JP3066850B2 - Binderless X-type zeolite molding and method for producing the same - Google Patents
Binderless X-type zeolite molding and method for producing the sameInfo
- Publication number
- JP3066850B2 JP3066850B2 JP4342398A JP34239892A JP3066850B2 JP 3066850 B2 JP3066850 B2 JP 3066850B2 JP 4342398 A JP4342398 A JP 4342398A JP 34239892 A JP34239892 A JP 34239892A JP 3066850 B2 JP3066850 B2 JP 3066850B2
- Authority
- JP
- Japan
- Prior art keywords
- type zeolite
- clay
- type
- binderless
- molded body
- 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.)
- Expired - Fee Related
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は粘土結合剤をほとんど含
まない、バインダーレスＸ型ゼオライト成形体およびそ
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 binderless X-type zeolite compact containing almost no clay binder and a method for producing the same.
【０００２】[0002]
【従来の技術】バインダーレスＸ型ゼオライト成形体の
製造法の一つとして、ＮａＸ型ゼオライト粉末とカオリ
ン型粘土と水酸化ナトリウムとを混合し、成形し、えら
れた成形体を乾燥し、焼成し、水酸化ナトリウムと珪酸
ナトリウムとの混合水溶液と接触させることによってカ
オリン型粘土をＸ型ゼオライトに転化させる方法が知ら
れている。2. Description of the Related Art As one method for producing a binderless X-type zeolite compact, a NaX-type zeolite powder, kaolin-type clay and sodium hydroxide are mixed and molded, and the obtained compact is dried and calcined. A method of converting kaolin-type clay into X-type zeolite by contacting with a mixed aqueous solution of sodium hydroxide and sodium silicate is known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、この方
法を含めこれまでのバインダーレス化技術では成形体中
のＸ型ゼオライト含有量を高くすることはかなり困難で
あって精々９５％程度にしかできなかった。However, with the conventional binderless technology including this method, it is very difficult to increase the content of the X-type zeolite in the molded product, and it is only possible to reduce it to about 95% at most. Was.
【０００４】本発明の目的は、このような従来の方法で
製造したものよりも、Ｘ型ゼオライト含有量が高く、従
って高い吸着特性を有するバインダーレスＸ型ゼオライ
ト成形体およびその製造方法を提供することにある。[0004] It is an object of the present invention to provide a binderless X-type zeolite compact having a higher content of X-type zeolite than that produced by such a conventional method and thus having high adsorption characteristics, and a method for producing the same. It is in.
【０００５】[0005]
【課題を解決するための手段】本発明のバインダーレス
Ｘ型ゼオライト成形体は、Ｘ型ゼオライト含有量が９８
ｗｔ％以上である点に特徴を有する。The binderless X-type zeolite compact of the present invention has an X-type zeolite content of 98%.
It is characterized in that it is not less than wt%.
【０００６】該ゼオライト成形体は、合成ＮａＸ型ゼオ
ライト粉末とカオリン型粘土と水酸化ナトリウムとを混
合し、成形し、えられた成形体を乾燥し、焼成し、水酸
化ナトリウムと珪酸ナトリウムとの混合水溶液と接触さ
せることによってバインダーレスＸ型ゼオライト成形体
を製造するにあたり、該カオリン型粘土として平均粒子
径１．５μｍ以上のものを用いることによって製造する
ことができる。The zeolite compact is prepared by mixing a synthetic NaX-type zeolite powder, kaolin-type clay and sodium hydroxide, molding, drying and calcining the obtained compact, and forming a mixture of sodium hydroxide and sodium silicate. In producing a binderless X-type zeolite molded article by contacting with a mixed aqueous solution, it can be produced by using a kaolin-type clay having an average particle diameter of 1.5 μm or more.
【０００７】このカオリン型粘土の平均粒子径が小さす
ぎると、えられる成形体のＸ型ゼオライト含有率が低下
する。これは、粘土の水酸化ナトリウムと珪酸ナトリウ
ムとの混合水溶液への溶解、ゼオライト結晶核の生成お
よびその成長が成形体の表面から進行し、粘土の粒子径
が小さいとその進行が速すぎて成形体の細孔が表面で潰
れ、成形体内部への結晶化液の拡散が妨げられ、成形体
内部に粘土が取り残され、かつ、Ｘ型ゼオライト以外の
例えばＡ型ゼオライト、Ｐ型ゼオライトなどが生成する
ことによるものと考えられる。また、えられる成形体の
吸着容量が低下するが、それはＸ型ゼオライト含有量が
低くなることによるだけでなく、細孔容積が小さくなっ
てガスが拡散されにくくなることもその原因であると考
えられる。いっぽう、粘土の平均粒子径が１．５μｍ以
上のように大きくなると、ゼオライト結晶と粘土との間
にできる細孔容積も大きくなり、また、粘土の溶解およ
びそれに次ぐゼオライト結晶核の析出はそれほど速くな
いので、成形体内部へ結晶化液が十分拡散し、均一に結
晶化され、高純度なバインダーレスＸ型ゼオライト成形
体が得られる。通常入手することのできるカオリン型粘
土の平均粒子径がもっとも大きいものは約５μｍのもの
であるが、本発明の成形体の製造にはそのように大きい
ものも好適に使用することができる。If the average particle size of the kaolin-type clay is too small, the X-type zeolite content of the obtained molded article will decrease. This is because the dissolution of clay in a mixed aqueous solution of sodium hydroxide and sodium silicate, the formation and growth of zeolite crystal nuclei proceed from the surface of the compact, and if the clay particle size is small, the progress is too fast to form the compact. The pores of the body are crushed on the surface, diffusion of the crystallization liquid into the inside of the molded body is hindered, clay is left inside the molded body, and other than the X-type zeolite, for example, A-type zeolite, P-type zeolite, etc. are generated. It is thought that it is due to doing. In addition, the adsorption capacity of the obtained molded body is decreased, not only because the X-type zeolite content is reduced, but also because the pore volume is reduced and the gas is difficult to diffuse. Can be On the other hand, when the average particle size of the clay is as large as 1.5 μm or more, the pore volume formed between the zeolite crystal and the clay also increases, and the dissolution of the clay and the subsequent precipitation of the zeolite crystal nucleus are so fast. Since there is no such material, the crystallization liquid is sufficiently diffused into the inside of the molded body, uniformly crystallized, and a high-purity binderless X-type zeolite molded body can be obtained. Usually, the largest available kaolin-type clay having an average particle diameter of about 5 μm is used, but such a large kaolin-type clay can be suitably used for producing the molded article of the present invention.
【０００８】上記バインダーレスＸ型ゼオライト成形体
の製造方法の好ましい実施態様は、合成Ｘ型ゼオライト
粉末、該合成Ｘ型ゼオライト粉末との合計に対して２０
〜２５ｗｔ％の平均粒子径１．５μｍ以上のカオリン型
粘土および該カオリン型粘土中のアルミニウムに対しＮ
ａＯＨ／Ａｌモル比０．２５以下の水酸化ナトリウムか
らなる混合物を成形し、得られた成形体を乾燥し、焼成
した後、濃度１．５〜２．５ｍｏｌ／ｌの水酸化ナトリ
ウムと０．１〜０．２ｍｏｌ／ｌの珪酸ナトリウムとの
混合水溶液と接触させて成形体中のカオリン型粘土を純
粋なＸ型ゼオライトに転化させることを特徴とするバイ
ンダーレスＸ型ゼオライト成形体の製造方法、であり、
以下それについてさらに詳しく説明する。[0008] In a preferred embodiment of the method for producing a binderless X-type zeolite molded product, the total amount of the synthetic X-type zeolite powder and the synthetic X-type zeolite powder is 20%.
-25 wt% of kaolin-type clay having an average particle size of 1.5 µm or more and aluminum in the kaolin-type clay
A mixture composed of sodium hydroxide having an aOH / Al molar ratio of 0.25 or less is molded, the obtained molded body is dried and calcined, and then sodium hydroxide having a concentration of 1.5 to 2.5 mol / l and 0.1 mol / l are added. A method for producing a binderless X-type zeolite molded body, comprising contacting an aqueous solution of 1 to 0.2 mol / l with sodium silicate to convert kaolin-type clay in the molded body into pure X-type zeolite; And
Hereinafter, this will be described in more detail.
【０００９】これに用いられる合成ＮａＸ型ゼオライト
は、公知の方法、すなわちアルミン酸ナトリウムと珪酸
ナトリウムとから合成すればよい。The synthetic NaX-type zeolite used for this may be synthesized by a known method, that is, from sodium aluminate and sodium silicate.
【００１０】ＮａＸ型ゼオライト粉末とカオリン型粘土
と水酸化ナトリウムとの混合物に、押出し成形動力を低
減させるための潤滑剤を加え、水分の調整をしながら全
てが均一になるよう混合混練した後、十分捏和する。こ
のように、未焼成の粘土を用いて造粒成形することによ
り成形体の物理的強度を高めることができ、成形後焼成
によって反応性に富むメタカオリン型粘土に転移させる
ことにより、高純度なバインダーレスＸ型ゼオライト成
形体を得ることができる。[0010] To a mixture of NaX type zeolite powder, kaolin type clay and sodium hydroxide, a lubricant for reducing the power of extrusion molding is added, and after mixing and kneading so that all become uniform while adjusting the water content, Knead well. As described above, the physical strength of the molded body can be increased by granulating and molding using the unfired clay, and the high-purity binder can be obtained by transferring to a metakaolin-type clay having high reactivity by firing after molding. A less X-type zeolite molded article can be obtained.
【００１１】また、添加するカオリン型粘土が、ＮａＸ
型ゼオライト粉末との合計に対して２０ｗｔ％に満たな
い場合は、造粒成形性が低下するばかりでなく、十分な
物理的強度を有する成形体を得ることが困難である。い
っぽう、２５ｗｔ％をこえると天然物である粘土中に存
在する不純物、例えば石英質あるいは酸化鉄などの量が
増えることとなり高いＸ型ゼオライト純分を有する成形
体を得ることができない。Further, the kaolin type clay to be added is NaX
If the amount is less than 20 wt% with respect to the total amount of the zeolite powder, not only the granulation moldability is reduced, but also it is difficult to obtain a molded body having sufficient physical strength. On the other hand, if the content exceeds 25 wt%, the amount of impurities, such as quartz or iron oxide, present in the clay, which is a natural product, increases, and a molded article having a high pure X-type zeolite cannot be obtained.
【００１２】また、水酸化ナトリウムの量はカオリン型
粘土中のアルミニウムに対し、ＮａＯＨ／Ａｌモル比
０．２５以下でなければならない。この比が０．２５を
こえると、成形後の乾燥時にＡ型ゼオライトやヒドロキ
シソ−ダライトのような不純物が生成することもある。
これは、Ｘ型ゼオライトの結晶化温度領域にＡ型ゼオラ
イトの結晶化温度領域が含まれているからである。Further, the amount of sodium hydroxide must be not more than 0.25 in a molar ratio of NaOH / Al with respect to aluminum in the kaolin-type clay. If this ratio exceeds 0.25, impurities such as A-type zeolite and hydroxysodalite may be formed during drying after molding.
This is because the crystallization temperature region of the A-type zeolite is included in the crystallization temperature region of the X-type zeolite.
【００１３】このようにして十分捏和した、造粒物を押
出し成形し、たとえば１．５ｍｍ柱状の押出し成形体に
する。もっとも、球状あるいは顆粒状でもかまわない。The granulated product sufficiently kneaded in this manner is extruded and formed into, for example, a 1.5 mm columnar extruded product. However, it may be spherical or granular.
【００１４】所望の形に成形した後、通常の温度で成形
体中に含まれる水分を約４０％程度まで下げるよう乾燥
する。次いでこの成形体をカオリン型粘土が焼結し、メ
タカオリン型粘土に転移する温度５５０℃以上、好まし
くは６００℃で焼成しカオリン型粘土を焼結させるとと
もに、カオリン型粘土中に含まれる有機物、押出し動力
を低減させるために添加した潤滑剤などを分解燃焼させ
て不純物をまったく含まない成形体とする。After molding into a desired shape, drying is carried out at a normal temperature to reduce the water content in the molded body to about 40%. Next, the molded body is sintered at a temperature of 550 ° C. or higher, preferably 600 ° C., at which the kaolin-type clay is sintered and transformed into metakaolin-type clay, to sinter the kaolin-type clay, and to extrude the organic substances contained in the kaolin-type clay and extrude the same. A lubricant or the like added to reduce the power is decomposed and burned to form a compact containing no impurities.
【００１５】焼成した成形体を飽和水分吸着量程度まで
加湿する。この操作は、必須ではないが、結晶化工程で
水酸化ナトリウムおよび珪酸ナトリウム混合溶液との接
触において急激な水分吸着あるいはそれに伴う発熱など
でおこりうる成形体のヒビ割れ、剥離などを防止するに
は好ましい操作である。The fired compact is humidified to a saturated moisture adsorption amount. This operation is not essential, but in order to prevent cracking, peeling, etc. of the molded body which may occur due to rapid moisture adsorption or accompanying heat generation in contact with the mixed solution of sodium hydroxide and sodium silicate in the crystallization step. This is the preferred operation.
【００１６】以上のような操作で成形し、焼成し、加湿
した成形体を濃度１．５〜２．５ｍｏｌ／ｌの水酸化ナ
トリウムおよび０．１〜０．２ｍｏｌ／ｌの珪酸ナトリ
ウム混合水溶液に浸漬し、通常Ｘ型ゼオライトを合成す
る温度条件、すなわち４０℃で１時間の熟成操作をした
後、９０℃に昇温して結晶化させる。The molded article which has been molded, fired and humidified by the above-described operation is converted into a mixed aqueous solution of sodium hydroxide having a concentration of 1.5 to 2.5 mol / l and sodium silicate having a concentration of 0.1 to 0.2 mol / l. After immersion and aging for 1 hour at a temperature condition for synthesizing an X-type zeolite, that is, at 40 ° C., the temperature is raised to 90 ° C. for crystallization.
【００１７】この工程における水酸化ナトリウムの濃度
を２．５ｍｏｌ／ｌより高くすれば結晶化時間は短縮さ
れるが、成形体表面に近いほど粘土の溶解が速く進み、
小さいゼオライト結晶核が生成し、結晶化することによ
って、成形体表面から細孔が潰され、その結果成形体内
部への結晶化液の拡散が妨げられ、完全に均一な結晶化
ができないばかりか、成形体内部に粘土が取り残される
こともある。また、時として不純物、例えばＡ型ゼオラ
イトやＰ型ゼオライトが生成することもある。従って得
られる成形体中のＸ型ゼオライト純分は低いものとな
る。いっぽう、水酸化ナトリウムの濃度を１．５ｍｏｌ
／ｌ未満にすると結晶化速度が遅くなり大きい結晶を生
成できる反面、結晶化時間が必要以上に長くなり、不純
物などができやすく好ましくない。また、珪酸ナトリウ
ムの濃度は、０．１〜０．２ｍｏｌ／ｌの範囲でよい。
これは、成形体中のＳｉＯ2／Ａｌ2Ｏ3モル比２のカオ
リン型粘土を、ＳｉＯ2／Ａｌ2Ｏ3モル比２．５のＸ型
ゼオライトに転化させるだけの量が水酸化ナトリウムと
の混合水溶液中にあれば十分であることを意味する。If the concentration of sodium hydroxide in this step is higher than 2.5 mol / l, the crystallization time is shortened, but the closer to the surface of the molded body, the faster the dissolution of clay proceeds,
The formation and crystallization of small zeolite crystal nuclei cause the pores to be crushed from the surface of the molded product, thereby preventing the diffusion of the crystallization liquid into the molded product and not only preventing uniform crystallization. However, the clay may be left inside the molded body. In some cases, impurities such as A-type zeolite and P-type zeolite are generated. Therefore, the X-type zeolite pure content in the obtained compact is low. Meanwhile, the concentration of sodium hydroxide was 1.5 mol
If the ratio is less than / l, the crystallization speed becomes slow and a large crystal can be produced, but the crystallization time becomes unnecessarily long and impurities are easily formed, which is not preferable. Further, the concentration of sodium silicate may be in the range of 0.1 to 0.2 mol / l.
This a SiO 2 / Al 2 O 3 molar ratio of 2 kaolin clay in the shaped body, the amount of only be converted into X-type zeolite of SiO 2 / Al 2 O 3 molar ratio of 2.5 and sodium hydroxide In a mixed aqueous solution of
【００１８】熟成の条件は４０℃以下、１時間以上であ
れば問題なくあまり制約されない。結晶化温度は９０℃
以上、結晶化時間は８時間以上であればよいが、あまり
高すぎる温度、例えば９５℃以上になるとＰ型ゼオライ
ト生成領域になり好ましくない。また、時間についても
同様に必要以上長くすることはない。The conditions for aging are not particularly limited as long as they are 40 ° C. or lower and 1 hour or longer without any problem. Crystallization temperature is 90 ° C
As described above, the crystallization time may be 8 hours or more. However, if the temperature is too high, for example, 95 ° C. or more, the region becomes a P-type zeolite generation region, which is not preferable. Similarly, the time is not made longer than necessary.
【００１９】このようにして、添加したカオリン型粘土
が結晶化すなわち実質的に１００％Ｘ型ゼオライトへの
転化を終了した成形体を水酸化ナトリウムおよび珪酸ナ
トリウム混合溶液中から取出し、水あるいは温水で十分
洗浄した後、成形体を通常の温度で乾燥する。活性化す
るには、この乾燥品をさらに焼成すればよい。In this manner, the molded body in which the added kaolin-type clay has been crystallized, that is, substantially converted to 100% X-type zeolite, is taken out of the mixed solution of sodium hydroxide and sodium silicate, and is taken out with water or hot water. After sufficient washing, the molded body is dried at a normal temperature. For activation, the dried product may be further fired.
【００２０】[0020]
【作用】カオリン型粘土の平均粒子径が小さすぎるとバ
インダーレス化率が低下し、成形体の吸着容量が低下す
る理由は、該粘土の水酸化ナトリウムおよび珪酸ナトリ
ウム混合溶液への溶解およびそれに次ぐゼオライト結晶
核の析出が速くなることにあると考えられる。すなわ
ち、粘土の溶解、ゼオライト結晶核の生成およびその成
長は成形体の表面から進行し、粘土の粒子径が小さいと
その進行が速すぎて成形体の細孔が表面で潰れ、成形体
内部への結晶化液の拡散が妨げられ、成形体内部に粘土
が取り残され、均一に結晶化がされず、それによって高
純度なバインダーレスＸ型ゼオライト成形体を得ること
ができなくなるものと考えられる。さらには、不純物す
なわちＸ型ゼオライト以外の例えばＡ型ゼオライト、Ｐ
型ゼオライトなどの生成を伴うことも考えられる。この
ように平均粒子径の小さい粘土を用いた成形体をバイン
ダーレス化した場合、結晶含有量が低下するばかりでな
く、吸着剤の細孔容積が小さくなりガスの拡散が悪くな
ることも考えられる。それに対し本発明におけるように
粘土の平均粒子径が１．５μｍ以上と大きくなると、ゼ
オライト結晶と粘土との間にできる細孔容積も大きくな
り、また、粘土の溶解およびそれに次ぐゼオライト結晶
核の析出がそれほど速くないので、成形体内部へ結晶化
液が十分拡散し、均一に結晶化して、高純度なバインダ
ーレスＸ型ゼオライト成形体を得ることができる。When the average particle size of the kaolin-type clay is too small, the binderless conversion rate is reduced, and the adsorption capacity of the molded body is reduced because the clay is dissolved in a mixed solution of sodium hydroxide and sodium silicate and the second. It is considered that the precipitation of zeolite crystal nuclei is accelerated. That is, the dissolution of the clay, the formation of the zeolite crystal nuclei, and the growth thereof proceed from the surface of the molded body. It is considered that the diffusion of the crystallization liquid is hindered, the clay is left inside the molded body, and the crystallization is not uniformly performed, whereby a high-purity binderless X-type zeolite molded body cannot be obtained. Furthermore, impurities, ie, A-type zeolites other than X-type zeolites, P-type zeolites
It is also conceivable that this involves the formation of zeolite. When the molded body using the clay having a small average particle diameter is made binderless, not only the crystal content is reduced, but also the pore volume of the adsorbent becomes small and gas diffusion may be deteriorated. . On the other hand, when the average particle size of the clay is as large as 1.5 μm or more as in the present invention, the pore volume formed between the zeolite crystal and the clay is also large, and the dissolution of the clay and the subsequent precipitation of the zeolite crystal nuclei are performed. Is not so fast, the crystallization liquid sufficiently diffuses into the inside of the molded product, and is uniformly crystallized, so that a high-purity binderless X-type zeolite molded product can be obtained.
【００２１】[0021]
【発明の効果】以上の説明からあきらかなように、本発
明のバインダーレスＸ型ゼオライト成形体は、Ｘ型ゼオ
ライト成形体含有率が高く、したがって吸着容量が高
い。また、本発明の製造方法によれば、Ｘ型ゼオライト
成形体含有率の高いバインダーレスＸ型ゼオライト成形
体を容易にうることができる。As is apparent from the above description, the binderless X-type zeolite molded article of the present invention has a high content of the X-type zeolite molded article, and therefore has a high adsorption capacity. Further, according to the production method of the present invention, a binderless X-type zeolite molded article having a high content of the X-type zeolite molded article can be easily obtained.
【００２２】[0022]
【実施例】以下、実施例および比較例によって、発明の
効果を具体的に説明する。EXAMPLES The effects of the present invention will be specifically described below with reference to examples and comparative examples.
【００２３】使用したカオリン型粘土は、不純物含有量
の少ないジョ−ジアカオリンである。The kaolin-type clay used is jodiakaolin having a low impurity content.
【００２４】Ｘ型ゼオライト結晶含有率は水分吸着量に
よって、また、不純物の有無はＸ線回折による結晶解析
によって測定した。The content of X-type zeolite crystals was measured by the amount of absorbed water, and the presence or absence of impurities was measured by crystal analysis by X-ray diffraction.
【００２５】＜水分吸着量＞バインダーレス化した成形
体を３５０℃で６０分間活性化し、冷却後、温度２５
℃、相対湿度８０％のデシケ−タ−中で１６時間以上放
置し、成形体に吸着された平衡水分吸着量を測定した。<Amount of Moisture Adsorption> The binderless molded body was activated at 350 ° C. for 60 minutes, cooled, and cooled to a temperature of 25 ° C.
The mixture was allowed to stand for 16 hours or more in a desiccator at 80 ° C. and a relative humidity of 80%, and the amount of equilibrium water adsorbed on the molded body was measured.
【００２６】以下の具体例における「部」は重量によ
る。"Parts" in the following specific examples are by weight.
【００２７】実施例１ 合成Ｎａ−Ｘ型ゼオライト粉末１００部に対して、平均
粒子径４．８μｍのカオリン型粘土２５部（Ａｌ含有
率：２４ｗｔ％）、水酸化ナトリウム２部（ＮａＯＨ／
Ａｌモル比０．２２）を混合し、さらに潤滑剤としてＣ
ＭＣ（カルボキシメチルセルロ−ス）３部を加えた後、
押出し成形しうるよう水分の調整を行ないながらミック
スマ−ラ−造粒器で十分捏和した。このものを二軸型押
出し機で直径１．５ｍｍの成形体に押出し成形し、乾燥
した後、長さ１０ｍｍ程度に整粒した。次いで、マッフ
ル炉を用いて６００℃雰囲気中で２時間焼成してカオリ
ン型粘土を焼結させるとともに、カオリン型粘土中に含
まれる有機物あるいは不純物、また、押出し動力を低減
させるために添加した潤滑剤などを分解燃焼させた後、
大気中で冷却して水分が約３５％程度になるよう加湿し
た。この成形体１００ｇ（活性化重量）をステンレス製
反応容器中で濃度２．０ｍｏｌ／ｌの水酸化ナトリウム
および０．２ｍｏｌ／ｌ珪酸ナトリウムの混合溶液に浸
漬して４０℃で１時間熟成し、さらに９０℃に昇温した
後、１０時間放置して結晶化を完結させ、水で十分洗浄
し乾燥した。Example 1 25 parts of kaolin-type clay having an average particle diameter of 4.8 μm (Al content: 24 wt%) and 2 parts of sodium hydroxide (NaOH / 100 parts) were prepared based on 100 parts of synthetic Na-X type zeolite powder.
Al molar ratio of 0.22) and C as a lubricant.
After adding 3 parts of MC (carboxymethyl cellulose),
The mixture was kneaded sufficiently with a mix muller while adjusting the water content so that it could be extruded. This was extruded into a molded body having a diameter of 1.5 mm by a twin-screw extruder, dried, and sized to a length of about 10 mm. Next, the kaolin-type clay is sintered by firing in a muffle furnace in a 600 ° C. atmosphere for 2 hours, and organic substances or impurities contained in the kaolin-type clay, and a lubricant added for reducing the extrusion power. After decomposing and burning
It was cooled in the air and humidified so that the water content was about 35%. 100 g (activated weight) of the molded body was immersed in a mixed solution of 2.0 mol / l sodium hydroxide and 0.2 mol / l sodium silicate in a stainless steel reaction vessel and aged at 40 ° C. for 1 hour. After the temperature was raised to 90 ° C., the solution was left for 10 hours to complete crystallization, washed sufficiently with water, and dried.
【００２８】上述の方法で水分吸着量を測定した結果、
３４．５％であった。合成Ｎａ−Ｘゼオライト結晶粉末
の平衡水分吸着量３５．０％を基準にして該成形体の結
晶含有率は９８．６％と求まる。As a result of measuring the amount of adsorbed water by the above method,
34.5%. Based on the equilibrium water adsorption of the synthetic Na-X zeolite crystal powder of 35.0%, the crystal content of the compact is determined to be 98.6%.
【００２９】また、このものをＸ線回折による結晶解析
の結果、他の相すなわち不純物は認められなかった。As a result of X-ray diffraction analysis of this product, no other phase, that is, no impurities were found.
【００３０】実施例２〜９ 比較例１〜６ 実施例１と同様な操作によって、バインダーレスＸ型ゼ
オライト成形体を調整した。いくらかの例では粘土結合
剤の平均粒子径、また水酸化ナトリウムと珪酸ナトリウ
ム溶液の濃度を変えて調整した。変更した条件および結
晶含有率を上述の方法で測定した結果を表１に示す。Examples 2 to 9 Comparative Examples 1 to 6 A binderless X-type zeolite compact was prepared in the same manner as in Example 1. In some cases, the average particle size of the clay binder and the concentration of the sodium hydroxide and sodium silicate solutions were adjusted. Table 1 shows the results obtained by measuring the changed conditions and the crystal content by the above method.
【００３１】[0031]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平３−295805（ＪＰ，Ａ) 特開 昭61−222919（ＪＰ，Ａ) 特開 昭57−149818（ＪＰ，Ａ) 特開 平２−6846（ＪＰ，Ａ) 特公 昭39−11602（ＪＰ，Ｂ１) 米国特許3906076（ＵＳ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 3/20 - 39/54 ＣＡ（ＳＴＮ) 特許ファイル（ＰＡＴＯＬＩＳ)──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-3-295805 (JP, A) JP-A-61-222919 (JP, A) JP-A-57-149818 (JP, A) JP-A-2- 6846 (JP, A) JP-B-39-11602 (JP, B1) US Patent 3,906,076 (US, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01B 3/20-39/54 CA (STN) Patent file (PATOLIS)
Claims (2)
あることを特徴とするバインダーレスＸ型ゼオライト成
形体。1. A binderless X-type zeolite molded product having an X-type zeolite content of 98% by weight or more.
粘土と水酸化ナトリウムとを混合し、成形し、えられた
成形体を乾燥し、焼成し、水酸化ナトリウムと珪酸ナト
リウムとの混合水溶液と接触させることによってバイン
ダーレスＸ型ゼオライト成形体を製造するにあたり、該
カオリン型粘土として平均粒子径１．５μｍ以上のもの
を用いることを特徴とする、バインダーレスＸ型ゼオラ
イト成形体の製造方法。2. A synthetic NaX-type zeolite powder, a kaolin-type clay and sodium hydroxide are mixed and molded, the obtained molded body is dried and calcined, and is contacted with a mixed aqueous solution of sodium hydroxide and sodium silicate. A method for producing a binderless X-type zeolite molded body, wherein a kaolin-type clay having an average particle diameter of 1.5 μm or more is used for producing a binderless X-type zeolite molded body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4342398A JP3066850B2 (en) | 1992-12-22 | 1992-12-22 | Binderless X-type zeolite molding and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4342398A JP3066850B2 (en) | 1992-12-22 | 1992-12-22 | Binderless X-type zeolite molding and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06183725A JPH06183725A (en) | 1994-07-05 |
| JP3066850B2 true JP3066850B2 (en) | 2000-07-17 |
Family
ID=18353418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4342398A Expired - Fee Related JP3066850B2 (en) | 1992-12-22 | 1992-12-22 | Binderless X-type zeolite molding and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3066850B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100504000C (en) * | 2006-01-20 | 2009-06-24 | 哈尔滨工业大学 | Concrete beam with transition region and prestressed concrete beam with or without cement |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2766476B1 (en) * | 1997-07-22 | 1999-09-03 | Ceca Sa | IMPROVED ZEOLITIC ADSORBENT FOR THE SEPARATION OF AIR GASES AND PROCESS FOR OBTAINING SAME |
| FR2766475B1 (en) * | 1997-07-22 | 1999-09-03 | Ceca Sa | PROCESS FOR OBTAINING GRANULAR BODIES IN LSX ZEOLITE WITH LOW RATE OF INERT BINDER |
| FR2803282B1 (en) | 2000-01-04 | 2002-02-15 | Ceca Sa | ZEOLITES X EXCHANGED IN PARTICULAR TO LITIUM, THEIR PREPARATION PROCESS AND THEIR USE AS NITROGEN ADSORBENTS IN THE SEPARATION OF AIR GASES |
| JP4686889B2 (en) * | 2000-04-20 | 2011-05-25 | 東ソー株式会社 | Method for purifying hydrogen gas |
| FR2811313B1 (en) | 2000-07-07 | 2002-08-30 | Ceca Sa | PROCESS FOR THE PREPARATION OF ZEOLITES X AND LSX AGGLOMERATED AND EXCHANGED WITH LITHIUM |
| US6506236B2 (en) † | 2001-03-28 | 2003-01-14 | Air Products And Chemicals, Inc. | Process for reducing the level of carbon dioxide in a gaseous mixture |
| US7820869B2 (en) * | 2008-06-30 | 2010-10-26 | Uop Llc | Binderless adsorbents and their use in the adsorptive separation of para-xylene |
| US8992884B2 (en) * | 2009-11-30 | 2015-03-31 | Chevron U.S.A. Inc. | Preparation of X zeolite |
| JP2011194337A (en) * | 2010-03-19 | 2011-10-06 | Ube Industries Ltd | Agent and method for removing hydrofluorocarbon |
| DE102012020217A1 (en) * | 2012-10-15 | 2014-04-17 | Chemiewerk Bad Köstritz GmbH | Binder-free compact zeolitic moldings and process for their preparation |
| EP3422363B1 (en) | 2016-02-26 | 2021-04-21 | Ebara Corporation | Method for processing radioactive iodine-containing fluid |
| CN116474717A (en) * | 2022-01-15 | 2023-07-25 | 中国石油化工股份有限公司 | Cascade pore canal composite molecular sieve adsorbent and preparation method thereof |
-
1992
- 1992-12-22 JP JP4342398A patent/JP3066850B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100504000C (en) * | 2006-01-20 | 2009-06-24 | 哈尔滨工业大学 | Concrete beam with transition region and prestressed concrete beam with or without cement |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06183725A (en) | 1994-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3066850B2 (en) | Binderless X-type zeolite molding and method for producing the same | |
| US4818508A (en) | Process for preparing molecular sieve bodies | |
| EA001175B1 (en) | Method for obtaining lsx zeolite granular agglomerates with low inert binding material ratio | |
| JP3066430B2 (en) | Method for producing zeolite X-shaped compact | |
| JPH11513969A (en) | Method for producing molecular sieve complex compound | |
| JP2002519188A (en) | Molecular sieve adsorbent for gas purification and method for producing the same | |
| CN111573650B (en) | Method for preparing mesoporous carbon powder with high specific surface area | |
| JP2782744B2 (en) | Method for producing binderless zeolite molded body | |
| JPH04198011A (en) | Production of molded article of binderless x type zeolite | |
| JPH03275527A (en) | Porous silica glass powder | |
| JPH03295805A (en) | X-type zeolite molded body and its production | |
| JP3066427B2 (en) | High-strength A-type zeolite compact and method for producing the same | |
| JP2005219955A (en) | Crystalline inorganic porous material and its production method | |
| JP3518319B2 (en) | Activated low silica X-type zeolite compact | |
| JPH06183727A (en) | Cax type zeolite molding and its production | |
| JP3772412B2 (en) | Low-abrasion zeolite bead molded body and method for producing the same | |
| JPH03146414A (en) | Production of porous binderless 3a-type zeolite formed body | |
| JP2000211915A (en) | Formed compact containing low-silica x type zeolite, its production and use thereof | |
| JP3334664B2 (en) | Adsorbent for gas separation | |
| JPH1053410A (en) | Production of low-silica x-type zeolite | |
| JP2004143035A (en) | Crystalline inorganic porous material and its producing method | |
| JP3733655B2 (en) | Calcium X-type zeolite compact and method for producing the same | |
| JPH07172820A (en) | A type zeolite molded body and its production | |
| JP2002085966A (en) | Carbon dioxide absorbing material, its production method and combustion equipment | |
| RU2218304C2 (en) | Method to produce synthetic zeolite of x-type |
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: 20000411 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090519 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090519 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100519 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110519 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120519 Year of fee payment: 12 |
|
| LAPS | Cancellation because of no payment of annual fees |