JPH04342416A - Production of a type zeolite - Google Patents
Production of a type zeoliteInfo
- Publication number
- JPH04342416A JPH04342416A JP14543691A JP14543691A JPH04342416A JP H04342416 A JPH04342416 A JP H04342416A JP 14543691 A JP14543691 A JP 14543691A JP 14543691 A JP14543691 A JP 14543691A JP H04342416 A JPH04342416 A JP H04342416A
- Authority
- JP
- Japan
- Prior art keywords
- ion concentration
- ion
- aqueous solution
- mol
- liter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 27
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 17
- 239000010457 zeolite Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 aluminate ion Chemical class 0.000 claims abstract description 54
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 abstract description 26
- 239000013078 crystal Substances 0.000 abstract description 25
- 239000000243 solution Substances 0.000 abstract description 16
- 239000012213 gelatinous substance Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- BFRXZIMAUMUZJH-UHFFFAOYSA-M [OH-].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] Chemical compound [OH-].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] BFRXZIMAUMUZJH-UHFFFAOYSA-M 0.000 description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005216 hydrothermal crystallization Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、気体分子や低分子有機
化合物の吸着材等として有用なＡ型ゼオライトを効率良
く製造することのできる方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for efficiently producing type A zeolite, which is useful as an adsorbent for gas molecules and low-molecular organic compounds.
【０００２】0002
【従来の技術】Ａ型ゼオライトは、通常、アルミノシリ
ケートゲルを熱水結晶化（ｈｙｄｒｏｔｈｅｒｍａｌ
ｃｒｉｓｔａｌｌｉｚａｔｉｏｎ）することによって製
造される。即ちアルミノシリケートゲルは、たとえば高
塩基性アルミン酸ナトリウム水溶液にシリカゾル水溶液
を加え、あるいは高塩基性珪酸ナトリウム水溶液に水酸
化アルミニウム粉末を加えて混合することにより簡単に
得ることができ、生成したアルミノシリケートゲルを加
熱すると、ゲル中でＡ型ゼオライトの結晶核生成と結晶
成長が徐々に進行し、その全部もしくは大部分が結晶質
のＡ型ゼオライトに変わっていく。[Prior Art] Type A zeolite is usually produced by hydrothermal crystallization of aluminosilicate gel.
crystallization). That is, aluminosilicate gel can be easily obtained by, for example, adding a silica sol aqueous solution to a highly basic aqueous sodium aluminate solution, or adding aluminum hydroxide powder to a highly basic aqueous sodium silicate solution and mixing. When the gel is heated, crystal nucleation and crystal growth of A-type zeolite gradually progress in the gel, and all or most of it changes to crystalline A-type zeolite.
【０００３】ところでＡ型ゼオライトは、熱力学的にみ
ると準安定相結晶であるため、熱水結晶化の際に必要以
上の熱と時間を与えると安定相結晶であるヒドロキシソ
ーダライトにまで変化してしまう。従ってその製造に当
たっては、いかにして安定相結晶への変化を抑えて準安
定相結晶状態で止めるか、という点に主眼を置いた研究
が行なわれている（特公昭５６−３７１６６号，特開昭
５７−３７１３ 号，同５８−２１３６２６ 号等）。By the way, A-type zeolite is a metastable phase crystal from a thermodynamic point of view, so if more heat and time than necessary are applied during hydrothermal crystallization, it will change to hydroxysodalite, a stable phase crystal. Resulting in. Therefore, in manufacturing them, research is being conducted with a focus on how to suppress the change to a stable phase crystal and stop it in a metastable phase crystal state (Japanese Patent Publication No. 56-37166, No. 57-3713, No. 58-213626, etc.).
【０００４】Ａ型ゼオライトの原料としてアルミノシリ
ケートゲルを使用するのは、ゲル状態で結晶化を進める
ことによって、結晶成長時におけるアルミン酸イオンと
珪酸イオンの自由な移動に制限を与え、両イオンの自由
な再配列を防止することによって、必要以上の熱エネル
ギーが加わった場合でも安定相への相変態が起こらない
様にすることを意図したものである。[0004] The use of aluminosilicate gel as a raw material for A-type zeolite is achieved by promoting crystallization in a gel state, which limits the free movement of aluminate ions and silicate ions during crystal growth. By preventing free rearrangement, it is intended to prevent phase transformation to a stable phase from occurring even when excessive thermal energy is applied.
【０００５】しかしながらこの様な方法を採用した場合
でも、結晶化工程で過剰の熱エネルギーが加わると（温
度が高過ぎたり、反応時間が長過ぎると）、各イオンの
動きが活発となって安定相への再配列を起こし、ヒドロ
キシソーダライトが生成してくる。またゲルネットワー
ク構造が強固過ぎてゲル内における各イオンの移動が過
度に制限されると、結晶化反応自体が起こり難くなって
準安定相結晶の生成率が上がらなくなる。そこで従来は
できるだけ穏和な条件下で選択的にＡ型ゼオライトを生
成させるための要件として、アルミノシリケートゲル生
成時におけるナトリウムイオン、アルミン酸イオン、珪
酸イオンの各濃度を調整し、ゲルネットワーク構造の強
さを抑制する方向で研究が進められている。However, even when such a method is adopted, if excessive thermal energy is applied during the crystallization process (if the temperature is too high or the reaction time is too long), the movement of each ion becomes active and the stability becomes unstable. Phase rearrangement occurs and hydroxysodalite is produced. Furthermore, if the gel network structure is too strong and the movement of each ion within the gel is excessively restricted, the crystallization reaction itself becomes difficult to occur and the production rate of metastable phase crystals does not increase. Therefore, in order to selectively produce A-type zeolite under as mild conditions as possible, conventionally, the concentrations of sodium ions, aluminate ions, and silicate ions were adjusted during aluminosilicate gel production to strengthen the gel network structure. Research is underway in the direction of suppressing this.
【０００６】ゲルネットワーク構造の強さは、アルミノ
シリケートゲル生成時における水酸化ナトリウム濃度が
高いほど低下することが知られているが、高ｐＨ領域で
の原料溶液は安定でありアルミノシリケート系化合物の
析出は起こらない。そこでアルミノシリケート系化合物
の析出限界領域近傍のｐＨでアルミン酸イオンと珪酸イ
オンの比を適正に調整することによって、比較的穏和な
条件下で結晶化を行なう方法も知られている［Ｎｅｗ
Ｄｅｖｅｌｏｐｍｅｎｔｓ ｉｎＺｅｏｌｉｔｅ Ｓｃ
ｉｅｎｃｅ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ，Ｐｒｏｃ
ｅｅｄｉｎｇｓ ｏｆ ７ｔｈ Ｉｎｔｅｒｎａｔｉｏ
ｎａｌ Ｚｅｏｌｉｔｅ Ｃｏｎｆｅｒｅｎｃｅ Ｔｏ
ｋｙｏ，Ａｕｇｕｓｔ１７ 〜２２（１９８６）］ 。It is known that the strength of the gel network structure decreases as the sodium hydroxide concentration increases during aluminosilicate gel formation, but the raw material solution in a high pH region is stable and the strength of the aluminosilicate compound is No precipitation occurs. Therefore, a method is known in which crystallization is performed under relatively mild conditions by appropriately adjusting the ratio of aluminate ions and silicate ions at a pH near the precipitation limit region of aluminosilicate compounds [New
Developments in Zeolite Sc
ience and Technology,Proc.
eedings of 7th International
nal Zeolite Conference To
kyo, August 17-22 (1986)].
【０００７】この方法は、前述の様にアルミノシリケー
トゲルを原料として熱水結晶化する方法とは異なり、高
ｐＨ域で結晶化を行なうのでゲルネットワーク構造が弱
く、穏和な条件下でも結晶化が進行する。しかしながら
この方法でも、ゲルネットワーク強度が弱い分だけアル
ミン酸イオンと珪酸イオンは動き易くなり、安定相結晶
の生成は避けられない。しかもアルミノシリケート系化
合物の析出限界領域近傍という微妙な条件下において競
合する準安定相結晶析出反応と安定相結晶析出反応の両
反応を、原料溶液の各イオン濃度や加熱温度、加熱時間
のみで制御することは困難であり、準安定相結晶析出反
応の選択性を十分に高めることは容易でない。[0007] This method differs from the method of hydrothermal crystallization using aluminosilicate gel as a raw material, as described above, because crystallization is performed in a high pH range, the gel network structure is weak, and crystallization does not occur even under mild conditions. proceed. However, even with this method, aluminate ions and silicate ions move easily due to the weak gel network strength, and the formation of stable phase crystals is unavoidable. Moreover, both the metastable phase crystal precipitation reaction and stable phase crystal precipitation reaction, which compete under delicate conditions near the precipitation limit region of aluminosilicate compounds, can be controlled only by the concentration of each ion in the raw material solution, heating temperature, and heating time. It is difficult to do so, and it is not easy to sufficiently increase the selectivity of the metastable phase crystal precipitation reaction.
【０００８】[0008]
【発明が解決しようとする課題】本発明は以上の様な従
来技術の問題点に着目してなされたものであって、その
目的は、安定相結晶であるヒドロキシソーダライトを生
成させることなく、準安定相結晶であるＡ型ゼオライト
を効率良く製造することのできる方法を提供しようとす
るものである。SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art as described above, and its purpose is to solve the problem without producing hydroxysodalite, which is a stable phase crystal. The present invention aims to provide a method that can efficiently produce A-type zeolite, which is a metastable phase crystal.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決すること
のできた本発明に係る製造法の構成は、アルミン酸イオ
ン濃度が０．１ 〜０．５ モル／リットル、ナトリウ
ムイオン濃度が０．０３〜３モル／リットルである水溶
液と、珪酸イオン濃度が０．０２〜０．１ モル／リッ
トル、ナトリウムイオン濃度が０．０５〜４モル／リッ
トルである水溶液とを、夫々調製しておき、これらを６
０℃未満の温度でゲル状物が生成しない様に混合し、次
いで６０〜１００℃に加熱してＡ型ゼオライトを析出さ
せるところに要旨を有するものである。このとき、各水
溶液のイオン濃度は、混合状態における各イオン濃度が
アルミン酸イオン濃度：０．０５〜０．１５モル／リッ
トル，珪酸イオン濃度：０．０１〜０．０５モル／リッ
トル，ナトリウムイオン濃度：０．０５〜３．０ モル
／リットルとなる様に調整することにより、Ａ型ゼオラ
イトをより効率良く得ることができる。[Means for Solving the Problems] The structure of the production method according to the present invention that can solve the above problems is that the aluminate ion concentration is 0.1 to 0.5 mol/liter and the sodium ion concentration is 0.03. An aqueous solution having a concentration of ~3 mol/liter, an aqueous solution having a silicate ion concentration of 0.02 to 0.1 mol/liter, and a sodium ion concentration of 0.05 to 4 mol/liter are respectively prepared. 6
The gist is that the mixture is mixed at a temperature below 0°C so that no gel-like substance is formed, and then heated to 60 to 100°C to precipitate type A zeolite. At this time, the ion concentrations of each aqueous solution in the mixed state are aluminate ion concentration: 0.05 to 0.15 mol/liter, silicate ion concentration: 0.01 to 0.05 mol/liter, and sodium ion concentration. By adjusting the concentration to be 0.05 to 3.0 mol/liter, type A zeolite can be obtained more efficiently.
【００１０】0010
【作用】本発明では、上記の様にアルミン酸イオンを含
む水酸化ナトリウム水溶液［以下アルミン酸イオン含有
水溶液（Ｘ） ということがある］と珪酸イオンを含む
水酸化ナトリウム水溶液［以下、珪酸イオン含有水溶液
（Ｙ） ということがある］を別々に調製し、これらを
ゲル状物が生成しない様に６０℃未満の温度で均一に混
合［以下、混合液 （Ｘ ＋Ｙ）ということがある］し
た後、これを所定の温度に加温するものであり、それに
より後記実施例でも明らかにする如く、ヒドロキシソー
ダライトを生ずることなくＡ型ゼオライトを高収率で製
造することができる。[Operation] In the present invention, as described above, a sodium hydroxide aqueous solution containing aluminate ions [hereinafter sometimes referred to as aluminate ion-containing aqueous solution (X)] and a sodium hydroxide aqueous solution containing silicate ions [hereinafter referred to as a silicate ion-containing aqueous solution (X)] are used. After separately preparing an aqueous solution (Y)] and uniformly mixing them at a temperature below 60°C to prevent the formation of gel-like substances [hereinafter sometimes referred to as mixed solution (X + Y)]. This is heated to a predetermined temperature, thereby making it possible to produce A-type zeolite in high yield without producing hydroxysodalite, as will be made clear in the examples below.
【００１１】但し本発明の目的を達成するためには、夫
々の水溶液（Ｘ），（Ｙ） を調製する段階で、アルミ
ン酸イオン含有水溶液（Ｘ） については、アルミン酸
イオン濃度を０．１〜０．３ モル／リットルにすると
共にナトリウムイオン濃度を０．０５〜３モル／リット
ルとし、また珪酸イオン含有水溶液（Ｙ） については
、珪酸イオンを０．０２〜０．１モル／リットルに設定
すると共にナトリウムイオン濃度を０．０５〜４モル／
リットルに調整し、これらを６０℃未満の温度でゲル状
物が生成しない様に均一に混合した後、次いで６０〜１
００ ℃に加熱することによってＡ型ゼオライトの結晶
を析出させる。However, in order to achieve the purpose of the present invention, at the stage of preparing each of the aqueous solutions (X) and (Y), the aluminate ion concentration of the aluminate ion-containing aqueous solution (X) must be adjusted to 0.1. ~0.3 mol/liter and the sodium ion concentration is set to 0.05 to 3 mol/liter, and for the silicate ion-containing aqueous solution (Y), the silicate ion is set to 0.02 to 0.1 mol/liter. At the same time, the sodium ion concentration is increased from 0.05 to 4 mol/
After uniformly mixing these at a temperature of less than 60°C so as not to form a gel, then 60 to 1
By heating to 00°C, type A zeolite crystals are precipitated.
【００１２】混合前の各水溶液（Ｘ），（Ｙ） におい
て、夫々のアルミン酸イオン濃度または珪酸イオン濃度
が低過ぎたり、あるいは両水溶液（Ｘ），（Ｙ） のナ
トリウムイオン濃度が高過ぎると、２液混合後所定温度
に加温してもＡ型ゼオライトの結晶析出が起こらない。
また逆にアルミン酸イオン濃度や珪酸イオン濃度が高過
ぎたり、あるいはナトリウムイオン濃度が低過ぎると、
２液混合直後にゲル状の析出物（主としてアルミノシリ
ケートゲル）が生成し、その後で所定温度に加温しても
生成したゲルの相変化は起こらず、結晶質のＡ型ゼオラ
イトが得られなくなる。[0012] If the aluminate ion concentration or silicate ion concentration of each of the aqueous solutions (X) and (Y) before mixing is too low, or the sodium ion concentration of both the aqueous solutions (X) and (Y) is too high, , even if the two liquids are mixed and heated to a predetermined temperature, crystal precipitation of type A zeolite does not occur. Conversely, if the aluminate ion concentration or silicate ion concentration is too high, or the sodium ion concentration is too low,
Immediately after mixing the two liquids, a gel-like precipitate (mainly aluminosilicate gel) is generated, and even if heated to a certain temperature afterwards, the phase change of the gel does not occur, making it impossible to obtain crystalline A-type zeolite. .
【００１３】尚２液混合時におけるゲル状物の生成を防
止すると共に、その後の加温でＡ型ゼオライトの晶出を
効率良く進めるには、２液混合後の各イオン濃度が、ア
ルミン酸イオン濃度：０．０５〜０．１５モル／リット
ル，珪酸イオン濃度：０．０１〜０．０５モル／リット
ルと，ナトリウムイオン濃度：０．０５〜３．０ モル
／リットルとなる様に、両水溶液（Ｘ），（Ｙ） のイ
オン濃度と配合比率を調整するのがよい。[0013] In order to prevent the formation of a gel-like substance when the two liquids are mixed and to efficiently promote the crystallization of type A zeolite by subsequent heating, the concentration of each ion after mixing the two liquids must be adjusted to Both aqueous solutions were prepared so that the concentration: 0.05 to 0.15 mol/liter, the silicate ion concentration: 0.01 to 0.05 mol/liter, and the sodium ion concentration: 0.05 to 3.0 mol/liter. It is best to adjust the ion concentration and blending ratio of (X) and (Y).
【００１４】また２液混合時の温度が６０℃を超えると
、２液が均一に混合される前の各イオン濃度に偏りがあ
る状態のときに部分的にゲル状物が生成し、このゲル状
物は再溶解せず且つその後の加温によってもＡ型ゼオラ
イト結晶に変わらないので、やはり満足な収率が得られ
なくなる。従って２液を混合する際には、液温が６０℃
を超えない様に、より好ましくは５０℃以下に保たれる
様に注意しなければならない。[0014] Furthermore, if the temperature when mixing the two liquids exceeds 60°C, a gel-like substance is partially formed when the concentrations of each ion are uneven before the two liquids are mixed uniformly. Since the crystals do not redissolve and do not change into A-type zeolite crystals even after subsequent heating, a satisfactory yield cannot be obtained. Therefore, when mixing two liquids, the liquid temperature should be 60℃.
Care must be taken not to exceed 50°C, more preferably to keep the temperature below 50°C.
【００１５】また両水溶液の特にナトリウムイオン濃度
は、２液混合時における一時的なイオン濃度の偏りを極
力少なくできる様、同一濃度に調整しておくことが望ま
しい。更に各水溶液（Ｘ），（Ｙ） のアルミン酸イオ
ン濃度及び珪酸イオン濃度については、上記規定範囲の
上限領域に近いほど、またナトリウムイオン濃度につい
ては下限領域に近いほど、混合時におけるゲル状物の生
成はより確実に防止できる様になる。[0015] In addition, it is desirable that the sodium ion concentrations in both aqueous solutions, in particular, be adjusted to the same concentration so that temporary deviation in ion concentration during mixing of the two solutions can be minimized. Furthermore, the closer the aluminate ion concentration and silicate ion concentration of each aqueous solution (X) and (Y) are to the upper limit of the above specified range, and the closer the sodium ion concentration is to the lower limit, the more likely the gel-like substance will be formed during mixing. The generation of can be more reliably prevented.
【００１６】しかもゲル析出反応を起こし易い両水溶液
（Ｘ），（Ｙ） の混合に当たっては、混合の順序も重
要となる。上記した各イオン濃度領域においてはゲル状
物の生成反応は、珪酸イオン濃度の変化よりもアルミン
酸イオン濃度の変化に影響され易く、珪酸イオン含有水
溶液（Ｙ） にアルミン酸イオン含有水溶液（Ｘ） を
加えたときはゲル状物を生じないが、その逆にするとゲ
ル状物を生ずることがある。従って２液混合の手段とし
ては、混合系において珪酸イオン濃度に対するアルミン
酸イオン濃度が局部的に高くなることのない様、アルミ
ン酸イオン含有水溶液（Ｘ） に珪酸イオン含有水溶液
（Ｙ） を混入させる方法、或は両者を同時に空容器に
加えて混合する方法等を採用することが望まれる。この
２液混合工程で十分な攪拌を加えるべきであることは勿
論である。Furthermore, when mixing the aqueous solutions (X) and (Y), which tend to cause gel precipitation reactions, the order of mixing is also important. In each of the above-mentioned ion concentration ranges, the gel-like product formation reaction is more easily affected by changes in the aluminate ion concentration than by changes in the silicate ion concentration, and the silicate ion-containing aqueous solution (Y) is mixed with the aluminate ion-containing aqueous solution (X). When adding , no gel-like material is formed, but when the opposite is done, a gel-like material may be formed. Therefore, as a means of mixing two liquids, an aqueous solution containing aluminate ions (X) is mixed with an aqueous solution containing silicate ions (Y) so that the aluminate ion concentration relative to the silicate ion concentration does not locally increase in the mixing system. It is desirable to adopt a method such as a method in which the two components are added to an empty container at the same time and mixed. Needless to say, sufficient stirring should be applied in this two-liquid mixing step.
【００１７】かくして得られる所定イオン濃度の混合液
を６０〜１００ ℃、より好ましくは７０〜９０℃に加
温すると、アルミノシリケートゲルを生ずることなく、
また安定相のヒドロキシソーダライト結晶を生ずること
なく、準安定相であるＡ型ゼオライト結晶のみが選択的
に生成する。このとき温度が６０℃未満ではＡ型ゼオラ
イト結晶が生成せず、また１００ ℃を超えるとヒドロ
キシソーダライトへの相変化が急速に進行し、Ａ型ゼオ
ライトの生成率及び純度が低下する。[0017] When the thus obtained mixed solution having a predetermined ion concentration is heated to 60 to 100°C, more preferably 70 to 90°C, the mixture is heated to a temperature of 60 to 100°C, more preferably 70 to 90°C, without forming an aluminosilicate gel.
In addition, only type A zeolite crystals, which are a metastable phase, are selectively produced without producing hydroxysodalite crystals, which are a stable phase. At this time, if the temperature is less than 60°C, A-type zeolite crystals will not be formed, and if it exceeds 100°C, the phase change to hydroxysodalite will proceed rapidly, and the production rate and purity of A-type zeolite will decrease.
【００１８】[0018]
実施例
アルミン酸イオン０．２５モル／リットルとナトリウム
イオン１．０ モル／リットルを含む水溶液（Ａ液）と
、珪酸イオン０．１ モル／リットルとナトリウムイオ
ン１．０ モル／リットルを含む水溶液（Ｂ液）、及び
１０．０モル／リットルの水酸化ナトリウム水溶液（Ｃ
液）を準備した。Example An aqueous solution containing 0.25 mol/liter of aluminate ion and 1.0 mol/liter of sodium ion (solution A), and an aqueous solution containing 0.1 mol/liter of silicate ion and 1.0 mol/liter of sodium ion (solution A). B solution), and 10.0 mol/liter aqueous sodium hydroxide solution (C
liquid) was prepared.
【００１９】そして上記Ａ液、Ｂ液、Ｃ液及び純水を表
１に示す比率で混合して水溶液（Ｘ）及び（Ｙ） を調
製（両水溶液のナトリウムイオン濃度は略同一になる様
に調整）し、これらを室温（約２５℃）で混合した。尚
混合に当たっては、水溶液（Ｙ） を攪拌しつつ水溶液
（Ｘ） を攪拌しを加えることにより、ゲル状物が生成
しない様に混合した。次いで混合液を昇温して所定時間
保持し、Ａ型ゼオライトを晶出させた。混合液の各イオ
ン濃度及び加温条件を表１に一括して示す。得られた晶
出物をＸ線回折により固定したところ、すべてＡ型ゼオ
ライトであり、ヒドロキシソーダライトの生成は認めら
れなかった。Aqueous solutions (X) and (Y) were prepared by mixing the above A, B, C and pure water in the ratio shown in Table 1 (so that the sodium ion concentrations of both aqueous solutions were approximately the same). (adjustment) and these were mixed at room temperature (about 25°C). During the mixing, the aqueous solution (X) was stirred while the aqueous solution (Y) was stirred, so that a gel-like substance was not formed. Next, the temperature of the mixed solution was raised and maintained for a predetermined period of time to crystallize type A zeolite. Table 1 shows the concentration of each ion and heating conditions in the mixed solution. When the obtained crystallized product was fixed by X-ray diffraction, it was found that all of the crystallized products were type A zeolite, and no formation of hydroxysodalite was observed.
【００２０】[0020]
【表１】[Table 1]
【００２１】比較例
上記実施例と同様の方法で水溶液（Ｘ） 及び（Ｙ）
を調製した後、表２に示す如く、異なる条件で両液の混
合及び加温を行い、生成物の状態を観察した。原料溶液
の調製法、混合法、原料イオン濃度、加温条件及び生成
物の状態を表２に一括して示す。Comparative Example Aqueous solutions (X) and (Y) were prepared in the same manner as in the above example.
After the preparation, both solutions were mixed and heated under different conditions as shown in Table 2, and the state of the product was observed. Table 2 shows the preparation method of the raw material solution, the mixing method, the raw material ion concentration, the heating conditions, and the state of the product.
【００２２】[0022]
【表２】[Table 2]
【００２３】表２のＮｏ．１〜５はいずれも本発明の規
定要件を欠く比較例であり、以下に示す如くＡ型ゼオラ
イト結晶を得ることができない。
Ｎｏ．１：原料溶液のうち水溶液（Ｙ） の珪酸イオン
濃度が低く、且つ混合状態での珪酸イオン濃度も低過ぎ
るため、所定の熱を加えても析出物が生成しない。
Ｎｏ．２：原料溶液のイオン濃度は適正であるが、混合
時の温度が高過ぎるため混合時にゲル化し、その後加熱
を行なっても結晶を得ることができない。
Ｎｏ．３：原料溶液のうち水溶液（Ｘ） の珪酸イのア
ルミン酸イオン濃度が高く、且つ混合状態でのアルミン
酸イオン濃度も高過ぎるため、混合直後に非晶質の不溶
物が生成し、この不溶物はその後の加熱処理によっても
Ａ型ゼオライト結晶への相変化を起こさない。
Ｎｏ．４：原料溶液のうち水溶液（Ｘ） のアルミン酸
イオン濃度が低く、混合状態でのアルミン酸イオン濃度
も低過ぎるため、混合後所定の熱を加えても析出物が生
成しない。
Ｎｏ．５：２液混合時の温度が高過ぎる比較例であり、
混合後に生成する晶出物の大部分は安定相のヒドロキシ
ソーダライトであった。[0023] No. of Table 2. Examples 1 to 5 are all comparative examples that lack the specified requirements of the present invention, and as shown below, type A zeolite crystals cannot be obtained. No. 1: The silicate ion concentration of the aqueous solution (Y) among the raw material solutions is low, and the silicate ion concentration in the mixed state is also too low, so no precipitates are formed even when a predetermined amount of heat is applied. No. 2: Although the ion concentration of the raw material solution is appropriate, the temperature during mixing is too high, resulting in gelation during mixing, and crystals cannot be obtained even if heated thereafter. No. 3: Among the raw material solutions, the concentration of aluminate ions of silicate in the aqueous solution (X) is high, and the concentration of aluminate ions in the mixed state is also too high, so amorphous insoluble matter is generated immediately after mixing, and this insoluble matter is The material does not undergo a phase change to type A zeolite crystals even after subsequent heat treatment. No. 4: Among the raw material solutions, the aluminate ion concentration in the aqueous solution (X) is low, and the aluminate ion concentration in the mixed state is also too low, so no precipitates are formed even if a predetermined amount of heat is applied after mixing. No. 5: Comparative example where the temperature when mixing the two liquids is too high,
Most of the crystallized material formed after mixing was a stable phase of hydroxysodalite.
【００２４】[0024]
【発明の効果】本発明は以上の様に構成されており、安
定相のヒドロキシソーダライトを生成させることなく、
準安定相のＡ型ゼオライトを収率良く製造し得ることに
なった。[Effects of the Invention] The present invention is constructed as described above, and without producing stable phase hydroxysodalite,
It became possible to produce metastable phase A-type zeolite with good yield.
Claims (2)
．３ モル／リットル、ナトリウムイオン濃度が０．０
５〜３モル／リットルである水溶液と、珪酸イオン濃度
が０．０２〜０．１ モル／リットル、ナトリウムイオ
ン濃度が０．０５〜４モル／リットルである水溶液とを
、夫々調製しておき、これらを６０℃未満の温度でゲル
状物が生成しない様に混合し、次いで６０〜１００ ℃
に加熱してＡ型ゼオライトを析出させることを特徴とす
るＡ型ゼオライトの製造法。Claim 1: Aluminate ion concentration is 0.1 to 0
．． 3 mol/liter, sodium ion concentration 0.0
Prepare an aqueous solution having a concentration of 5 to 3 mol/liter, an aqueous solution having a silicate ion concentration of 0.02 to 0.1 mol/liter, and a sodium ion concentration of 0.05 to 4 mol/liter, respectively. These are mixed at a temperature below 60°C so that no gel is formed, and then heated at a temperature of 60 to 100°C.
A method for producing A-type zeolite, which comprises heating to precipitate A-type zeolite.
ルミン酸イオン濃度：０．０５〜０．１５モル／リット
ル，珪酸イオン濃度：０．０１〜０．０５モル／リット
ル，ナトリウムイオン濃度：０．０５〜３．０ モル／
リットルとする請求項１記載の製造法。2. The concentrations of each ion in the mixed state are as follows: aluminate ion concentration: 0.05 to 0.15 mol/liter, silicate ion concentration: 0.01 to 0.05 mol/liter, and sodium ion concentration: 0. 05-3.0 mol/
The manufacturing method according to claim 1, wherein the volume is liter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3145436A JP2806079B2 (en) | 1991-05-20 | 1991-05-20 | Method for producing type A zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3145436A JP2806079B2 (en) | 1991-05-20 | 1991-05-20 | Method for producing type A zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04342416A true JPH04342416A (en) | 1992-11-27 |
| JP2806079B2 JP2806079B2 (en) | 1998-09-30 |
Family
ID=15385203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3145436A Expired - Fee Related JP2806079B2 (en) | 1991-05-20 | 1991-05-20 | Method for producing type A zeolite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2806079B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031591A (en) * | 2006-07-28 | 2008-02-14 | Nisshinbo Ind Inc | Method for producing cellulosic fiber structure |
| JP2008031592A (en) * | 2006-07-28 | 2008-02-14 | Nisshinbo Ind Inc | Method for producing cellulosic fiber structure |
-
1991
- 1991-05-20 JP JP3145436A patent/JP2806079B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008031591A (en) * | 2006-07-28 | 2008-02-14 | Nisshinbo Ind Inc | Method for producing cellulosic fiber structure |
| JP2008031592A (en) * | 2006-07-28 | 2008-02-14 | Nisshinbo Ind Inc | Method for producing cellulosic fiber structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2806079B2 (en) | 1998-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1725498B1 (en) | Synthesis of zsm-48 crystals with heterostructural, non zsm-48, seeding | |
| Cundy et al. | Crystallisation of zeolitic molecular sieves: direct measurements of the growth behaviour of single crystals as a function of synthesis conditions | |
| JP3293636B2 (en) | Method for producing crystalline layered sodium silicate | |
| GB1580928A (en) | Manufacture of low silica faujasites | |
| JPH0583483B2 (en) | ||
| JPS60127222A (en) | Manufacture of recycling zeolite l | |
| JPH0566323B2 (en) | ||
| CN101205073A (en) | Method for preparing aluminium-containing MCM-41 molecular sieve | |
| CN113603110A (en) | Template-free preparation method of porous LSX zeolite molecular sieve | |
| US11434140B2 (en) | Hierarchical zeolites and preparation method therefor | |
| US7361328B2 (en) | Method of preparing ZSM-5 using variable temperature without organic template | |
| CN106315612B (en) | A kind of preparation method of low silica-alumina ratio X-type molecular sieve | |
| JPH04342416A (en) | Production of a type zeolite | |
| CN101863492A (en) | Synthesis method of 4A-type zeolite | |
| CN110627087A (en) | Method for synthesizing low-silicon faujasite raw powder by liquid phase seed crystal method | |
| EP0681991B1 (en) | Clinoptilolite and method for synthesizing the same | |
| JPH0297416A (en) | Method for synthesizing truly spherical pentasyl type zeolite powder | |
| KR102020445B1 (en) | Method for preparation of mordenite zeolite capable of particle size control | |
| CN113336240A (en) | Method for preparing single/double crystal ZSM-5 zeolite based on kaolin mineral regulation and control | |
| EP3778485A1 (en) | Method for preparing zsm-5 zeolite | |
| JP2793375B2 (en) | Method for producing p-type zeolite | |
| CN111848428A (en) | Preparation method of gamma-type glycine and gamma-type glycine | |
| JPH05139722A (en) | Method for production of crystal zeolite | |
| JPH07247114A (en) | Production of zeolite beta | |
| KR920008517B1 (en) | Process for separating off barium from water-soluble strontium salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19980623 |
|
| LAPS | Cancellation because of no payment of annual fees |