JPH05163015A - Production of zeolite x type molded product - Google Patents
Production of zeolite x type molded productInfo
- Publication number
- JPH05163015A JPH05163015A JP3349742A JP34974291A JPH05163015A JP H05163015 A JPH05163015 A JP H05163015A JP 3349742 A JP3349742 A JP 3349742A JP 34974291 A JP34974291 A JP 34974291A JP H05163015 A JPH05163015 A JP H05163015A
- Authority
- JP
- Japan
- Prior art keywords
- type zeolite
- silica
- type
- molded product
- low
- 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
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 63
- 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 63
- 239000010457 zeolite Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 75
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 62
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- 239000004927 clay Substances 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 60
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 150000002500 ions Chemical class 0.000 abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 238000002425 crystallisation Methods 0.000 description 12
- 230000008025 crystallization Effects 0.000 description 12
- 239000013078 crystal Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011734 sodium Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000005469 granulation Methods 0.000 description 6
- 230000003179 granulation Effects 0.000 description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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
- 239000000654 additive Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 229910052708 sodium 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
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
(57)【要約】
【構成】シリカ／アルミナモル比が２．５より低いＸ型
ゼオライト成形体を製造するに際し、シリカ／アルミナ
モル比が２．５より低いＸ型ゼオライト粉末、カオリン
型粘土、水酸化ナトリウム及び水酸化カリウムを含む成
形体を結晶化することを特徴とするＸ型ゼオライト成形
体の製造方法。
【効果】高純度な低シリカＸ型ゼオライト成形体を製造
することが可能である。このようにして合成された低シ
リカＸ型ゼオライト成形体は、そのままあるいはほかの
イオン、例えば、Ｃａでイオン交換され、吸着容量の大
きい成形体として吸着分離剤などに使用することができ
る。(57) [Summary] [Structure] X-type zeolite powder having a silica / alumina molar ratio of less than 2.5, kaolin-type clay, and hydroxide for producing an X-type zeolite compact having a silica / alumina molar ratio of less than 2.5. A method for producing an X-type zeolite molded body, which comprises crystallizing a molded body containing sodium and potassium hydroxide. [Effect] It is possible to produce a high-purity low-silica X-type zeolite compact. The low-silica X-type zeolite molded product thus synthesized can be used as it is or as a molded product having a large adsorption capacity after being ion-exchanged with other ions, for example, Ca, as an adsorption separator.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、結合剤含有量の少ない
シリカ／アルミナモル比の低いＸ型ゼオライト成形体の
製造方法に関するものである。更に詳しくは、著しく高
い吸着容量を有し、例えば窒素と酸素とを主成分とする
混合ガスから吸着分離法によって酸素を分離、濃縮する
などの目的で使用するのに適したシリカ／アルミナモル
比の低いＸ型ゼオライト成形体の製造方法に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an X-type zeolite compact having a low binder / silica / alumina molar ratio. More specifically, it has a remarkably high adsorption capacity, for example, a silica / alumina molar ratio suitable for use for the purpose of separating and concentrating oxygen from a mixed gas containing nitrogen and oxygen as main components by an adsorption separation method. The present invention relates to a method for producing a low X-type zeolite compact.
【０００２】[0002]
【従来の技術】通常、合成されたＸ型ゼオライトのシリ
カ／アルミナモル比は２．５であるが、合成時にＮａＯ
Ｈに加えＫＯＨを共存させることによって、そのシリカ
／アルミナモル比を２．０にまで下げることができる。
ゼオライトのシリカ／アルミナモル比を下げることは、
結晶中のアルミニウム原子の数が増加することであり、
従って、カチオンの数が増加することとなる。一般にゼ
オライトへの窒素、酸素などの分子の吸着は物理吸着と
呼ばれ、このカチオンの数が多いほどその吸着容量は増
加することとなる。ここでは、以下、シリカ／アルミナ
モル比が２．５より低いＸ型ゼオライトを低シリカＸ型
ゼオライトと呼ぶこととする。低シリカＸ型ゼオライト
の製造方法については、特開昭５３−８４００号公報、
特開昭６１−２２２９１９号公報、特開昭６４−５６１
１２号公報などに記載されている。2. Description of the Related Art Usually, a synthesized X-type zeolite has a silica / alumina molar ratio of 2.5.
The coexistence of KOH in addition to H can reduce the silica / alumina molar ratio to 2.0.
Lowering the silica / alumina molar ratio of the zeolite
Is to increase the number of aluminum atoms in the crystal,
Therefore, the number of cations will increase. Generally, the adsorption of molecules such as nitrogen and oxygen on zeolite is called physical adsorption, and the larger the number of cations, the larger the adsorption capacity. Hereafter, the X-type zeolite having a silica / alumina molar ratio of less than 2.5 will be referred to as a low-silica X-type zeolite. Regarding the method for producing the low silica X-type zeolite, JP-A-53-8400,
JP-A-61-2222919, JP-A-64-561
No. 12, for example.
【０００３】通常、Ｘ型ゼオライトを、吸着分離剤など
として工業的に利用する場合には、合成したＸ型ゼオラ
イト粉末に、結合剤として粘土等を添加し、ペレットあ
るいはビーズのような成形体にして使用される。添加さ
れる粘土の量は約２５重量部であり、従って、ゼオライ
ト成形体の有する吸着容量は、ゼオライト粉末が有する
吸着容量に対し、粘土の添加分だけ減少してしまうこと
となる。その解決の為に、粘土をほとんど含有しない成
形体、即ち、バインダーレス成形体の製造方法がこれま
で提案されている。その中で、低シリカＸ型ゼオライト
成形体のバインダーレス化の方法については、特開昭６
１−２２２９１９号公報に記載されている。これは低シ
リカＸ型ゼオライト粉末を使用することなく、カオリン
を原料とする成形体をメタカオリンに転化した後、結晶
化することにより、低シリカＸ型ゼオライト成形体を製
造する方法である。その方法によると、高純度の低シリ
カＸ型ゼオライト成形体を得るためにには、多量の細孔
形成物質（有機物）をカオリンの成形体製造時に添加
し、加熱し、燃焼させて多孔質のメタカオリン成形体と
し、その後結晶化することが必要である。しかしながら
この方法では有機物の燃焼により極めて大きな発熱を伴
う結果、温度制御が難しく、成形体の細孔をうまく制御
することが極めて困難となり、それ故、高純度な低シリ
カＸ型ゼオライト成形体を得ることが難しい。Usually, when X-type zeolite is industrially used as an adsorption / separation agent, clay or the like is added as a binder to the synthesized X-type zeolite powder to form a molded body such as pellets or beads. Used. The amount of clay to be added is about 25 parts by weight, so that the adsorption capacity of the zeolite compact is reduced by the amount of clay added to the adsorption capacity of the zeolite powder. In order to solve the problem, a method for producing a molded body containing almost no clay, that is, a binderless molded body has been proposed so far. Among them, Japanese Patent Application Laid-Open No. Sho 6-86 (1999) discloses a method for making a low-silica X-type zeolite molded product binderless.
No. 1-222219. This is a method for producing a low silica X-type zeolite compact by converting a compact made of kaolin as a raw material into metakaolin and then crystallizing it without using the low-silica X-type zeolite powder. According to the method, in order to obtain a high-purity low-silica X-type zeolite molded body, a large amount of a pore-forming substance (organic substance) is added at the time of manufacturing the kaolin molded body, and the mixture is heated and burned to make it porous. It is necessary to obtain a metakaolin molded product and then crystallize it. However, in this method, combustion of organic substances causes extremely large heat generation, and as a result, it is difficult to control the temperature and it is extremely difficult to control the pores of the molded product very well. Therefore, a highly purified low silica X-type zeolite molded product is obtained. Difficult to do.
【０００４】[0004]
【発明が解決しようとする課題】本発明は以上の様な困
難を回避した低シリカＸ型ゼオライトを９０重量％以上
含有するＸ型ゼオライト成形体を製造する方法を提供す
るものである。SUMMARY OF THE INVENTION The present invention provides a method for producing an X-type zeolite compact containing 90% by weight or more of low silica X-type zeolite, which avoids the above difficulties.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、低シリカ
Ｘ型ゼオライト成形体の製造における各因子について鋭
意検討を行い本発明に至った。Means for Solving the Problems The inventors of the present invention have made extensive studies on each factor in the production of a low-silica X-type zeolite molded product, and arrived at the present invention.
【０００６】即ち、本発明の要旨は、低シリカＸ型ゼオ
ライト成形体を製造するに際し、シリカ／アルミナモル
比が２．５より低いＸ型ゼオライト粉末、カオリン型粘
土、水酸化ナトリウム及び水酸化カリウムを含む成形体
を結晶化することにより、Ａ型ゼオライト等の不純物の
生成を抑制し、高純度な低シリカＸ型ゼオライト成形体
を製造する方法である。That is, the gist of the present invention is to produce X-type zeolite powder having a silica / alumina molar ratio of less than 2.5, kaolin-type clay, sodium hydroxide and potassium hydroxide in producing a low-silica X-type zeolite compact. It is a method for producing a highly pure low silica X-type zeolite molded body by suppressing the generation of impurities such as A-type zeolite by crystallizing the molded body containing the same.
【０００７】以下、本発明を説明する。The present invention will be described below.
【０００８】本発明で、使用する低シリカＸ型ゼオライ
ト粉末は、特開昭５３−８４００号公報、特開昭６４−
５６１１２号公報などに記載されている方法で製造すれ
ばよい。例えば、特開昭５３−８４００号公報には、ナ
トリウム、カリウム、アルミネートおよびシリケートの
各イオンを含有する溶液を混合し、下記の組成 ＳｉＯ２／Ａｌ２Ｏ３ １．３〜２．２ （Ｎａ２Ｏ＋Ｋ２Ｏ）／ＳｉＯ２ ２．０〜４．５ Ｎａ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ） ０．６〜０．９ Ｈ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ） １０〜３５ 混合物を得、約５０℃の温度で結晶化が完了するまでの
十分な時間結晶化させることにより、低シリカＸ型ゼオ
ライト粉末を得る方法が開示されている。この低シリカ
Ｘ型ゼオライト粉末１００重量部に対し、カオリン型粘
土を１０〜５０重量部、水酸化ナトリウム及び水酸化カ
リウム、さらに造粒助剤として有機系、無機系の添加剤
を加え、十分混合し混練する。得られた捏和物を通常の
押出し成形機で押出し成形する。捏和物に練り込む水酸
化ナトリウム及び水酸化カリウムの添加量は、成形体中
のカオリン型粘土に含まれるアルミニウム量に対し、モ
ル比で表わして、（Ｎａ２Ｏ＋Ｋ２Ｏ）／Ａｌ２Ｏ３比
が０．２〜３．０となることが好ましい。この比が低す
ぎると結晶化が十分進行せず、高すぎるとＡ型ゼオライ
トなどの不純物が生成するからである。また、水酸化ナ
トリウムと水酸化カリウムの比は、モル比で表わして、
Ｎａ２Ｏ／（Ｎａ２Ｏ＋Ｋ２Ｏ）比が０．１〜０．９の
範囲に入ることが好ましい。練り込みを行わずに、必要
な水酸化ナトリウムと水酸化カリウムの全量を、熟成・
結晶化時に使用する水溶液中に添加した場合には、不純
物であるＡ型ゼオライト、ソーダライトなどが共生した
り、あるいは、添加したカオリン型粘土が低シリカＸ型
ゼオライトへとうまく転化せず、目標とする高純度に到
達しない。未焼成のカオリン型粘土を使用した場合に
は、成形体を６００℃で焼成し、カオリン型粘土を反応
性に富むメタカオリンに転化する。この焼成した成形体
を、ＮａＯＨとＫＯＨ水溶液中において、４０〜１００
℃の温度で数時間〜数日間保持し、熟成・結晶化するこ
とによって、９０重量％以上の低シリカＸ型ゼオライト
を含むゼオライト成形体が得られる。The low silica X-type zeolite powder used in the present invention is disclosed in JP-A-53-8400 and JP-A-64-
It may be manufactured by the method described in Japanese Patent No. 56112. For example, in JP-A-53-8400, a solution containing each of ions of sodium, potassium, aluminate and silicate is mixed, and the following composition SiO 2 / Al 2 O 3 1.3 to 2.2 ( Na 2 O + K 2 O) / SiO 2 2.0-4.5 Na 2 O / (Na 2 O + K 2 O) 0.6-0.9 H 2 O / (Na 2 O + K 2 O) 10-35 Mixtures A method of obtaining a low-silica X-type zeolite powder by crystallization at a temperature of about 50 ° C. for a sufficient time until crystallization is disclosed is disclosed. To 100 parts by weight of this low silica X-type zeolite powder, 10 to 50 parts by weight of kaolin clay, sodium hydroxide and potassium hydroxide, and organic and inorganic additives as granulation aids are added and mixed well. Then knead. The kneaded material thus obtained is extruded by a usual extrusion molding machine. The addition amount of sodium hydroxide and potassium hydroxide kneaded into the kneaded product is expressed by a molar ratio with respect to the amount of aluminum contained in the kaolin-type clay in the molded body, and is (Na 2 O + K 2 O) / Al 2 O. It is preferable that the 3 ratio is 0.2 to 3.0. This is because if this ratio is too low, crystallization does not proceed sufficiently, and if it is too high, impurities such as A-type zeolite are generated. Also, the ratio of sodium hydroxide and potassium hydroxide is represented by the molar ratio,
The Na 2 O / (Na 2 O + K 2 O) ratio preferably falls within the range of 0.1 to 0.9. Aging the required amount of sodium hydroxide and potassium hydroxide without kneading.
When added to the aqueous solution used for crystallization, impurities such as A-type zeolite and sodalite coexist, or the added kaolin-type clay does not convert to low-silica X-type zeolite, And do not reach high purity. When uncalcined kaolin-type clay is used, the molded body is calcined at 600 ° C. to convert the kaolin-type clay into highly reactive metakaolin. The fired compact was placed in an aqueous solution of NaOH and KOH at 40 to 100%.
By holding at a temperature of ° C for several hours to several days and aging and crystallization, a zeolite compact containing 90 wt% or more of low silica X-type zeolite can be obtained.
【０００９】[0009]
【発明の効果】本発明の方法によれば、高純度な低シリ
カＸ型ゼオライト成形体を製造することが可能である。
このようにして合成された低シリカＸ型ゼオライト成形
体は、そのままあるいはほかのイオン、例えば、Ｃａで
イオン交換され、吸着容量の大きい成形体として吸着分
離剤などに使用することができる。According to the method of the present invention, it is possible to produce a high-purity low silica X-type zeolite compact.
The low-silica X-type zeolite molded product thus synthesized can be used as it is or as a molded product having a large adsorption capacity after being ion-exchanged with other ions, for example, Ca, as an adsorption separator.
【００１０】[0010]
【実施例】以下、実施例により本発明を具体的に説明す
る。EXAMPLES The present invention will be specifically described below with reference to examples.
【００１１】実施例１ まず、シリカ／アルミナモル比２．０の低シリカＸ型ゼ
オライト粉末を以下の手順によって合成した。Example 1 First, a low silica X-type zeolite powder having a silica / alumina molar ratio of 2.0 was synthesized by the following procedure.
【００１２】水酸化アルミニウム１，０４０ｇを５０ｗ
ｔ％水酸化ナトリウム水溶液１，３３５ｇに撹拌しなが
ら溶解し、溶液（ａ）を得た。５，０００ｇの水に８
５．３ｗｔ％水酸化カリウム１，４３５ｇを溶解し、こ
の溶液を５０ｗｔ％水酸化ナトリウム水溶液２，３３５
ｇと混合し、溶液（ｂ）を得た。ケイ酸ナトリウム（Ｎ
ａ２Ｏ ９．６ｗｔ％、ＳｉＯ２ ３０．９ｗｔ％）
２，２６６ｇを添加し、冷却しながら５分間混合した。
ゲル化の後、３６℃で２日間熟成し、続いて７０℃で１
６時間結晶化した。得られた粉末を純水で十分に洗浄
し、１００℃で一晩乾燥した。ドライ換算で１，４１０
ｇの粉末を得た。その化学組成は、モル比で表わして、
０．７５Ｎａ２Ｏ・０．２５Ｋ２Ｏ・Ａｌ２Ｏ３・２．
０ＳｉＯ２であった。また、結晶中のＫイオンを全てＮ
ａイオン交換したＮａ型ゼオライトの格子定数をＸ線回
折からもとめた結果、２５．０２オングストロームであ
って、この値からもシリカ／アルミナモル比は２．００
と算出された。さらに、この低シリカＸ型ゼオライト粉
末の相対湿度８０％に於ける水分吸着容量は、３２．４
％であった。50 w of aluminum hydroxide 1,040 g
It was dissolved in 1,335 g of a t% aqueous sodium hydroxide solution with stirring to obtain a solution (a). 8 in 5,000g of water
Dissolve 5.3 wt% potassium hydroxide (1,435 g), and use this solution as a 50 wt% sodium hydroxide aqueous solution (2,335).
It was mixed with g to obtain a solution (b). Sodium silicate (N
a 2 O 9.6 wt%, SiO 2 30.9 wt%)
2,266 g were added and mixed for 5 minutes with cooling.
After gelation, aged at 36 ° C for 2 days, then at 70 ° C for 1 day.
Crystallized for 6 hours. The obtained powder was thoroughly washed with pure water and dried at 100 ° C overnight. 1,410 in dry conversion
g of powder was obtained. Its chemical composition, expressed as a molar ratio,
0.75Na 2 O · 0.25K 2 O · Al 2 O 3 · 2.
It was 0 SiO 2 . In addition, all K ions in the crystal are N
As a result of finding the lattice constant of the a-ion-exchanged Na-type zeolite from X-ray diffraction, the result was 25.02 angstroms, and from this value, the silica / alumina molar ratio was 2.00.
Was calculated. Furthermore, the water adsorption capacity of this low silica X-type zeolite powder at a relative humidity of 80% is 32.4.
%Met.
【００１３】この低シリカＸ型ゼオライト粉末２２２ｇ
に、カオリン型粘土を５６ｇ、水酸化ナトリウム１５
ｇ、水酸化カリウム７ｇ及び造粒助剤としてカルボキシ
メチルセルロースを８ｇ添加し、また、押出し成形が可
能となるよう適当量の水を加えて、十分に混合・混練し
た。得られた捏和物を通常の押出し成形機で直径１．５
ｍｍの太さで押出し成形した。この成形体を１１０℃で
乾燥後、６００℃で２時間焼成し、カオリン型粘土をメ
タカオリンにした。冷却後、水に浸漬し、吸着された空
気などの気体をできる限り水と置換した後、水酸化ナト
リウム９０ｇ及び水酸化カリウム４２ｇを含む水溶液８
００ｃｃ中に投入した。４０℃で２日間、続いて９０℃
で２日間放置して結晶化を行った。結晶化終了後、得ら
れた成形体と母液を分離して、成形体に付着した水酸化
ナトリウム及び水酸化カリウムなどを十分に水で洗浄し
た後に、１１０℃で乾燥した。Ｘ線回折によって結晶解
析を行った結果、Ｘ型ゼオライト以外の結晶相は全く認
められず、カオリン型粘土がＸ型ゼオライトに転移して
いることを確認した。また、一部をＮａ型にし、その格
子定数を測定したところ、２５．０３オングストローム
であり、算出されたシリカ／アルミナモル比は１．９６
であった。また、このゼオライト成形体の相対湿度８０
％に於ける水分吸着容量は、３１．４％であり、Ｘ型ゼ
オライトの含有率は９７％であった。222 g of this low silica X-type zeolite powder
56g of kaolin clay and 15g of sodium hydroxide
g, 7 g of potassium hydroxide and 8 g of carboxymethyl cellulose as a granulation aid, and an appropriate amount of water was added so that extrusion molding was possible, and the mixture was sufficiently mixed and kneaded. The kneaded material obtained is then subjected to a diameter of 1.5 with an ordinary extruder.
It was extruded with a thickness of mm. The molded body was dried at 110 ° C. and then calcined at 600 ° C. for 2 hours to convert the kaolin-type clay into metakaolin. After cooling, it is immersed in water and the gas such as adsorbed air is replaced with water as much as possible, and then an aqueous solution containing 90 g of sodium hydroxide and 42 g of potassium hydroxide 8
It was thrown in to 00cc. 2 days at 40 ° C, then 90 ° C
It was left to stand for 2 days for crystallization. After completion of crystallization, the obtained molded product and mother liquor were separated, and sodium hydroxide, potassium hydroxide and the like adhering to the molded product were sufficiently washed with water, and then dried at 110 ° C. As a result of crystal analysis by X-ray diffraction, no crystalline phase other than the X-type zeolite was observed, and it was confirmed that the kaolin-type clay was transferred to the X-type zeolite. Further, when a part thereof was made Na-type and its lattice constant was measured, it was 25.03 angstrom, and the calculated silica / alumina molar ratio was 1.96.
Met. In addition, the relative humidity of this zeolite molded body is 80
The water adsorption capacity in% was 31.4%, and the content of the X-type zeolite was 97%.
【００１４】実施例２ 実施例１で使用した低シリカＸ型ゼオライト粉末１３９
ｇに、６００℃で２時間焼成したカオリン型粘土を５６
ｇ、水酸化ナトリウム１５ｇ、水酸化カリウム７ｇ及び
造粒助剤としてカルボキシメチルセルロースを６ｇ添加
し、また、押出し成形が可能となるよう適当量の水を加
えて、十分に混合・混練し、捏和物を得た。その後は、
６００℃で２時間の焼成を行わなかった以外は実施例１
と同一処理を行った。Ｘ線回折によって結晶解析を行っ
た結果、Ｘ型ゼオライト以外の結晶相は全く認められ
ず、Ｎａ型の格子定数は、２５．０２オングストローム
であり、算出されたシリカ／アルミナモル比は２．００
であった。また、このゼオライト成形体の相対湿度８０
％に於ける水分吸着容量は、３０．８％であり、Ｘ型ゼ
オライトの含有率は９５％であった。Example 2 Low silica X-type zeolite powder 139 used in Example 1
56 g of kaolin-type clay calcined at 600 ° C. for 2 hours
g, 15 g of sodium hydroxide, 7 g of potassium hydroxide and 6 g of carboxymethyl cellulose as a granulation aid, and an appropriate amount of water is added to enable extrusion molding, and the mixture is thoroughly mixed and kneaded and kneaded. I got a thing. After that,
Example 1 except that the baking was not performed at 600 ° C. for 2 hours.
The same process was performed. As a result of crystal analysis by X-ray diffraction, no crystal phase other than X-type zeolite was observed, the Na-type lattice constant was 25.02 Å, and the calculated silica / alumina molar ratio was 2.00.
Met. In addition, the relative humidity of this zeolite molded body is 80
The water adsorption capacity in% was 30.8%, and the content of the X-type zeolite was 95%.
【００１５】実施例３ 実施例１で使用した低シリカＸ型ゼオライト粉末２２２
ｇに、カオリン型粘土を５６ｇ、水酸化ナトリウム３０
ｇ、水酸化カリウム１４ｇ及び造粒助剤としてカルボキ
シメチルセルロースを５ｇ添加し、また、押出し成形が
可能となるよう適当量の水を加えて、十分に混合・混練
した。得られた捏和物を実施例１と同様に成形、乾燥、
焼成処理を行った。冷却後、水に浸漬し、吸着された空
気などの気体をできる限り水と置換した後、水酸化ナト
リウム７５ｇ及び水酸化カリウム３５ｇを含む水溶液８
００ｃｃ中に投入した。５０℃で１０日間放置して結晶
化を行った。結晶化終了後、得られた成形体と母液を分
離して、成形体に付着した水酸化ナトリウム及び水酸化
カリウムなどを十分に水で洗浄した後に、１１０℃で乾
燥した。Ｘ線回折によって結晶解析を行った結果、Ｘ型
ゼオライト以外の結晶相は全く認められず、Ｎａ型の格
子定数を測定したところ、２５．０１オングストローム
であり、算出されたシリカ／アルミナモル比は２．０５
であった。また、このゼオライト成形体の相対湿度８０
％に於ける水分吸着容量は、３０．１％であり、Ｘ型ゼ
オライトの含有率は９３％であった。Example 3 Low silica X-type zeolite powder 222 used in Example 1
56 g of kaolin clay, 30 g of sodium hydroxide
g, 14 g of potassium hydroxide and 5 g of carboxymethyl cellulose as a granulation aid, and an appropriate amount of water was added to enable extrusion molding, and the mixture was sufficiently mixed and kneaded. The obtained kneaded product was molded, dried, and dried in the same manner as in Example 1.
A firing process was performed. After cooling, it is immersed in water to replace the adsorbed gas such as air with water as much as possible, and then an aqueous solution containing 75 g of sodium hydroxide and 35 g of potassium hydroxide 8
It was thrown in to 00cc. Crystallization was carried out by leaving it at 50 ° C. for 10 days. After completion of crystallization, the obtained molded product and mother liquor were separated, and sodium hydroxide, potassium hydroxide and the like adhering to the molded product were sufficiently washed with water, and then dried at 110 ° C. As a result of crystal analysis by X-ray diffraction, no crystal phase other than X-type zeolite was observed, and the Na-type lattice constant was measured to be 25.01 angstroms, and the calculated silica / alumina molar ratio was 2 .05
Met. In addition, the relative humidity of this zeolite molded body is 80
The water adsorption capacity in% was 30.1%, and the content of the X-type zeolite was 93%.
【００１６】比較例１ 実施例１で使用した、低シリカＸ型ゼオライト粉末２２
２ｇに、カオリン型粘土を５６ｇ、及び造粒助剤として
カルボキシメチルセルロースを８ｇ添加し、また、押出
し成形が可能となるよう適当量の水を加えて、十分に混
合・混練した。得られた捏和物を実施例１と同様に、成
形、乾燥、焼成処理を行った。冷却後、水に浸漬し、吸
着された空気などの気体をできる限り水と置換した後、
水酸化ナトリウム１０５ｇ及び水酸化カリウム４９ｇを
含む水溶液８００ｃｃ中に投入した。４０℃で２日間続
いて９０℃で２日間放置して結晶化を行った。結晶化終
了後、得られた成形体と母液を分離して、成形体に付着
した水酸化ナトリウム及び水酸化カリウムなどを十分に
水で洗浄した後に、１１０℃で乾燥した。Ｘ線回折によ
って結晶解析を行った結果、Ｘ型ゼオライト以外に不純
物であるＡ型のピークが観測された。Comparative Example 1 Low silica X-type zeolite powder 22 used in Example 1
To 2 g, 56 g of kaolin-type clay and 8 g of carboxymethyl cellulose as a granulation aid were added, and an appropriate amount of water was added so that extrusion molding was possible, and they were sufficiently mixed and kneaded. The obtained kneaded product was molded, dried and fired in the same manner as in Example 1. After cooling, after soaking in water and replacing the gas such as adsorbed air with water as much as possible,
It was put into 800 cc of an aqueous solution containing 105 g of sodium hydroxide and 49 g of potassium hydroxide. Crystallization was carried out by leaving the mixture at 40 ° C. for 2 days and then at 90 ° C. for 2 days. After completion of crystallization, the obtained molded product and mother liquor were separated, and sodium hydroxide, potassium hydroxide and the like adhering to the molded product were sufficiently washed with water, and then dried at 110 ° C. As a result of crystal analysis by X-ray diffraction, an A-type peak, which is an impurity, was observed in addition to the X-type zeolite.
【００１７】比較例２ 実施例１で使用した低シリカＸ型ゼオライト粉末５５５
ｇに、６００℃で２時間焼成したカオリン型粘土を５６
ｇ、及び造粒助剤としてカルボキシメチルセルロースを
１７ｇ添加し、また、押出し成形が可能となるよう適当
量の水を加えて、十分に混合・混練し、捏和物を得た。
直径１．５ｍｍの太さに成形し１１０℃で乾燥後、水に
浸漬し、吸着された空気などの気体をできる限り水と置
換した後、水酸化ナトリウム１０５ｇ及び水酸化カリウ
ム４９ｇを含む水溶液８００ｃｃ中に投入した。５０℃
で１０日間放置して結晶化を行った。結晶化終了後、得
られた成形体と母液を分離して、成形体に付着した水酸
化ナトリウム及び水酸化カリウムなどを十分に水で洗浄
した後に、１１０℃で乾燥した。Ｘ線回折によって結晶
解析を行った結果、Ｘ型ゼオライト以外に不純物である
Ａ型のピークが観測された。Comparative Example 2 Low silica X-type zeolite powder 555 used in Example 1
56 g of kaolin-type clay calcined at 600 ° C. for 2 hours
g, and 17 g of carboxymethylcellulose as a granulation aid, and an appropriate amount of water was added to enable extrusion molding, and the mixture was sufficiently mixed and kneaded to obtain a kneaded product.
800 cc of an aqueous solution containing 105 g of sodium hydroxide and 49 g of potassium hydroxide after forming into a diameter of 1.5 mm, drying at 110 ° C., immersing in water, substituting adsorbed gas such as air with water as much as possible. I put it in. 50 ° C
It was left for 10 days to crystallize. After completion of crystallization, the obtained molded product and mother liquor were separated, and sodium hydroxide, potassium hydroxide and the like adhering to the molded product were sufficiently washed with water, and then dried at 110 ° C. As a result of crystal analysis by X-ray diffraction, an A-type peak, which is an impurity, was observed in addition to the X-type zeolite.
Claims (1)
Ｘ型ゼオライト成形体を製造するに際し、シリカ／アル
ミナモル比が２．５より低いＸ型ゼオライト粉末、カオ
リン型粘土、水酸化ナトリウム及び水酸化カリウムを含
む成形体を結晶化することを特徴とするＸ型ゼオライト
成形体の製造方法。1. When producing an X-type zeolite compact having a silica / alumina molar ratio of less than 2.5, an X-type zeolite powder having a silica / alumina molar ratio of less than 2.5, kaolin clay, sodium hydroxide and hydroxide. A method for producing an X-type zeolite molded body, which comprises crystallizing a molded body containing potassium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3349742A JP3066430B2 (en) | 1991-12-10 | 1991-12-10 | Method for producing zeolite X-shaped compact |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3349742A JP3066430B2 (en) | 1991-12-10 | 1991-12-10 | Method for producing zeolite X-shaped compact |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05163015A true JPH05163015A (en) | 1993-06-29 |
| JP3066430B2 JP3066430B2 (en) | 2000-07-17 |
Family
ID=18405797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3349742A Expired - Fee Related JP3066430B2 (en) | 1991-12-10 | 1991-12-10 | Method for producing zeolite X-shaped compact |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3066430B2 (en) |
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