を表１に示す。また、このＦＡＵ型ゼオライトの電子顕微鏡写真を図３に示す。
[Comparative Example 1: Commercially available FAU-type zeolite]
A commercially available FAU-type zeolite (CBV100 manufactured by Zeolist) was used. The above-described measurements were performed on this FAU-type zeolite. Table 1 shows the results. An electron micrograph of this FAU-type zeolite is shown in FIG.
〔比較例２：易溶解性のシリカ粒子を使用〕
シード溶液に加えるＳｉ源として、遅溶解性シリカに代えて、溶解し易いシリカ粒子を用いた以外は実施例１と同様の方法でＦＡＵ型ゼオライトを製造した。この溶解し易いシリカ粒子として日本アエロジル社製品（AerosilTM380、比表面積405m２/g）を用いた。このＦＡＵ型ゼオライトについて、前述の測定を行った。この結果を表１に示す。また、このＦＡＵ型ゼオライトの電子顕微鏡写真を図４に示す。
[Comparative Example 2: Using easily soluble silica particles]
FAU-type zeolite was produced in the same manner as in Example 1, except that easily soluble silica particles were used instead of slow-dissolving silica as the Si source added to the seed solution. A product of Nippon Aerosil Co., Ltd. (Aerosil TM 380, specific surface area 405 m 2 /g) was used as the easily soluble silica particles. The above-described measurements were performed on this FAU-type zeolite. The results are shown in Table 1. An electron micrograph of this FAU-type zeolite is shown in FIG.
〔比較例３：原料溶液にシリカ粒子を加えない〕
Ｈ２ＳＯ４濃度２０.３質量％およびＡｌ濃度(Al２O３換算)７.０質量％の硫酸アルミニウム水溶液７.４kgに、Ｓｉ濃度(SiO２換算)２４質量％の３号水ガラス３５kgをゆっくり加えた後に、Ｎａ含有量(Na２O換算)７.７質量％およびＡｌ含有量(Al２O３換算)２２質量％のアルミン酸ナトリウム５.３kgを加え、１０分間撹拌して原料溶液を調製した。この原料溶液に実施例１の方法で得られたシード溶液２.４kgを加え、均一になるまで撹拌混合して水性混合液を調製した。この水性混合液のモル組成は、２.８Ｎａ２Ｏ：Ａｌ２Ｏ３：８.６ＳｉＯ２：１１３Ｈ２Ｏであった。以降の工程は実施例１と同様の方法で、ＦＡＵ型ゼオライトを調製した。このＦＡＵ型ゼオライトについて、前述の測定を行った。この結果を表１に示す。また、このＦＡＵ型ゼオライトの電子顕微鏡写真を図５に示す。
[Comparative Example 3: No silica particles are added to the raw material solution]
35 kg of No. 3 water glass with a Si concentration (calculated as SiO 2 ) of 24% by weight was added to 7.4 kg of an aluminum sulfate aqueous solution having an H 2 SO 4 concentration of 20.3% by weight and an Al concentration of 7.0% by weight (calculated as Al 2 O 3 ). was slowly added, then 5.3 kg of sodium aluminate having a Na content (in terms of Na 2 O) of 7.7% by mass and an Al content (in terms of Al 2 O 3 ) of 22% by mass was added, and stirred for 10 minutes to obtain the starting material. A solution was prepared. To this raw material solution, 2.4 kg of the seed solution obtained by the method of Example 1 was added and mixed with stirring until uniform to prepare an aqueous mixed solution. The molar composition of this aqueous mixture was 2.8 Na 2 O:Al 2 O 3 :8.6 SiO 2 :113 H 2 O. Subsequent steps were the same as in Example 1 to prepare FAU-type zeolite. The above-described measurements were performed on this FAU-type zeolite. The results are shown in Table 1. An electron micrograph of this FAU-type zeolite is shown in FIG.
〔比較例４：市販のＦＡＵ型ゼオライト〕
市販されているＦＡＵ型ゼオライト（ゼオリスト社製CBV712）を用いた。このＦＡＵ型ゼオライトについて、前述の測定を行った。この結果を表１に示す。
[Comparative Example 4: Commercially available FAU-type zeolite]
A commercially available FAU-type zeolite (CBV712 manufactured by Zeolist) was used. The above-described measurements were performed on this FAU-type zeolite. The results are shown in Table 1.
シード溶液に加えるＳｉ源として遅溶解性シリカ粒子（比表面積３７m２/g）を用いて調製された実施例１のＦＡＵ型ゼオライトは、一次粒子が丸みを帯びているものが多く（図２）、その球形度は０.７５である。一方、遅溶解性シリカ粒子に代えて易溶解性シリカ粒子（比表面積405m２/g）を用いて調製された比較例２のＦＡＵ型ゼオライトの一次粒子は殆どが八面体形状であり、一部に六角板状の一次粒子も含まれている（図４）。また、シード溶液に加えるＳｉ源としてシリカ粒子を用いずに調製された比較例３のＦＡＵ型ゼオライトは、六角板状の一次粒子が多く、一部に八面体形状の一次粒子も含まれている（図５）。比較例１の市販のＦＡＵ型ゼオライトも比較例３のＦＡＵ型ゼオライトに近い形状の一次粒子を含んでいる（図３）。このように、本発明のＦＡＵ型ゼオライトは、従来のＦＡＵ型ゼオライトの一次粒子よりも球形度が高く、球に近いことが確認された。 In the FAU-type zeolite of Example 1, which was prepared using slow-dissolving silica particles (specific surface area: 37 m 2 /g) as the Si source added to the seed solution, many of the primary particles were rounded (Fig. 2). , whose sphericity is 0.75. On the other hand, most of the primary particles of FAU-type zeolite in Comparative Example 2, which was prepared using easily soluble silica particles (specific surface area: 405 m 2 /g) instead of slowly soluble silica particles, had an octahedral shape, and some also contains hexagonal plate-like primary particles (Fig. 4). In addition, the FAU-type zeolite of Comparative Example 3, which was prepared without using silica particles as the Si source added to the seed solution, has many hexagonal plate-shaped primary particles, and some octahedral primary particles are also included. (Fig. 5). The commercially available FAU-type zeolite of Comparative Example 1 also contains primary particles having a shape similar to that of the FAU-type zeolite of Comparative Example 3 (FIG. 3). Thus, it was confirmed that the FAU-type zeolite of the present invention has a higher degree of sphericity than the primary particles of conventional FAU-type zeolite, and is closer to a sphere.
ＦＡＵ型ゼオライトの充填密度は、そのＳｉＯ２／Ａｌ２Ｏ３モル比、カチオンの種類、水分含有量が影響すると考えられることから、これらが同程度となるように調製したものを用いてその充填密度を比較した。一次粒子の球形度が０.６０以上である実施例１のＦＡＵ型ゼオライトは、その球形度が０.６０未満である比較例１、２のＦＡＵ型ゼオライトと比較して、充填密度が１０％以上高い。同様に、実施例２と比較例３のＦＡＵ型ゼオライトを比較しても、充填密度が１０以上高い。更に、実施例３と比較例４についても同様である。
The packing density of FAU-type zeolite is considered to be affected by its SiO 2 /Al 2 O 3 molar ratio, the type of cation, and the water content. Density was compared. The FAU-type zeolite of Example 1 whose primary particles have a sphericity of 0.60 or more has a packing density of 10% compared to the FAU-type zeolites of Comparative Examples 1 and 2 whose sphericity is less than 0.60. More expensive. Similarly, even when the FAU-type zeolites of Example 2 and Comparative Example 3 are compared, the packing density is higher by 10 or more. Further, the same applies to Example 3 and Comparative Example 4.
Claims (3)
（式[１]において、Ｘは球形度、Ａは画像解析による測定面積、Ｂは画像機解析によって測定した長径を直径とした真円の面積）
Ｘ＝Ａ／Ｂ ・・・[１] FAU-type zeolite whose primary particles have a sphericity of 0.60 or more, as represented by the following formula [1].
(In formula [1], X is sphericity, A is the area measured by image analysis, and B is the area of a perfect circle whose diameter is the major axis measured by image analysis)
X=A/B [1]
3. The production method according to claim 2, wherein silica particles having a specific surface area of 100 m< 2 >/g or less are used as the slow-dissolving silica particles.
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