JPH11314913A - High strength low wear zeolite granule and its production - Google Patents
High strength low wear zeolite granule and its productionInfo
- Publication number
- JPH11314913A JPH11314913A JP10124588A JP12458898A JPH11314913A JP H11314913 A JPH11314913 A JP H11314913A JP 10124588 A JP10124588 A JP 10124588A JP 12458898 A JP12458898 A JP 12458898A JP H11314913 A JPH11314913 A JP H11314913A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- clay
- strength
- parts
- wear
- 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.)
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- Separation Of Gases By Adsorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高強度低摩耗性ゼ
オライト粒状物及びその製造方法に関するものである。
さらに詳しくは、吸着分離剤として広く用いられ、例え
ば窒素と酸素とを主成分とする混合ガスから吸着法によ
って選択的に窒素を吸着させ、酸素を濃縮する圧力揺動
吸着法（以下、「ＰＳＡ法」という）用の吸着剤として
有用な結晶性の高強度低摩耗性ゼオライト粒状物及びそ
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 high-strength, low-wear zeolite granule and a method for producing the same.
More specifically, a pressure swing adsorption method (hereinafter, referred to as “PSA”), which is widely used as an adsorbent and separating agent, for example, selectively adsorbs nitrogen from a mixed gas containing nitrogen and oxygen as main components by an adsorption method and condenses oxygen. The present invention relates to a crystalline, high-strength, low-wear zeolite granule useful as an adsorbent for the "method") and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より、結晶性ゼオライトＸ型、Ａ型
を有効吸着成分として含有する成形体は広く吸着剤とし
て用いられている。特に最近は、空気中から酸素を濃縮
するための吸着剤としての用途が拡大し、優れた性能を
有する結晶性ゼオライト吸着剤が求められているため
に、ゼオライト成分として高吸着能を有する結晶性低シ
リカＸ型ゼオライトが注目されてきている。2. Description of the Related Art Conventionally, molded articles containing crystalline zeolites X and A as effective adsorbents have been widely used as adsorbents. In particular, recently, the use as an adsorbent for concentrating oxygen from the air is expanding, and a crystalline zeolite adsorbent with excellent performance is required. Low silica X-type zeolites have received attention.
【０００３】通常、吸着剤は成形され粒状物等の成形体
として用いられるが、一般にゼオライト成形体は、その
イオン交換可能なアルカリ金属カチオンを種々のイオン
に交換することにより、触媒特性や吸着特性を向上さ
せ、触媒や吸着剤として利用することができる。例え
ば、Ｘ型、Ａ型、あるいは低シリカＸ型ゼオライトのア
ルカリ金属カチオンの一部又は全部をＬｉイオンやＣａ
イオンに交換した粒状物は酸素ＰＳＡ剤として用いられ
ている。[0003] Usually, an adsorbent is molded and used as a molded product such as a granular material. In general, a zeolite molded product is obtained by exchanging the ion-exchangeable alkali metal cation with various ions to obtain a catalyst characteristic or an adsorption characteristic. And can be used as a catalyst or an adsorbent. For example, part or all of the alkali metal cation of X-type, A-type, or low-silica X-type zeolite may be converted to Li ion or Ca.
Granules exchanged with ions are used as oxygen PSA agents.
【０００４】殊にＰＳＡ剤等の吸着剤を製造する際、そ
の製品の強度特性及び吸着特性を推測するのに、成形体
中のカチオンをＬｉイオンやＣａイオン等に交換する前
すなわち、原料を混練、造粒成形、乾燥、焼成を行った
時点で、粒状物の耐圧強度及び耐摩耗性等を測定して強
度特性を、水分吸着量を測定して吸着特性を調べること
が行われる。すなわち、イオン交換前の焼成後で耐圧強
度及び耐摩耗性等の強度特性に優れるものは、イオン交
換、活性化後においても強度特性に優れており、また、
イオン交換前の焼成後で吸着能を表す指標の１つである
水分吸着能に優れるものは、イオン交換、活性化後にお
いても水分吸着能や窒素吸着能等の吸着特性に優れてい
ることから、ＰＳＡ剤等の製造途中でその最終製品の特
性を推測することができる。[0004] In particular, when producing an adsorbent such as a PSA agent, in order to estimate the strength characteristics and adsorption characteristics of the product, before exchanging cations in the molded body with Li ions, Ca ions, or the like, that is, the raw material is used. At the time of kneading, granulating, drying and baking, the strength characteristics are measured by measuring the pressure resistance and abrasion resistance of the granular material, and the adsorption characteristics are measured by measuring the amount of adsorbed moisture. That is, those having excellent strength characteristics such as pressure resistance and wear resistance after firing before ion exchange have excellent strength characteristics even after ion exchange and activation,
Those with excellent moisture adsorption capacity, which is one of the indices of adsorption capacity after calcination before ion exchange, have excellent adsorption properties such as water adsorption capacity and nitrogen adsorption capacity even after ion exchange and activation. , PSA agent, etc., during production, the characteristics of the final product can be estimated.
【０００５】ここで、ゼオライト成形体を製造する際に
用いられるバインダー成分を少なくすることにより吸着
能を有する成分が多くなり、成形体の吸着性能を向上さ
せることができる。また、目的の吸着物（以下、「被吸
着物」という）を効率的に吸脱着させるために、その大
きさあるいは径を小さくすることで高性能化できる。こ
れは成形体の径が大きくなると、境膜抵抗、拡散抵抗に
より吸脱着速度が低下し、吸着剤としての性能は低くな
るからである。[0005] Here, by reducing the amount of the binder component used in producing the zeolite molded article, the component having the adsorbing ability increases, and the adsorbing performance of the molded article can be improved. In addition, in order to efficiently adsorb and desorb a target adsorbate (hereinafter, referred to as an “adsorbed object”), the performance can be improved by reducing the size or diameter thereof. This is because, as the diameter of the molded body increases, the adsorption / desorption speed decreases due to the film resistance and diffusion resistance, and the performance as an adsorbent decreases.
【０００６】一方、吸着剤としての利用面における吸脱
着操作においては、振動又は相互接触が不可避であるた
め、耐圧強度、耐摩耗性といった強度特性が優れている
ことが求められている。しかしながら、成形体中のバイ
ンダー成分が少なかったり、その径が小さくなると、成
形体の強度は低下するため、小さな径でかつバインダー
成分の少ない吸着剤を高強度で調製することは極めて困
難であった。On the other hand, in the adsorption / desorption operation on the surface used as an adsorbent, since vibration or mutual contact is inevitable, it is required to have excellent strength characteristics such as pressure resistance and wear resistance. However, when the amount of the binder component in the molded body is small or the diameter thereof is small, the strength of the molded body is reduced. Therefore, it is extremely difficult to prepare an adsorbent having a small diameter and a small amount of the binder component with high strength. .
【０００７】例えば、バインダーとして粘土を使用する
と比較的強度特性に優れる粒状物を製造することがで
き、特にカオリン系やベントナイト系等の板状結晶を有
する粘土を使用した場合、耐圧強度や耐摩耗性等の強度
特性に、特に優れた粒状物を得ることができる。しか
し、ここでゼオライトとして低シリカＸ型ゼオライトを
用いると、その構造の不安定さゆえに、造粒成形、焼成
した際にゼオライトが熱劣化を受け、吸着特性が低下す
るという問題があった。For example, when clay is used as a binder, granules having relatively excellent strength characteristics can be produced. In particular, when a clay having a plate-like crystal such as kaolin or bentonite is used, compression strength and abrasion resistance are reduced. Granules having particularly excellent strength properties such as properties can be obtained. However, when a low silica X-type zeolite is used as the zeolite, there is a problem in that the zeolite is thermally degraded during granulation molding and firing due to the instability of its structure, and the adsorption characteristics are reduced.
【０００８】また、セピオライト系やアタパルジャイト
系等の針状結晶を有する粘土をバインダーとして使用
し、低シリカＸ型ゼオライトを造粒成形、焼成した場
合、熱劣化はほとんどなく、それ故粒状物の吸着特性に
は優れるが、耐圧強度及び耐摩耗性等の強度特性が得に
くく、また、強度特性を改善するために高バインダー量
で成形した場合、粒状物の強度特性は向上するが、吸着
能に大きく寄与するゼオライト成分含量が下がるために
吸着剤の単位体積当たりの吸着特性が低下するという問
題があった。Further, when clay having needle-like crystals such as sepiolite or attapulgite is used as a binder, and low silica X-type zeolite is granulated and fired, there is almost no thermal deterioration, and therefore adsorption of particulate matter Although excellent in properties, it is difficult to obtain strength properties such as pressure resistance and abrasion resistance, and when molded with a high binder amount to improve strength properties, the strength properties of granular materials are improved, but adsorption performance is reduced. Since the content of the zeolite component, which greatly contributes, is reduced, there is a problem that the adsorption characteristics per unit volume of the adsorbent are reduced.
【０００９】すなわち、強度物性に優れた吸着剤を得る
ことと吸着性能に優れた吸着剤を得ることとは相反する
ことが多く、両性能を併せ持つ性能の吸着剤が望まれて
いた。That is, obtaining an adsorbent excellent in strength physical properties and obtaining an adsorbent excellent in adsorption performance are often contradictory, and an adsorbent having both performances has been desired.
【００１０】[0010]
【発明が解決しようとする課題】本発明の目的は、この
ような背景及び課題において、従来の結晶性ゼオライト
成形体よりも吸着剤として優れた特性を有する、すなわ
ち水分等の吸着能が高く、径が小さく、さらに耐圧強度
及び耐摩耗性に優れた、高強度低摩耗性ゼオライト粒状
物及びその製造方法を提供することにある。殊にゼオラ
イト成分として結晶性の低シリカＸ型ゼオライトを用い
た場合であっても、このような吸着能、強度物性に優れ
たゼオライト粒状物及びその製造方法を提供することに
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide, in such a background and problems, characteristics that are superior to conventional crystalline zeolite molded articles as adsorbents, that is, they have a high ability to adsorb moisture and the like. It is an object of the present invention to provide a high-strength low-wear zeolite granule having a small diameter and excellent pressure resistance and wear resistance, and a method for producing the same. In particular, it is an object of the present invention to provide a zeolite granule excellent in such adsorptive capacity and strength properties even when a crystalline low silica X-type zeolite is used as a zeolite component, and a method for producing the same.
【００１１】[0011]
【課題を解決するための手段】本発明者等は上記課題を
解決するために、結晶性低シリカＸ型ゼオライト成形体
の造粒成形方法に関して鋭意検討を重ねた結果、その径
が小さく、バインダー量を少なくし、かつ吸着特性に優
れる成形体を高強度で耐摩耗性に優れたものとするに
は、バインダーの選択及びその組成が極めて重要である
ことを見出し、本発明を完成するに至った。Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on a method for granulating and molding a crystalline low-silica X-type zeolite. It has been found that the selection of the binder and the composition thereof are extremely important in order to reduce the amount and to make the molded article having excellent adsorption characteristics high in strength and excellent in wear resistance, and have completed the present invention. Was.
【００１２】以下に本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１３】まず、本発明の高強度低摩耗性ゼオライト
粒状物（以下、単に「本発明粒状物」と略す）について
説明する。First, the high-strength, low-wear zeolite granules of the present invention (hereinafter simply referred to as “the granules of the present invention”) will be described.
【００１４】ここで本明細書においては、「粒状物」は
柱状、ペレット状又は球状の成形体をも意味することが
あり、「直径」とは粒状物の中で最も短い部分の径（長
さ）を意味する。As used herein, the term "granular material" may also mean a columnar, pellet, or spherical molded article, and "diameter" may mean the diameter (length) of the shortest portion of the granular material. Means).
【００１５】本発明粒状物は、ゼオライト及びバインダ
ーからなり、高強度であり、低摩耗性であり、含有する
ゼオライト成分が全量の８０重量％以上であり、かつそ
の直径が０．５〜２．５ｍｍである。The granules of the present invention are composed of zeolite and a binder, have high strength, low abrasion, contain at least 80% by weight of the total amount of zeolite, and have a diameter of 0.5 to 2. 5 mm.
【００１６】ここで、高強度とは耐圧強度が大きいこと
を意味する。耐圧強度は実施例において示されるよう
に、ＪＩＳ−Ｚ−８８４１に記載の造粒物−強度試験方
法に記載されている造粒物の圧壊強度試験方法に基づ
き、木屋式硬度計を用い、試験片である粒状物の直径方
向に一定速度で加圧板を押し付けて圧縮負荷を加えたと
き、粒状物が耐えることができる最大荷重（単位はｋｇ
ｆ）として表されるものを意味する。本発明粒状物の耐
圧強度としては２ｋｇｆ以上であることが好ましい。こ
の理由は、粒状物の耐圧強度が２ｋｇｆ未満では粒状物
を吸着剤として充填塔に充填する際に破損が多くなるな
ど、その利用面において好ましくないからである。Here, high strength means that the pressure resistance is high. As shown in the examples, the compressive strength was tested using a Kiya type hardness tester based on the crushing strength test method of the granulated material described in JIS-Z-8841. When a compressive load is applied by pressing a pressure plate at a constant speed in the diameter direction of a granular material as a piece, the maximum load that the granular material can withstand (unit: kg
f) means what is represented. The compressive strength of the granular material of the present invention is preferably 2 kgf or more. The reason for this is that if the pressure-resistant strength of the granular material is less than 2 kgf, damage is increased when the granular material is packed into a packed tower as an adsorbent, which is not preferable in terms of utilization.
【００１７】また、低摩耗性とは実施例において示され
るように、ＪＩＳ−Ｋ−１４６４に記載の粒子強度の測
定法に準じて算出される摩耗率を意味し、本発明粒状物
はその摩耗率が１％以下であることが好ましい。この範
囲にあれば、粒状物を吸着剤として使用する場合、吸着
塔へ充填したりあるいは吸脱着操作を繰り返す際に粉化
が生じにくくすることで、弁、バルブ等のトラブルを招
いたり、圧力損失が上昇して吸着分離能が低下する等の
問題を回避できるからである。Further, as shown in the examples, the low wear property means a wear rate calculated according to the particle strength measuring method described in JIS-K-1464, and the present invention is characterized by its wear rate. Preferably, the rate is 1% or less. Within this range, when the particulate matter is used as an adsorbent, it is difficult to cause powdering when filling the adsorption tower or repeating the adsorption / desorption operation, causing troubles for valves, valves, etc. This is because problems such as an increase in loss and a decrease in adsorption separation ability can be avoided.
【００１８】本発明粒状物中のゼオライト成分は被吸着
物を吸着し得る能力を有するものであり、Ｘ型、Ａ型、
あるいは低シリカＸ型ゼオライトが挙げられる。これら
のゼオライトは１種以上を混合して用いることもでき、
また、純度を考慮すれば合成品であることが好ましい。
これらの内、イオン交換能を高くし、また、細孔容積を
大きくしてガス吸着能を高めるためにＳｉＯ2／Ａｌ2Ｏ
3モル比１．９〜２．１の結晶性の低シリカＸ型ゼオラ
イトであることが好ましい。なお、低シリカＸ型ゼオラ
イトのＳｉＯ2／Ａｌ2Ｏ3モル比は理論的には２．０で
あるが、化学組成分析の測定上のバラツキ等を考慮すれ
ば１．９〜２．１の範囲となることは明らかである。The zeolite component in the granular material of the present invention has an ability to adsorb the substance to be adsorbed.
Alternatively, a low silica X-type zeolite may be used. These zeolites can be used as a mixture of one or more,
In addition, a synthetic product is preferable in consideration of purity.
Of these, SiO 2 / Al 2 O is used to increase the ion exchange capacity and increase the pore volume to increase the gas adsorption capacity.
3 is preferably a crystalline low-silica X-type zeolite in a molar ratio of 1.9 to 2.1. The SiO 2 / Al 2 O 3 molar ratio of the low-silica X-type zeolite is 2.0 in theory, but is 1.9 to 2.1 in consideration of the variation in measurement of the chemical composition analysis. It is clear that it is a range.
【００１９】また、本発明粒状物中のゼオライト成分の
含量としては、粒状物全量の８０重量％以上が好まし
い。含量が８０重量％未満の場合その吸着容量が不十分
となり、吸着剤の必要量が増大するため好ましくない。The content of the zeolite component in the granules of the present invention is preferably at least 80% by weight of the total amount of the granules. When the content is less than 80% by weight, the adsorption capacity becomes insufficient and the required amount of the adsorbent increases, which is not preferable.
【００２０】本発明粒状物中のバインダー成分は本発明
粒状物を成形体として成形する際に必須のものであり、
本発明の目的を達成できるものであれば特に制限される
ものではないが、針状結晶を有する粘土と板状結晶を有
する粘土とをともに有していることが好ましい。この理
由は、針状結晶を有する粘土は粒状物を焼成処理する際
の熱劣化を抑制する効果があり、また、板状結晶を有す
る粘土は粒状物の熱劣化の要因となる反面その強度を高
める効果が顕著であり、少量の添加であれば熱劣化を抑
えて強度を向上することができるため、両者を適切な組
成で有した本発明粒状物が優れた強度を有し、かつ吸着
容量の大きいことに寄与できるからである。The binder component in the granules of the present invention is indispensable when the granules of the present invention are molded as a molded article.
There is no particular limitation as long as the object of the present invention can be achieved, but it is preferable to have both clay having needle-like crystals and clay having plate-like crystals. The reason for this is that clay having needle-like crystals has the effect of suppressing thermal degradation during firing of granular materials, and clay having plate-like crystals causes thermal degradation of granular materials, but on the other hand, the strength of the clay is reduced. The effect of increasing the content is remarkable, and if added in a small amount, the thermal degradation can be suppressed and the strength can be improved, so that the granular material of the present invention having both of them in an appropriate composition has excellent strength and adsorption capacity Because it can contribute to the greatness of
【００２１】このようなバインダーとして有効な板状結
晶を有する粘土としては、カオリン系、ベントナイト
系、タルク系、バイロフィライト系、モリサイト系、バ
ーキュロライト系、モンモリロナイト系、クロライト
系、ハロイサイト系等の粘土を挙げることができ、これ
らの内でもカオリン系、ベントナイト系の粘土が好まし
く、これらは１種単独のみならず２種以上をバインダー
として有していることが好ましい。Examples of such a clay having plate-like crystals effective as a binder include kaolin-based, bentonite-based, talc-based, vilophyllite-based, molysite-based, verculolite-based, montmorillonite-based, chlorite-based, and halloysite-based clays. And the like. Of these, kaolin-based and bentonite-based clays are preferable, and these preferably have not only one kind alone but also two or more kinds as a binder.
【００２２】また、針状結晶を有する粘土としては、セ
ピオライト系、アタパルジャイト系、アスベスト系等の
粘土を挙げることができ、これらの内でもセピオライト
系、アタパルジャイト系の粘土が好ましい。Examples of the clay having acicular crystals include sepiolite-based, attapulgite-based, and asbestos-based clays. Of these, sepiolite-based and attapulgite-based clays are preferable.
【００２３】本発明粒状物中のバインダー成分における
板状結晶を有する粘土と針状結晶を有する粘土の量とし
ては、本発明粒状物中のゼオライト分を除いた分量の中
で任意の量であればよいが、ゼオライト成分含量が減少
し得られる粒状物の吸着容量が低下するのを抑えたり、
得られる粒状物の形状を保持するために、無水物換算で
用いられるゼオライト粉末１００重量部に対して、針状
結晶を有する粘土は５〜２０重量部、板状結晶を有する
粘土は１〜５重量部であることが好ましい。The amount of the clay having plate-like crystals and the amount of clay having needle-like crystals in the binder component in the granular material of the present invention may be any amount in the amount excluding the zeolite component in the granular material of the present invention. It is sufficient to suppress the decrease in the adsorption capacity of the obtained granular material by reducing the content of the zeolite component,
To maintain the shape of the obtained granules, 5 to 20 parts by weight of clay having needle-like crystals and 1 to 5 parts by weight of clay having plate-like crystals are used for 100 parts by weight of zeolite powder used in terms of anhydride. It is preferably in parts by weight.
【００２４】本発明粒状物の径としては、その直径が
０．５〜２．５ｍｍが好ましい。直径が０．５ｍｍ未満
では十分な強度が得られず、２．５ｍｍを越える場合に
は十分な吸脱着速度が得られないため吸着剤としての性
能が低くなり、好ましくない。The diameter of the granular material of the present invention is preferably 0.5 to 2.5 mm. If the diameter is less than 0.5 mm, sufficient strength cannot be obtained, and if it exceeds 2.5 mm, a sufficient adsorbing / desorbing speed cannot be obtained, so that the performance as an adsorbent decreases, which is not preferable.
【００２５】本発明粒状物中のカチオン種は特に限定さ
れず、アルカリ金属、アルカリ土類金属等のカチオンを
粒状物中のカチオンと交換することで所望のカチオンを
有した粒状物とすることができる。The cation species in the granular material of the present invention is not particularly limited, and a cation such as an alkali metal or an alkaline earth metal is exchanged for the cation in the granular material to obtain a granular material having a desired cation. it can.
【００２６】次に本発明粒状物の製造方法について説明
する。Next, a method for producing the granular material of the present invention will be described.
【００２７】本発明粒状物の製造方法は、ゼオライト粉
末と、無水物換算でゼオライト粉末１００重量部に対し
て、バインダー成分２５重量部以下及び水分５０〜７０
重量部からなる混合物を混練し、造粒成形、乾燥、焼成
することからなっており、さらに必要に応じて、焼成後
にイオン交換、活性化を実施することもできる。以下に
各工程について説明する。The method for producing the granular material according to the present invention is characterized in that the binder component is 25 parts by weight or less and the water content is 50 to 70 parts per 100 parts by weight of zeolite powder and zeolite powder in terms of anhydride.
It consists of kneading a mixture consisting of parts by weight, granulating, drying and calcining. If necessary, ion exchange and activation can be carried out after calcining. Hereinafter, each step will be described.
【００２８】＜混練＞本発明の方法に用いられるゼオラ
イト粉末の種類としては、Ｘ型、Ａ型、あるいは低シリ
カＸ型ゼオライトであり、好ましくはＳｉＯ2／Ａｌ2Ｏ
3モル比１．９〜２．１の低シリカＸ型ゼオライトであ
る。<Kneading> The type of zeolite powder used in the method of the present invention is X-type, A-type or low-silica X-type zeolite, preferably SiO 2 / Al 2 O.
3 is a low silica X-type zeolite in a molar ratio of 1.9 to 2.1.
【００２９】また、バインダー成分としては、セピオラ
イト系、アタパルジャイト系等の針状結晶を有する粘土
及び、カオリン系、ベントナイト系等の板状結晶を有す
る粘土を用いるとよく、殊に針状結晶を有する粘土は２
種以上を用いるとよい。As the binder component, clay having needle-like crystals such as sepiolite and attapulgite and clay having plate-like crystals such as kaolin and bentonite are preferably used, and particularly, needle-like crystals. Clay is 2
More than one species may be used.
【００３０】用いられるバインダーの使用量としては、
ゼオライト粉末１００重量部（無水物換算）に対して、
針状結晶を有する粘土は５〜２０重量部、板状結晶を有
する粘土は１〜５重量部である。この理由は、バインダ
ー成分が多くなることでゼオライト成分含量が減少して
得られる粒状物の吸着容量が低下するのを抑えたり、得
られる粒状物の形状を保持するためである。The amount of the binder used is as follows:
For 100 parts by weight of zeolite powder (anhydrous equivalent),
The clay having needle-like crystals is 5 to 20 parts by weight, and the clay having plate-like crystals is 1 to 5 parts by weight. The reason for this is to suppress a decrease in the adsorption capacity of the obtained granular material due to a decrease in the content of the zeolite component due to an increase in the binder component, or to maintain the shape of the obtained granular material.
【００３１】水分の使用量としては、混練の容易さとい
った操作面や得られる粒状体の強度の低下を避けるため
に、ゼオライト粉末１００重量部（無水物換算）に対し
て、５０〜７０重量部の範囲が好ましい。また、水分と
してはそのまま、あるいは温水として用いることもでき
る。The amount of water used is 50 to 70 parts by weight with respect to 100 parts by weight of zeolite powder (in terms of anhydride) in order to avoid a decrease in the operation surface such as ease of kneading and the strength of the obtained granules. Is preferable. Moreover, it can also be used as water as it is or as warm water.
【００３２】これらの前記した原料を混練するが、混練
の温度、時間等の条件については通常用いられる条件で
良く、また、混練に用いる機種に特に限定はないが、擂
潰機、ニーダー、ミックスマラー等が例示できる。The above-mentioned raw materials are kneaded, and conditions such as kneading temperature and time may be the same as those usually used, and there is no particular limitation on a model used for kneading. Muller etc. can be illustrated.
【００３３】＜造粒成形＞次に、混練された混合物を造
粒して粒状物とする。ここでの造粒の方法は特に限定さ
れるものではないが、転動造粒、撹拌造粒、流動造粒、
押し出し造粒等が挙げられ、これらの後に転動整粒を行
って粒状物表面の形状を整えることもできる。<Granulation molding> Next, the kneaded mixture is granulated to obtain granules. The method of granulation here is not particularly limited, but tumbling granulation, stirring granulation, fluidized granulation,
Extrusion granulation and the like can be mentioned, and after that, rolling and sizing can be performed to adjust the shape of the surface of the granular material.
【００３４】造粒機種は特に制限されるものではない。
また、転動整粒機には、回転数等を調整することにより
転動造粒機を転用する事ができる。The granulation machine is not particularly limited.
A rolling granulator can be diverted to a rolling granulator by adjusting the number of revolutions and the like.
【００３５】＜乾燥・焼成＞乾燥、焼成の方法として
は、公知の方法を用いて実施することができる。ここ
で、乾燥の温度及び機種に制限はないが、例えば１２０
℃程度で振動流動乾燥機等での乾燥を行うことができ
る。<Drying / Firing> The drying and firing methods can be carried out using known methods. Here, the drying temperature and the type are not limited.
Drying with a vibrating fluidized drier or the like can be performed at about ° C.
【００３６】焼成の温度としては、得られる粒状物の形
状を安定に保持するために３５０〜６５０℃の条件にて
行うことが好ましい。このような焼成に用いられる機種
としては、シャフトキルン、ロータリーキルン等が例示
できる。The firing temperature is preferably from 350 to 650 ° C. in order to stably maintain the shape of the obtained granular material. Examples of a model used for such firing include a shaft kiln and a rotary kiln.
【００３７】また、得られた粒状物の大きさを均一に揃
えるために、造粒成形や乾燥・焼成の際に篩い等により
分級してもよい。Further, in order to make the size of the obtained granules uniform, the granules may be classified by a sieve or the like during granulation molding, drying and firing.
【００３８】以上のような製造条件から、本発明粒状物
の特徴を有する成形体を得ることができる。From the above production conditions, a molded article having the characteristics of the granular material of the present invention can be obtained.
【００３９】本発明粒状物は、その径が小さく、さらに
耐圧強度及び耐摩耗性に優れているため、公知の方法を
用いてＣａあるいはＬｉ等にイオン交換し、活性化した
ものは、吸着剤として種々の分野において使用すること
ができる。例えば、ＰＳＡ法や温度揺動吸着法によるガ
ス吸着分離等に使用することができ、さらに具体的に
は、空気中の窒素を吸着させ、残りの成分中の酸素濃度
を高めた高酸素濃度のガスを得て、鉄鋼、ガラス等の製
造において用いたり、医療分野への適用もできる。Since the granular material of the present invention has a small diameter and excellent pressure resistance and abrasion resistance, it is ion-exchanged with Ca or Li using a known method and activated. Can be used in various fields. For example, it can be used for gas adsorption separation by the PSA method or the temperature swing adsorption method. More specifically, it is possible to adsorb nitrogen in the air and increase the oxygen concentration in the remaining components. The gas can be obtained and used in the production of steel, glass, etc., or applied to the medical field.
【００４０】本発明粒状物が、その直径を減少させた場
合でも、吸着分離剤に必須の耐圧強度及び耐摩耗性を損
なわずして吸着能を高くできる理由は、バインダーとし
て針状結晶を有する粘土と板状結晶を有する粘土を適量
使用することにより、強度特性を向上させながらゼオラ
イト含量を増大させることにある。The reason that the granular material of the present invention can have a high adsorptivity without impairing the pressure resistance and abrasion resistance essential for the adsorptive separation agent even when its diameter is reduced is that needle-like crystals are used as the binder. An object of the present invention is to increase the zeolite content while improving strength properties by using an appropriate amount of clay and clay having plate crystals.
【００４１】[0041]
【実施例】以下、本発明を実施例を用いてさらに詳細に
説明するが、本発明はこれらに限定されるものではな
い。なお、各評価は以下に示した方法によって実施した 〜耐圧強度〜 耐圧強度の測定においては、ＪＩＳ−Ｚ−８８４１に記
載の造粒物−強度試験方法に記載されている造粒物の圧
壊強度試験方法に基づき、木屋式硬度計を用い、常温、
常圧の雰囲気において、試験片である粒状物の直径方向
に、一定速度で加圧板を押し付けて圧縮負荷を加えたと
き、粒状物が耐えることができる最大荷重（単位はｋｇ
ｆ）を測定することで実施した。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, each evaluation was implemented by the method shown below.-Compressive strength-In the measurement of compressive strength, the crushing strength of the granulated material described in the granulated material-strength test method described in JIS-Z-8841 Based on the test method, using a Kiya type hardness meter, at room temperature,
In a normal pressure atmosphere, when a compressive load is applied by pressing a pressing plate at a constant speed in the diameter direction of a granular material as a test piece, the maximum load that the granular material can withstand (unit: kg
This was performed by measuring f).
【００４２】具体的には、木屋式デジタル硬度計（ＫＨ
Ｔ−２０型）により測定した。すなわち、造粒、乾燥後
のゼオライト粒状物をふるいにより分級し、直径１．２
ｍｍ〜２．０ｍｍの粒状物を分取した。この分級した粒
状物を焼成し、耐圧強度測定用粒状物を取り出し、直径
方向の耐圧強度を、直径５ｍｍの円柱状の加圧板を装着
した、木屋式硬度計により測定した。加圧板はステンレ
ス製のものを使用し、加圧速度は０．８ｍｍ／秒とし
た。このようにして３０個の粒状物の耐圧強度測定を行
った。Specifically, a Kiya type digital hardness tester (KH
T-20). That is, the granulated and dried zeolite granules are classified by sieving to obtain a diameter of 1.2.
Granules having a size of 2.0 mm to 2.0 mm were collected. The classified granules were fired, and the granules for measuring the compressive strength were taken out, and the compressive strength in the diameter direction was measured by a Kiya hardness tester equipped with a cylindrical pressure plate having a diameter of 5 mm. The pressing plate used was made of stainless steel, and the pressing speed was 0.8 mm / sec. In this way, the compression strength measurement of 30 granular materials was performed.
【００４３】尚、以下の実施例、比較例で示される表１
において、耐圧強度は得られた測定結果の平均値±標準
偏差として表した。Table 1 shown in the following Examples and Comparative Examples
In Table 1, the compressive strength was expressed as an average value ± standard deviation of the obtained measurement results.
【００４４】〜摩耗率〜 摩耗率はＪＩＳ−Ｋ−１４６４（１９６２年版）に記載
の粒子強度の測定法に準じて算出した。すなわち、試料
である粒状物をあらかじめ温度２５℃、相対湿度８０％
のデシケーター中で平衡になるまで１６時間以上放置し
た。ついで、試料約７０ｇを８５０μｍ、３５５μｍ及
び受け皿をセットしたふるい（東京スクリーン社製、型
式：ＪＩＳ Ｚ−８８０１）を用いて３分間ふるい分け
し、次いで、付着物等を取り除いた前記のふるいに、８
５０μｍふるい上に残った試料５０ｇを正確に秤り取
り、同時に５個の１０円玉銅貨をセットし、１５分間振
動する。受け皿に落ちた試料をＸｇとして次の（１）式
で摩耗率を算出した。Abrasion Rate The abrasion rate was calculated according to the particle strength measurement method described in JIS-K-1464 (1962 edition). That is, a granular material as a sample was previously prepared at a temperature of 25 ° C. and a relative humidity of 80%.
In the desiccator for more than 16 hours. Then, about 70 g of the sample was sieved for 3 minutes using a sieve (manufactured by Tokyo Screen Co., Ltd., model: JIS Z-8801) in which 850 μm, 355 μm and a saucer were set, and then 8 sieves were removed from the sieve.
50 g of the sample remaining on the 50 μm sieve is accurately weighed, and at the same time, five 10-yen coins are set and shaken for 15 minutes. The wear rate was calculated by the following equation (1) using the sample dropped on the pan as Xg.
【００４５】 摩耗率（重量％）＝（Ｘ／５０）×１００ （１） 〜水分吸着量〜 粒状物を相対湿度８０％のデシケーター中で１６時間以
上放置した。この水和後の試料の９００℃における強熱
減量を試料の水分吸着量とした。Abrasion rate (% by weight) = (X / 50) × 100 (1) —Amount of adsorbed moisture—The granules were left in a desiccator at a relative humidity of 80% for 16 hours or more. The loss on ignition of the sample after hydration at 900 ° C. was defined as the water adsorption of the sample.
【００４６】以下の実施例、比較例における「部」は重
量部である。"Parts" in the following Examples and Comparative Examples are parts by weight.
【００４７】実施例１ 低シリカＸ型ゼオライト１００部、アタパルジャイト系
粘土１０部、カオリン系粘土５部を混合し、加水後ミッ
クスマーラーで充分に捏和し、撹拌造粒機で直径１〜２
ｍｍの球状品を多く含む状態に造粒成形した後、マルメ
ライザーで転動整粒し、形の整った球状品を得た。これ
を１２０℃で乾燥したのち、分級して直径１．２〜２．
０ｍｍの球状品を分取し、管状炉で空気流通下において
６００℃雰囲気中で２時間焼成してバインダーを焼結さ
せた後、密閉容器中で冷却した。Example 1 100 parts of low silica X-type zeolite, 10 parts of attapulgite clay and 5 parts of kaolin clay were mixed, and after kneading, the mixture was kneaded sufficiently with a mix muller and the mixture was stirred for 1-2 minutes in a granulator.
After granulation molding to include a large number of spherical products having a diameter of mm, the resultant was subjected to rolling and sizing with a marmellaizer to obtain spherical products having a well-shaped shape. After drying at 120 ° C., it was classified and the diameter was 1.2-2.
A spherical product having a diameter of 0 mm was collected, fired in a tubular furnace in an atmosphere of air at 600 ° C. for 2 hours to sinter the binder, and then cooled in a closed vessel.
【００４８】この焼成品の耐圧強度、これを水和したも
のの摩耗率、及び水分吸着能を上記記載の方法により測
定し、各測定値はまとめて表１に示した。The pressure resistance of this calcined product, the abrasion rate of the hydrated product, and the water adsorbing ability were measured by the methods described above. The measured values are shown in Table 1.
【００４９】[0049]
【表１】 [Table 1]
【００５０】実施例２ 低シリカＸ型ゼオライト１００部、セピオライト系粘土
１２部、カオリン系粘土３部を混合し、加水、捏和後、
撹拌造粒機で直径１〜２ｍｍの球状品を多く含む状態に
造粒成形した後、マルメライザーで転動整粒し、形の整
った球状品を得た。その後は実施例１と同様にして処理
した後、この焼成品の耐圧強度、これを水和したものの
摩耗率、及び水分吸着能を測定し、まとめて表１に示し
た。Example 2 100 parts of low silica X-type zeolite, 12 parts of sepiolite clay and 3 parts of kaolin clay were mixed, and after adding water and kneading,
After granulating and shaping into a state containing many spherical products having a diameter of 1 to 2 mm with a stirring granulator, rolling and sizing was performed with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５１】実施例３ 低シリカＸ型ゼオライト１００部、セピオライト系粘土
１１部、ベントナイト系粘土５部を混合し、加水、捏和
後、撹拌造粒機で直径１〜２ｍｍの球状品を多く含む状
態に造粒成形した後、マルメライザーで転動整粒し、形
の整った球状品を得た。その後は実施例１と同様にして
処理した後、この焼成品の耐圧強度、これを水和したも
のの摩耗率及び水分吸着能を測定し、まとめて表１に示
した。Example 3 100 parts of low-silica X-type zeolite, 11 parts of sepiolite clay and 5 parts of bentonite clay were mixed, mixed with water and kneaded, and then contained a large amount of spherical products having a diameter of 1 to 2 mm by a stirring granulator. After granulation and molding into a state, it was tumbled and sized with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５２】実施例４ 低シリカＸ型ゼオライト１００部、セピオライト系粘土
１０部、カオリン系粘土３部，ベントナイト系粘土２部
を混合し、加水、捏和後、撹拌造粒機で直径１〜２ｍｍ
の球状品を多く含む状態に造粒成形した後、マルメライ
ザーで転動整粒し、形の整った球状品を得た。その後は
実施例１と同様にして処理した後、この焼成品の耐圧強
度、これを水和したものの摩耗率及び水分吸着能を測定
し、まとめて表１に示した。Example 4 100 parts of low silica X-type zeolite, 10 parts of sepiolite-based clay, 3 parts of kaolin-based clay, and 2 parts of bentonite-based clay were mixed, added with water, kneaded, and then mixed with a stirring granulator to obtain a diameter of 1 to 2 mm.
Was granulated into a state containing a large number of spherical products, and then tumbled and sized with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５３】実施例５ 低シリカＸ型ゼオライト１００部、セピオライト系粘土
１０部、カオリン系粘土１部，ベントナイト系粘土４部
を混合し、加水、捏和後、撹拌造粒機で直径１〜２ｍｍ
の球状品を多く含む状態に造粒成形した後、カルボキシ
メチルセルロース１部を含んだ水を噴霧しながらマルメ
ライザーで転動整粒し、形の整った球状品を得た。その
後は実施例１と同様にして処理した後、この焼成品の耐
圧強度、これを水和したものの摩耗率及び水分吸着能を
測定し、まとめて表１に示した。Example 5 100 parts of low silica X-type zeolite, 10 parts of sepiolite-based clay, 1 part of kaolin-based clay, and 4 parts of bentonite-based clay were mixed, kneaded with water, and kneaded.
Was granulated into a state containing a large amount of spherical products, and then tumbled and sized with a marmellaizer while spraying water containing 1 part of carboxymethylcellulose to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５４】比較例１ 低シリカＸ型ゼオライト１００部、カオリン系粘土１２
部を混合し、加水、捏和後、撹拌造粒機で直径１〜２ｍ
ｍの球状品を多く含む状態に造粒成形した後、マルメラ
イザーで転動整粒し、形の整った球状品を得た。その後
は実施例１と同様にして処理した後、この焼成品の耐圧
強度、これを水和したものの摩耗率及び水分吸着能を測
定し、まとめて表１に示した。Comparative Example 1 100 parts of low silica X-type zeolite, kaolin clay 12
After mixing, water addition and kneading, the diameter was 1 to 2 m with a stirring granulator.
After granulation molding into a state containing a large number of spherical products of m, rolling and sizing was performed with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５５】この結果より、カオリン系粘土のみをバイ
ンダーとして使用した場合、高い強度特性は得られるも
のの、水分吸着率の低いものしか得られなかった。From these results, when only kaolin-based clay was used as a binder, high strength characteristics were obtained, but only those having a low water adsorption rate were obtained.
【００５６】比較例２ 低シリカＸ型ゼオライト１００部、ベントナイト系粘土
１４部を混合し、加水、捏和後、撹拌造粒機で直径１〜
２ｍｍの球状品を多く含む状態に造粒成形した後、マル
メライザーで転動整粒し、形の整った球状品を得た。そ
の後は実施例１と同様にして処理した後、この焼成品の
耐圧強度、これを水和したものの摩耗率及び水分吸着能
を測定し、まとめて表１に示した。Comparative Example 2 100 parts of low silica X-type zeolite and 14 parts of bentonite clay were mixed, and after adding water and kneading, mixing with a stirring granulator to obtain a diameter of 1 to 3.
After granulation and shaping into a state containing a large amount of 2 mm spherical products, rolling and sizing was performed with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５７】この結果より、ベントナイト系粘土のみを
バインダーとして使用した場合、高い強度特性は得られ
るものの、水分吸着率の低いものしか得られなかった。From these results, when only bentonite clay was used as the binder, high strength characteristics were obtained, but only those having a low water adsorption rate were obtained.
【００５８】比較例３ 低シリカＸ型ゼオライト１００部、セピオライト系粘土
１５部を混合し、加水、捏和後、撹拌造粒機で直径１〜
２ｍｍの球状品を多く含む状態に造粒成形した後、マル
メライザーで転動整粒し、形の整った球状品を得た。そ
の後は実施例１と同様にして処理した後、この焼成品の
耐圧強度、これを水和したものの摩耗率及び水分吸着能
を測定し、まとめて表１に示した。Comparative Example 3 100 parts of low-silica X-type zeolite and 15 parts of sepiolite-based clay were mixed, added with water, kneaded, and then mixed with a stirring granulator to obtain a diameter of 1 to 3.
After granulation and shaping into a state containing a large amount of 2 mm spherical products, rolling and sizing was performed with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００５９】この結果より、セピオライト系粘土のみを
バインダーとして使用した場合、高い水分吸着率は得ら
れるものの、強度特性の低いものしか得られなかった。From these results, when only the sepiolite-based clay was used as the binder, a high moisture adsorption rate was obtained, but only a low strength property was obtained.
【００６０】比較例４ 低シリカＸ型ゼオライト１００部、アタパルジャイト系
粘土１５部を混合し、加水、捏和後、撹拌造粒機で直径
１〜２ｍｍの球状品を多く含む状態に造粒成形した後、
マルメライザーで転動整粒し、形の整った球状品を得
た。その後は実施例１と同様にして処理した後、この焼
成品の耐圧強度、これを水和したものの摩耗率及び水分
吸着能を測定し、まとめて表１に示した。Comparative Example 4 100 parts of low silica X-type zeolite and 15 parts of attapulgite clay were mixed, kneaded with water, kneaded, and then granulated by a stirring granulator into a state containing many spherical products having a diameter of 1 to 2 mm. rear,
It was tumbled and sized with a marmellaizer to obtain a well-formed spherical product. Thereafter, the treatment was carried out in the same manner as in Example 1. Then, the pressure resistance of the fired product, the wear rate of the hydrated product, and the water adsorption capacity were measured.
【００６１】この結果より、アタパルジャイト系粘土の
みをバインダーとして使用した場合、高い水分吸着率は
得られるものの、強度特性の低いものしか得られなかっ
た。From these results, when only the attapulgite-based clay was used as the binder, a high water adsorption rate was obtained, but only low strength properties were obtained.
【００６２】[0062]
【発明の効果】以上の説明から明らかなように、本発明
の高強度低摩耗性ゼオライト粒状物は、水分吸着能が高
く、かつ耐圧強度及び耐摩耗性に優れている。また、本
発明の製造方法によれば、水分吸着能を損なわずして、
耐圧強度及び耐摩耗性に優れた高強度低摩耗性粒状物を
容易に得ることができる。As is apparent from the above description, the high-strength and low-wear zeolite granules of the present invention have a high water-absorbing ability, and are excellent in pressure resistance and wear resistance. Further, according to the production method of the present invention, without impairing the water adsorption capacity,
A high-strength, low-wear granular material having excellent pressure resistance and wear resistance can be easily obtained.
Claims (5)
低摩耗性ゼオライト粒状物において、前記ゼオライトが
全量の８０重量％以上であり、かつ直径が０．５〜２．
５ｍｍであることを特徴とする高強度低摩耗性ゼオライ
ト粒状物。1. A high-strength low-wear zeolite granule comprising a zeolite and a binder, wherein the zeolite accounts for at least 80% by weight of the total amount and a diameter of 0.5 to 2.
A high-strength, low-wear zeolite granule having a size of 5 mm.
１．９〜２．１の低シリカＸ型ゼオライトであり、かつ
バインダーが針状結晶を有する粘土及び板状結晶を有す
る粘土であることを特徴とする請求項１に記載の高強度
低摩耗性ゼオライト粒状物。2. The zeolite is a low silica X-type zeolite having a SiO 2 / Al 2 O 3 molar ratio of 1.9 to 2.1, and the binder is a clay having needle-like crystals and a clay having plate-like crystals. The high-strength low-wear zeolite granules according to claim 1, characterized in that:
はアタパルジャイト系の粘土であることを特徴とする請
求項２に記載の高強度低摩耗性ゼオライト粒状物。3. The high-strength, low-wear zeolite granule according to claim 2, wherein the clay having acicular crystals is a sepiolite-based or attapulgite-based clay.
又はベントナイト系の粘土であることを特徴とする請求
項２又は請求項３に記載の高強度低摩耗性ゼオライト粒
状物。4. The clay having plate-like crystals is kaolin-based and / or
4. The high-strength, low-abrasion zeolite granules according to claim 2 or 3, which is a bentonite clay.
のゼオライトと、無水物換算で前記ゼオライト粉末１０
０重量部に対して、針状結晶を有する粘土の粉末５〜２
０重量部、板状結晶を有する粘土の粉末１〜５重量部及
び水分５０〜７０重量部とを混練し、造粒成形、乾燥、
焼成することを特徴とする請求項２〜４のいずれかに記
載の高強度低摩耗性ゼオライト粒状物の製造方法。5. A SiO 2 / Al 2 O 3 molar ratio of 1.9 to 2.1.
And the zeolite powder 10 in terms of anhydride
5 to 2 parts by weight of a clay powder having acicular crystals with respect to 0 parts by weight.
0 parts by weight, 1 to 5 parts by weight of clay powder having plate crystals and 50 to 70 parts by weight of water are kneaded, granulated, dried,
The method for producing a high-strength low-wear zeolite granule according to any one of claims 2 to 4, characterized by firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10124588A JPH11314913A (en) | 1998-05-07 | 1998-05-07 | High strength low wear zeolite granule and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10124588A JPH11314913A (en) | 1998-05-07 | 1998-05-07 | High strength low wear zeolite granule and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11314913A true JPH11314913A (en) | 1999-11-16 |
Family
ID=14889187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10124588A Pending JPH11314913A (en) | 1998-05-07 | 1998-05-07 | High strength low wear zeolite granule and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11314913A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000128523A (en) * | 1998-10-19 | 2000-05-09 | Mitsubishi Chemicals Corp | Method for forming zeolite |
| WO2005108680A1 (en) * | 2004-05-12 | 2005-11-17 | Azumagumi Co., Ltd. | Water control structure, concrete block for water control construction, and method of water control construction therewith |
| WO2008153126A1 (en) * | 2007-06-14 | 2008-12-18 | Kyodo Printing Co., Ltd. | Process for production of adsorbent-containing formed bodies and adsorbent-containing formed bodies |
| JP2008307474A (en) * | 2007-06-14 | 2008-12-25 | Kyodo Printing Co Ltd | Method for manufacturing adsorbent-containing molding and adsorbent-containing molding |
| WO2010050417A1 (en) * | 2008-10-30 | 2010-05-06 | 東ソー株式会社 | High-strength zeolite bead molding and method for producing the same |
| JP2011230103A (en) * | 2010-04-30 | 2011-11-17 | Jx Nippon Oil & Energy Corp | Solid-shaped adsorbent and method of refining hydrocarbon |
| JP2011255376A (en) * | 2000-04-04 | 2011-12-22 | Tosoh Corp | Method for separation of carbon dioxide by adsorption |
| WO2019230841A1 (en) * | 2018-05-31 | 2019-12-05 | 東ソー株式会社 | Highly abrasion-resistant zeolite moulded article and method for producing same |
| WO2021107014A1 (en) | 2019-11-28 | 2021-06-03 | 東ソー株式会社 | Highly wear-resistant zeolite molded article, and method for manufacturing same |
-
1998
- 1998-05-07 JP JP10124588A patent/JPH11314913A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000128523A (en) * | 1998-10-19 | 2000-05-09 | Mitsubishi Chemicals Corp | Method for forming zeolite |
| JP2011255376A (en) * | 2000-04-04 | 2011-12-22 | Tosoh Corp | Method for separation of carbon dioxide by adsorption |
| WO2005108680A1 (en) * | 2004-05-12 | 2005-11-17 | Azumagumi Co., Ltd. | Water control structure, concrete block for water control construction, and method of water control construction therewith |
| WO2008153126A1 (en) * | 2007-06-14 | 2008-12-18 | Kyodo Printing Co., Ltd. | Process for production of adsorbent-containing formed bodies and adsorbent-containing formed bodies |
| JP2008307474A (en) * | 2007-06-14 | 2008-12-25 | Kyodo Printing Co Ltd | Method for manufacturing adsorbent-containing molding and adsorbent-containing molding |
| WO2010050417A1 (en) * | 2008-10-30 | 2010-05-06 | 東ソー株式会社 | High-strength zeolite bead molding and method for producing the same |
| JP2010132530A (en) * | 2008-10-30 | 2010-06-17 | Tosoh Corp | High-strength zeolite bead molding and method for producing the same |
| JP2011230103A (en) * | 2010-04-30 | 2011-11-17 | Jx Nippon Oil & Energy Corp | Solid-shaped adsorbent and method of refining hydrocarbon |
| WO2019230841A1 (en) * | 2018-05-31 | 2019-12-05 | 東ソー株式会社 | Highly abrasion-resistant zeolite moulded article and method for producing same |
| JP2019210207A (en) * | 2018-05-31 | 2019-12-12 | 東ソー株式会社 | Highly wear-resistant zeolite compact and its production method |
| WO2021107014A1 (en) | 2019-11-28 | 2021-06-03 | 東ソー株式会社 | Highly wear-resistant zeolite molded article, and method for manufacturing same |
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