JPH0674136B2 - Zeolite compact and manufacturing method thereof - Google Patents
Zeolite compact and manufacturing method thereofInfo
- Publication number
- JPH0674136B2 JPH0674136B2 JP61127208A JP12720886A JPH0674136B2 JP H0674136 B2 JPH0674136 B2 JP H0674136B2 JP 61127208 A JP61127208 A JP 61127208A JP 12720886 A JP12720886 A JP 12720886A JP H0674136 B2 JPH0674136 B2 JP H0674136B2
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- Japan
- Prior art keywords
- zeolite
- weight
- parts
- compact
- molded body
- Prior art date
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、ガス吸着剤に適したゼオライト成形体および
その製造法に関する。TECHNICAL FIELD The present invention relates to a zeolite compact suitable for a gas adsorbent and a method for producing the same.
［従来の技術］ 周知のようにゼオライト成形体は天然ガス中のH2O,CO2,
H2S,メルカプタンの除去、有機溶媒、各種工業ガスなど
の脱水・乾燥、iso−ブタンとｎ−ブタンとの分離、PSA
〔プレッシャー・スイング・アドソープション（Pressu
re Swing Adsorption）〕法による空気中の酸素と窒素
の分離、あるいは石油精製又は石油化学工業における触
媒等の各種の産業分野でその機能的吸着性のゆえに多用
されている。[Prior Art] As is well known, zeolite compacts are produced by using H 2 O, CO 2 ,
Removal of H 2 S and mercaptan, dehydration and drying of organic solvents and various industrial gases, separation of iso-butane and n-butane, PSA
[Pressure Swing Adsorption (Pressu
re Swing Adsorption)] is used for separation of oxygen and nitrogen in the air by the method, or in various industrial fields such as catalysts in the petroleum refining or petrochemical industries because of its functional adsorptivity.
このようなゼオライト成形体にあって、ゼオライト粉末
自体の特性が同一であってもその成形技術の如何によっ
て性能が異なることはよく知られるところである。It is well known that, in such a zeolite compact, even if the properties of the zeolite powder itself are the same, the performance differs depending on the molding technique.
ゼオライト成形体の製造法については、従来より数多く
の提案がなされている。Many proposals have hitherto been made regarding a method for producing a zeolite molded body.
ゼオライト成形体は結合剤を使用するものと使用しない
ものとに大別できるが、前者にあっては、粘土鉱物を結
合剤として使用するもの；例えば特公昭33-9872号公
報，特公昭35-769号公報，特公昭39-21821号公報，特公
昭46-32572号公報，特公昭46-27374号公報などが代表的
であり、粘土鉱物以外の無機質結合剤を使用するもの；
例えば特公昭42-90号公報，特公昭48-37513号公報，特
公昭44-14092号公報，特公昭47-67895号公報、有機質結
合剤を使用するもの；例えば特開昭48-39399号公報，特
開昭49-40321号公報，特公昭50-9748号公報，特開昭50-
120487号公報，特開昭54-69596号公報，特開昭54-21832
号公報等が代表的にあげられる。Zeolite compacts can be roughly classified into those with a binder and those without a binder. In the former case, a clay mineral is used as a binder; for example, JP-B-33-9872 and JP-B-35- Representative examples are Japanese Patent Publication No. 769, Japanese Patent Publication No. 39-21821, Japanese Patent Publication No. 46-32572, Japanese Patent Publication No. 46-27374, etc., which use an inorganic binder other than clay minerals;
For example, JP-B-42-90, JP-B-48-37513, JP-B-44-14092, JP-B-47-67895, and those using an organic binder; for example, JP-A-48-39399. , JP-A-49-40321, JP-B-50-9748, JP-A-50-
120487, JP-A-54-69596, JP-A-54-21832
Representative publications are listed.
［発明が解決しようとする問題点］ 一般に、ゼオライト成形体はゼオライト結晶の粘度特
性、成形法が特定される場合、成形体のマクロ孔容積は
成形する際の水分添加量で調整されるが、押出造粒を例
にとると本発明者らの実験によれば水分許容範囲は意外
と狭く、混練物の水分量（結晶水は除く）は約17〜23重
量％（湿潤重量基準）の範囲にあり、この範囲でのマク
ロ孔容積は約0.2〜0.3cm3/gの範囲でしか調節できな
い。[Problems to be Solved by the Invention] Generally, in the case of a zeolite molded body, when the viscosity characteristics of the zeolite crystal and the molding method are specified, the macropore volume of the molded body is adjusted by the amount of water added during molding, Taking extrusion granulation as an example, according to the experiments of the present inventors, the allowable moisture range is surprisingly narrow, and the water content (excluding water of crystallization) of the kneaded product is in the range of about 17 to 23% by weight (wet weight basis). Yes, the macropore volume in this range can only be adjusted in the range of about 0.2-0.3 cm 3 / g.
成形体において可能な限りマクロ孔容積を大きくするこ
とは性能向上となるから望ましいが、成形強度と矛盾す
る特性であるから自ずと限度がある。It is desirable to increase the volume of macropores in the molded product as much as possible in order to improve the performance, but it is naturally limited because it is a property that contradicts the molding strength.
特に最近、PSA法による吸着分離技術の発展に伴い、こ
れにゼオライト吸着剤が使用されるようになってきた
が、この場合、ゼオライト成形体の吸着速度が重要な特
性として注目されてきた。この吸着速度はゼオライト成
形体のマクロ孔容積に依存するので、成形体において如
何に強度を保持したマクロ孔容積の大きいものを得るか
が基本的問題である。In particular, recently, with the development of the adsorption separation technology by the PSA method, a zeolite adsorbent has been used for this, and in this case, the adsorption rate of the zeolite compact has been noted as an important characteristic. Since this adsorption rate depends on the macropore volume of the zeolite molded body, the fundamental problem is how to obtain a molded body having a large macropore volume that retains strength.
本発明は、上記のような結合剤を配合したゼオライト成
形体における基本的課題を解決すべく、改良を提供する
ものである。The present invention provides an improvement in order to solve the basic problem in the zeolite molded body containing the binder as described above.
［問題点を解決するための手段］ 本発明者らは上記の従来技術に鑑み鋭意研究を重ねたと
ころ、粘土鉱物を結合剤とするゼオライト成形体におい
て、パルプ短繊維を併用して成形すると、成形体の強度
を充分に保持できると共に成形体のマクロ孔容積が改善
することを知見し、本発明を完成した。[Means for Solving Problems] The inventors of the present invention have made extensive studies in view of the above-mentioned conventional techniques, and in a zeolite molded body using a clay mineral as a binder, when pulp short fibers are used in combination, The present invention has been completed by finding that the strength of the molded body can be sufficiently maintained and the macropore volume of the molded body is improved.
すなわち、本発明によれば、第１にゼオライトを無水物
換算当り70〜95重量％含有するゼオライト成形体であっ
て、該成形体はマクロ孔容積（ml/g）ミクロ孔容積（ml
/g）の比が１〜4.5で、かつマクロ孔容積が0.3〜0.7ml/
gの連続気孔を有することを特徴とするゼオライト成形
体が提供される。That is, according to the present invention, firstly, there is provided a zeolite compact containing 70 to 95% by weight of zeolite per anhydrous equivalent, wherein the compact has a macropore volume (ml / g) and a micropore volume (ml).
/ g) ratio is 1 to 4.5 and the macropore volume is 0.3 to 0.7 ml /
Provided is a zeolite shaped body having g continuous pores.
また、本発明によれば、第２に、平均粒子径１〜５μｍ
のゼオライト粉末100重量部（無水物換算）当り粘土鉱
物粉末５〜30重量部、繊維長1000μｍ以下のパルプ短繊
維１〜35重量部および有機水溶性高分子物質０〜３重量
部からなる混合物を適量の水の存在下で造粒成型および
乾燥して得られる成形体を500〜700℃における焼成によ
り有機成分を焼失せしめて、成形体に連続したマクロ孔
を付与せしめることを特徴とするゼオライト成形体の製
造法が提供される。Further, according to the present invention, secondly, the average particle diameter is 1 to 5 μm.
A mixture of 5 to 30 parts by weight of clay mineral powder, 1 to 35 parts by weight of pulp short fibers having a fiber length of 1000 μm or less, and 0 to 3 parts by weight of an organic water-soluble polymer substance per 100 parts by weight of zeolite powder (converted to anhydrous form). Zeolite molding characterized by granulating and drying in the presence of an appropriate amount of water to obtain a molded body, which is burned at 500 to 700 ° C. to burn off the organic component and to give the molded body continuous macropores. A method of making a body is provided.
［作 用］ 本発明におけるゼオライト粉末は、独特な三次元構造の
結晶性アルミノシリケートでいわゆるモレキュラーシー
ブの特性を有するものであれば特に限定はなく、合成品
又は天然品のいずれであってもよい。[Operation] The zeolite powder in the present invention is not particularly limited as long as it is a crystalline aluminosilicate having a unique three-dimensional structure and has so-called molecular sieve characteristics, and may be a synthetic product or a natural product. .
これらのゼオライトとしては、ゼオライトＡ、ゼオライ
トＸ、ゼオライトＹ、モルデナイト、ZSM-5などのハイ
シリカゼオライトなどがあげられ、通常は結晶形、粒子
径等のコントロールの点からみて合成品の方がすぐれて
いる。Examples of these zeolites include high-silica zeolites such as zeolite A, zeolite X, zeolite Y, mordenite, and ZSM-5. Usually, synthetic products are superior in terms of control of crystal form and particle size. ing.
かかるゼオライト粉末は平均粒子径１〜５μｍの範囲に
あるものがよく、出来るだけ粒度分布のシャープなもの
が好ましい。この範囲外のものは合成的に難しいとかあ
るいは吸着特性が劣るとかの傾向になり易く、実用性に
欠けるからである。The zeolite powder preferably has an average particle size in the range of 1 to 5 μm, and preferably has a particle size distribution as sharp as possible. This is because those outside this range tend to be difficult to synthesize synthetically or have poor adsorption properties, and are not practical.
なお、上記ゼオライト粉末においては周知のようにカチ
オン交換性があり、基本ゼオライトであるナトリウムア
ルミノシリケートのナトリウムイオンがその全部又は一
部を他の金属イオンとイオン交換された置換型ゼオライ
トであっても勿論差支えなく、むしろ必要に応じて置換
型ゼオライトを用いる場合も多い。置換できる陽イオン
としては、例えばH+,Li+,K+,Ca などが代表的にあげら
れる。As is well known in the above zeolite powder,
It has an on-exchange property and is a basic zeolite, sodium acetate.
The sodium ions of luminosilicate are all or one
Substituted Zeoli with ion exchanged with other metal ions
Of course, it does not matter, but rather replaces if necessary
Type zeolite is often used. Replaceable cation
For example, H+, Li+, K+, Ca And so on
Be done.
本発明にかかるゼオライト成形体は、上記のようなゼオ
ライトを無水物換算当り70〜95重量％含有するものであ
って、マクロ孔容積（ml/g）／ミクロ孔容積（ml/g）の
比が１〜4.5で、かつマクロ孔容積が0.3〜0.7ml/gの連
続気孔を有することを特徴とするものである。The zeolite molded article according to the present invention contains the above-mentioned zeolite in an amount of 70 to 95% by weight based on an anhydride, and has a macropore volume (ml / g) / micropore volume (ml / g) ratio. Is 1 to 4.5 and has a macropore volume of 0.3 to 0.7 ml / g continuous pores.
なお、ここでミクロ孔容積とはゼオライト自体の結晶構
造に基づく空孔容積であり、また、マクロ孔容積とはゼ
オライト成形体に基づく空孔容積で、それぞれ後述する
試験方法で与えられる。The micropore volume here is the pore volume based on the crystal structure of the zeolite itself, and the macropore volume is the pore volume based on the zeolite compact, which are given by the test methods described below.
上記において他の成分としては殆ど全ては結合剤として
の粘土鉱物が配合されている。In the above, as the other components, almost all of them are blended with clay minerals as a binder.
マクロ孔容積（ml/g）／ミクロ孔容積（ml/g）の比が１
〜4.5の範囲にすることにより吸着速度が高く強度の大
きい成形体とすることができる。この比が１未満の場合
は吸着性能に劣り、4.5を越える場合は成形体としての
強度が低く好ましくない。Macropore volume (ml / g) / micropore volume (ml / g) ratio is 1
By setting it in the range of up to 4.5, a molded product having a high adsorption rate and high strength can be obtained. If this ratio is less than 1, the adsorption performance will be poor, and if it exceeds 4.5, the strength as a molded body will be low, such being undesirable.
このように、本発明にかかるゼオライト成形体にあって
は、充分な成形強度を保持していながら連続気孔を有し
て従来よりマクロ孔容積が大きくそれ故にガスに対する
吸着速度にすぐれた特性を有するものである。As described above, in the zeolite molded body according to the present invention, while maintaining sufficient molding strength, it has continuous pores and has a larger macropore volume than in the past, and therefore has an excellent adsorption rate for gas. It is a thing.
次に、本発明にかかるゼオライト成形体は、平均粒子径
１〜５μｍのゼオライト粉末100重量部（無水物換算）
当り粘土鉱物粉末５〜30重量部、繊維長1000μｍ以下の
パルプ短繊維１〜35重量部および有機水溶性高分子物質
０〜３重量部からなる混合物を適量の水の存在下で造粒
成型および乾燥して得られる成形体を500〜700℃におけ
る焼成により有機成分を焼失せしめて、成形体に連続し
たマクロ孔を付与せしめることを特徴として製造するこ
とができる。Next, the zeolite compact according to the present invention is 100 parts by weight of zeolite powder having an average particle diameter of 1 to 5 μm (calculated as an anhydride).
A mixture of 5 to 30 parts by weight of clay mineral powder, 1 to 35 parts by weight of pulp short fibers having a fiber length of 1000 μm or less, and 0 to 3 parts by weight of organic water-soluble polymer substance is granulated and molded in the presence of an appropriate amount of water. The molded product obtained by drying can be manufactured by burning the molded product at 500 to 700 ° C. to burn off the organic component to give continuous macropores to the molded product.
出発原料としてゼオライト粉末は、前記したとおりであ
り、また粘土鉱物としては例えばスメクタイト属、カオ
リン系、パリゴルスカイト、ヘクトライトあるいはセピ
オライトなどの一種又は２種以上の粘土鉱物の微粉末が
あげられる。Zeolite powder as a starting material is as described above, and clay minerals include fine powders of one or more clay minerals such as smectite, kaolin, palygorskite, hectorite, and sepiolite.
更にパルプ短繊維としては、繊維長が10μｍ以上で1mm
以下であることが必要であり、好ましくは10〜100μｍ
の非晶質パルプがよい。繊維長がこの範囲外にあっては
成形体の焼成後における連続気孔が不充分であるか又は
連続気孔があっても成形強度が不充分である、あるいは
粉体混合が均一にならないなどの傾向にあって、目的と
する成形体特性を具備させる点から不適当であることに
よる。Furthermore, as pulp short fibers, if the fiber length is 10 μm or more, 1 mm
It is necessary to be below, preferably 10 to 100 μm
Amorphous pulp is preferred. If the fiber length is out of this range, the continuous pores after firing of the molded body will be insufficient, or the molding strength will be insufficient even if there are continuous pores, or the powder mixing will not be uniform. However, it is unsuitable from the viewpoint of providing the desired molded product characteristics.
なお、他の補助原料としてカルボキシメチルセルロー
ス、メチルセルロース、ポリビニルアルコール、ポリア
クリルアミドあるいはそれらの誘導体、澱粉およびその
誘導体、その他天然あるいは合成の水溶性高分子物質が
あげられ、これらの１種又は２種以上は必要に応じて用
いられる。Other auxiliary raw materials include carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, polyacrylamide or their derivatives, starch and its derivatives, and other natural or synthetic water-soluble polymer substances, and one or more of these may be used. Used as needed.
この理由は、この水溶性高分子物質は、成形体の乾燥時
強度をあげることができると共に、造粒工程において配
合原料を空気輸送などを伴う場合の発塵防止の作用があ
るが、出発原料の配合および成形の操作如何によっては
この補助原料なくしても充分可能であるために、必ずし
も不可欠な原料とすることがないからである。The reason for this is that this water-soluble polymer substance can increase the strength of the molded product when dried, and also has the function of preventing dust generation when the compounded raw materials are accompanied by pneumatic transportation in the granulation step. This is because, depending on the compounding and molding operations, the auxiliary raw material can be sufficiently used and is not necessarily an indispensable raw material.
かかる出発原料は、ゼオライト粉末を無水物換算で100
重量部当り粘土鉱物粉末５〜30重量部およびパルプ短繊
維１〜35重量部および水溶性高分子物質０〜３重量部の
組成割合で配合し、これに所望の水を添加して混練す
る。Such a starting material is 100% of zeolite powder in terms of anhydride.
5 to 30 parts by weight of clay mineral powder, 1 to 35 parts by weight of pulp short fibers, and 0 to 3 parts by weight of water-soluble polymeric substance are blended per part by weight, and desired water is added thereto and kneaded.
上記組成割合以外にあっては、強度とマクロ孔容積を同
時に満足する目的の形成体は得ることが難しい。Except for the above composition ratio, it is difficult to obtain a formed body for the purpose of simultaneously satisfying the strength and the macropore volume.
原料配合物の水の存在下における混練および造粒成形操
作は既にこの分野においては自明であり、本発明におい
ても特に限定することなく所望の手段で行えばよい。The kneading and granulation molding operations of the raw material mixture in the presence of water are already obvious in this field, and the present invention is not particularly limited and may be carried out by a desired means.
このことは造粒物の形状についても同様であるが、多く
の場合、造粒物の大きさはその製品の使用目的にもよる
が大体１〜10mmの範囲のものがよい。The same applies to the shape of the granulated product, but in most cases, the size of the granulated product is preferably in the range of 1 to 10 mm, although it depends on the intended use of the product.
造粒物の成形後は、その後の焼成工程において充分に耐
えるに必要な強度を持たせるためと、乾燥工程を必要と
する。これは通常100〜120℃で0.5〜２時間の範囲であ
る。After the granulated product is molded, a drying process is required in order to have sufficient strength to withstand the subsequent firing process. This is usually in the range of 100-120 ° C for 0.5-2 hours.
次いで500〜700℃、好ましくは550〜650℃において１〜
３時間、好ましくは1.5〜2.5時間造粒物を焼成して存在
する有機物と実質的に燃焼除去すると共にゼオライト水
の脱水による活性化、成形物の強度付与を行う。Then, at 500 to 700 ° C, preferably 550 to 650 ° C, 1 to
The granulated product is calcined for 3 hours, preferably 1.5 to 2.5 hours to substantially burn and remove the organic matter present, and at the same time, the zeolite water is activated by dehydration and the molded product is given strength.
この工程により、混練および造粒の際に均一に分散しか
つ互に絡み合って造粒物と混在した状態にあるパルプ短
繊維が燃焼して消失することによりそのスケルトンが連
続気孔を形成するので成形体の強度の劣化を伴うことな
く大きなマクロ孔容積をもつ成形体とすることができ
る。By this process, the pulp skeletal fibers that are uniformly dispersed during the kneading and granulation and are entangled with each other and mixed with the granulated product burn and disappear, so that the skeleton forms continuous pores. A molded body having a large macropore volume can be obtained without deteriorating the strength of the body.
得られたゼオライト成形体は、そのまま製品に供するこ
とができるが、必要に応じ分級し所望外の粒径品にあっ
ては粉砕後、適当な前工程へ戻すこともできる。The obtained zeolite compact can be directly used as a product, but if necessary, it can be classified, and if it has a particle size not desired, it can be pulverized and then returned to an appropriate pre-process.
実施例１ NaA型ゼオライト粉末（10.98Na2O・Al2O3・1.98SiO2・
3.9H2O）125重量部、カオリン系粘土15重量部、繊維長1
0〜100μｍの非晶質パルプ短繊維（山陽国策パルプ製、
パルプフロックＷ−１）５重量部を混合後、水40重量部
を加えてニーダーで20分混練する。次いで押出造粒機
（不二パウダル（株）製）を用いて、ダイス径3mmをセ
ットし、押出成形し円柱状成形物を得た。得られた成形
物を110℃、２時間乾燥後、600℃、２時間焼成して直径
3mmのゼオライト成形体ペレットを得た。Example 1 NaA-type zeolite powder (10.98 Na 2 O.Al 2 O 3 1.98SiO 2
3.9H 2 O) 125 parts by weight, kaolin-based clay 15 parts by weight, fiber length 1
Amorphous pulp short fibers of 0-100 μm (made by Sanyo Kokusaku Pulp,
After mixing 5 parts by weight of pulp floc W-1), 40 parts by weight of water is added, and the mixture is kneaded with a kneader for 20 minutes. Next, a die diameter of 3 mm was set using an extrusion granulator (manufactured by Fuji Paudal Co., Ltd.) and extrusion molding was performed to obtain a columnar molded product. The molded product obtained is dried at 110 ° C for 2 hours and then fired at 600 ° C for 2 hours to obtain a diameter
3 mm zeolite compact pellets were obtained.
実施例２ 実施例１で用いたNaA型ゼオライト粉末250重量部を、水
2000重量部に分散し、このゼオライトスラリーに塩化カ
ルシウム（２水塩）160重量部を溶解し、10時間撹拌し
ながらカルシウムイオン交換を行う。イオン交換後、
過水洗して120℃で３時間乾燥後粉砕して、CaA型ゼオラ
イト246重量部を得た。この乾燥品を分析した結果、Ca
イオン交換率が74％の5A型ゼオライトであることが確認
された。このCaA型ゼオライト123重量部、α化澱粉（松
谷化学工業（株）製マツノリンCM）２重量部、カオリン
系粘土10重量部、モンモリロライト系粘土10重量部、繊
維長10〜100μｍの非晶質、パルプ短繊維（山陽国策パ
ルプ製、KCフロックＷ−50（Ｓ））10重量部を混合後、
水42重量部を加えてニーダーで20分混練する。Example 2 250 parts by weight of the NaA-type zeolite powder used in Example 1 was mixed with water.
Dispersed in 2000 parts by weight, 160 parts by weight of calcium chloride (dihydrate) is dissolved in this zeolite slurry, and calcium ion exchange is performed while stirring for 10 hours. After ion exchange,
It was washed with water, dried at 120 ° C. for 3 hours, and then pulverized to obtain 246 parts by weight of CaA-type zeolite. As a result of analyzing this dried product, Ca
It was confirmed that the 5A type zeolite had an ion exchange rate of 74%. 123 parts by weight of this CaA type zeolite, 2 parts by weight of pregelatinized starch (Matsutani Chemical Industry Co., Ltd. Matsunoline CM), 10 parts by weight of kaolin clay, 10 parts by weight of montmorillonite clay, amorphous fiber having a fiber length of 10 to 100 μm After mixing 10 parts by weight of quality, short pulp fiber (KC Flock W-50 (S) from Sanyo Kokusaku Pulp),
Add 42 parts by weight of water and knead with a kneader for 20 minutes.
次いで押出造粒機（不二パウダル（株）製）を用いてダ
イス径1.5mmをセットし、押出成形し円柱状成形物を得
た。得られた成形物を110℃で２時間乾燥後600℃、２時
間焼成して直径1.5mmのゼオライト成形体ペレットを得
た。Next, a die diameter of 1.5 mm was set using an extrusion granulator (manufactured by Fuji Paudal Co., Ltd.) and extrusion molding was performed to obtain a columnar molded product. The obtained molded product was dried at 110 ° C. for 2 hours and then calcined at 600 ° C. for 2 hours to obtain zeolite molded pellets having a diameter of 1.5 mm.
実施例３ NaX型ゼオライト粉末（Na2O・Al2O3・2.5SiO2・nH2O）1
28重量部（含水率22％）、モンモリロナイト系粘土（ク
ニミネ工業（株）製クニゲルVA）15重量部、カオリン系
粘土10重量部、繊維長10〜100μｍの非晶質パルプ短繊
維（山陽国策パルプ製、パルプフロックＷ−５）20重量
部を、混合後、水46重量部を加えて、ニーダーで20分混
練する。次いで押出造粒機（不二パウダル（株）製）を
用いてダイス（径3mm）をセットし、押出成形した。得
られた円柱状成形物を110℃で２時間乾燥後、750℃、30
分間焼成しNaX型ゼオライトペレットを得た。Example 3 NaX-type zeolite powder (Na 2 O · Al 2 O 3 · 2.5SiO 2 · nH 2 O) 1
28 parts by weight (water content 22%), montmorillonite clay (Kunimine VA Co., Ltd., Kunigel VA) 15 parts by weight, kaolin clay 10 parts by weight, amorphous pulp short fibers with a fiber length of 10 to 100 μm (Sanyo Kokusaku Pulp) After mixing 20 parts by weight of pulp floc W-5) manufactured by Manufacture Co., 46 parts by weight of water is added and kneaded for 20 minutes with a kneader. Next, a die (diameter 3 mm) was set using an extrusion granulator (manufactured by Fuji Paudal Co., Ltd.), and extrusion molding was performed. The obtained cylindrical molded product was dried at 110 ° C for 2 hours, then at 750 ° C, 30
It was calcined for a minute to obtain NaX type zeolite pellets.
実施例４ Naモルデナイト粉末（Na2O・Al2O3・10SiO2・nH2O）114
重量部（含水率12％）、カオリン系粘土30重量部、実施
例１と同じパルプ短繊維30重量部を混合後、皿型造粒機
（直径70cm、回転数14rpm）で、水を噴霧しながら転動
造粒を行なった。水添加量は、35重量部であった。得ら
れた造粒物を110℃で２時間乾燥後、700℃、１時間焼成
し、球状多孔性モルデナイト成形品を得た。Example 4 Na mordenite powder (Na 2 O · Al 2 O 3 · 10SiO 2 · nH 2 O) 114
After mixing 30 parts by weight of kaolin clay with 30 parts by weight of kaolin clay (30% by weight of water), 30 parts by weight of the same pulp short fibers as in Example 1 were sprayed with water using a plate type granulator (diameter 70 cm, rotation speed 14 rpm). While rolling, granulation was performed. The amount of water added was 35 parts by weight. The obtained granulated product was dried at 110 ° C. for 2 hours and then calcined at 700 ° C. for 1 hour to obtain a spherical porous mordenite molded product.
実施例５ 天然モルデナイト粉末（クニミネ工業（株）製ゼオライ
ト150）105重量部、スメクタイト属粘土（クニミネ工業
（株）製クニゲルVA）20重量部、実施例２と同じパルプ
短繊維10重量部を混合後、皿型造粒機を用い、α化澱粉
（松谷化学工業（株）製マツノリンCM）４％溶液を噴霧
しながら、転動造粒を行なった。水添加量は34重量部で
あった。得られた造粒物を110℃で２時間乾燥後、700
℃、１時間焼成し、球状多孔性天然モルデナイト成形品
を得た。Example 5 105 parts by weight of natural mordenite powder (Kunimine Industry Co., Ltd. zeolite 150), 20 parts by weight of smectite genus clay (Kunimine Industry Co., Ltd. Kunigel VA), and 10 parts by weight of the same pulp short fibers as in Example 2 were mixed. After that, rolling granulation was performed using a plate type granulator while spraying a 4% solution of pregelatinized starch (Matsunoline CM manufactured by Matsutani Chemical Industry Co., Ltd.). The amount of water added was 34 parts by weight. After drying the obtained granules at 110 ° C for 2 hours, 700
Firing at 1 ° C. for 1 hour gave a spherical porous natural mordenite molded product.
比較例１ 実施例２においてパルプ短繊維を添加せずに、Na−Ａ型
ゼオライト粉末125重量部、カオリン粘土15重量部を混
合後、水40重量部を加えてニーダーで20分混練後、押出
造粒機を用いて（不二パウダル（株）製）ダイス径3mm
をセットし、押出成形し実施例２と同じように操作して
円柱状成形物を得た。得られた成形物を110℃、２時間
乾燥後、600℃、２時間焼成して直径3mmのゼオライト成
形体ペレットを得た。Comparative Example 1 In Example 2, 125 parts by weight of Na-A type zeolite powder and 15 parts by weight of kaolin clay were mixed without adding short pulp fibers, 40 parts by weight of water was added, and the mixture was kneaded in a kneader for 20 minutes and then extruded. Die diameter 3mm using a granulator (manufactured by Fuji Paudal Co., Ltd.)
Was set, extrusion-molded, and operated in the same manner as in Example 2 to obtain a cylindrical molded product. The obtained molded product was dried at 110 ° C. for 2 hours and then calcined at 600 ° C. for 2 hours to obtain a zeolite molded product pellet having a diameter of 3 mm.
＜評価方法＞ （１）ゼオライト粉末の粒度測定 コールターカウンター（TA-II型）を用いて粒度測定
し、平均粒子径として表わす。<Evaluation Method> (1) Particle Size Measurement of Zeolite Powder The particle size is measured using a Coulter counter (TA-II type) and expressed as an average particle size.
（２）ゼオライトミクロ孔容積の測定 NaA型ゼオライト、CaA型ゼオライト、NaX型ゼオライト
およびモルデナイトなどの成形前の各種ゼオライト粉末
を、温度25℃、相対湿度60％の恒温恒湿槽中で、５日間
吸湿処理後、800℃で焼成し、吸着した水分の容積より
下式より、空孔容積を求めた。(2) Measurement of zeolite micropore volume Various types of zeolite powder such as NaA type zeolite, CaA type zeolite, NaX type zeolite and mordenite before forming are placed in a thermo-hygrostat at a temperature of 25 ° C and a relative humidity of 60% for 5 days. After the moisture absorption treatment, it was baked at 800 ° C., and the pore volume was calculated from the volume of the adsorbed water by the following formula.
（３）圧縮破壊強度 富山産業（株）製錠剤破壊強度測定装置TH-203型で100
個の試料を測定しその平均値を求めた。 (3) Compressive Fracture Strength 100 by the tablet fracture strength measuring device TH-203 manufactured by Toyama Sangyo Co., Ltd.
Each sample was measured and the average value was calculated.
（４）マクロ孔容積の測定 成形体試料1.0gを採取し、水銀圧入式ポロシメーター
（カンタクローム社製、AUTOSCAN-33）で10〜2300Kg/cm
2まで加圧し、細孔半径で約32〜0.0032μｍまでの全マ
クロ孔容積を測定した。(4) Measurement of macropore volume 1.0 g of a molded body sample was sampled with a mercury injection porosimeter (AUTOSCAN-33 manufactured by Kantachrome Co., Ltd.) at 10 to 2300 Kg / cm.
The pressure was increased to 2 , and the total macropore volume up to about 32-0.0032 μm in pore radius was measured.
＜物性測定結果＞ 第１表に示すとおり。<Physical property measurement results> As shown in Table 1.
［発明の効果］ 本発明によれば、0.3〜0.7ml/gという大きなマクロ孔容
積と充分な成形強度をもつゼオライト成形体を容易に得
ることができる。 [Effects of the Invention] According to the present invention, it is possible to easily obtain a zeolite compact having a large macropore volume of 0.3 to 0.7 ml / g and a sufficient compacting strength.
このようなゼオライト成形体はガス吸着速度が速いので
PSA法は勿論、その他各種の工業分野における吸着剤、
あるいは触媒として効果的に利用することができる。Since such a zeolite compact has a high gas adsorption rate,
Not only the PSA method, but also other adsorbents in various industrial fields,
Alternatively, it can be effectively used as a catalyst.
Claims (5)
含有するゼオライト成形体であって、該成形体はマクロ
孔容積（ml/g）／ミクロ孔容積（ml/g）の比が１〜4.5
で、かつマクロ孔容積が0.3〜0.7ml/gの連続気孔を有す
ることを特徴とするゼオライト成形体。1. Zeolite is 70 to 95% by weight per anhydrate equivalent.
A zeolite compact containing, wherein the compact has a macropore volume (ml / g) / micropore volume (ml / g) ratio of 1 to 4.5.
And a zeolite compact having continuous pores having a macropore volume of 0.3 to 0.7 ml / g.
ばれた少なくとも１種のＡ型、Ｙ型、Ｘ型又はモルデナ
イト型のいずれかのゼオライト粉末である特許請求の範
囲第１項記載のゼオライト成形体。2. The zeolite powder is at least one type A, Y, X or mordenite type zeolite powder selected from H, Li, K, Na or Ca. The molded zeolite article according to item.
状、だ円形又は棒状のいずれかの成形体である特許請求
の範囲第１項記載のゼオライト成形体。3. The zeolite molded body according to claim 1, wherein the molded body is a spherical, elliptical or rod-shaped molded body having a maximum diameter in the range of 1 to 10 mm.
重量部（無水物換算）当り、粘土鉱物粉末５〜30重量
部、繊維長1000μｍ以下のパルプ短繊維１〜35重量部お
よび有機水溶性高分子物質０〜３重量部からなる混合物
を適量の水の存在下で造粒成型および乾燥して得られる
成形体を500〜700℃における焼成により有機成分を焼失
せしめて、成形体に連続したマクロ孔を付与せしめるこ
とを特徴とするゼオライト成形体の製造法。4. A zeolite powder 100 having an average particle size of 1 to 5 μm.
An appropriate amount of a mixture of 5 to 30 parts by weight of clay mineral powder, 1 to 35 parts by weight of pulp short fibers having a fiber length of 1000 μm or less, and 0 to 3 parts by weight of organic water-soluble polymer substance per part by weight (anhydrous equivalent) is added. The production of a zeolite compact characterized by granulating and drying the compact in the presence of 500 ° C. to 700 ° C. to burn off the organic component to give continuous macropores to the compact. Law.
囲にある非晶質パルプ短繊維である特許請求の範囲第４
項記載のゼオライト成形体の製造法。5. A short pulp fiber is an amorphous pulp short fiber having a fiber length in the range of 10 to 100 μm.
The method for producing a molded zeolite article according to item.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61127208A JPH0674136B2 (en) | 1986-06-03 | 1986-06-03 | Zeolite compact and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61127208A JPH0674136B2 (en) | 1986-06-03 | 1986-06-03 | Zeolite compact and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283812A JPS62283812A (en) | 1987-12-09 |
| JPH0674136B2 true JPH0674136B2 (en) | 1994-09-21 |
Family
ID=14954396
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61127208A Expired - Fee Related JPH0674136B2 (en) | 1986-06-03 | 1986-06-03 | Zeolite compact and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0674136B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694476A (en) * | 2017-07-25 | 2018-02-16 | 江苏远鸿新材料科技有限公司 | A kind of moulding manufacture method of high intensity ball-type drier |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297282A (en) * | 1987-05-29 | 1988-12-05 | Showa Senpu Kk | Production of zeolite compact |
| JP3217101B2 (en) * | 1991-12-12 | 2001-10-09 | 日本化学工業株式会社 | Method for producing air purifier |
| GR1002917B (en) * | 1997-06-06 | 1998-06-01 | / | Porous material used as an air refining and sanitation filter. it is used for the absorption of odors, vapors and toxic gases, for the oxidation of the insatiate organic gases, as well as for the destruction of the suspended microorganisms. ... |
| JP4517406B2 (en) * | 1998-03-04 | 2010-08-04 | 東ソー株式会社 | Low-silica X-type zeolite bead molded body and method for producing the same |
| US6743745B2 (en) * | 2002-01-22 | 2004-06-01 | Zeochem | Process for production of molecular sieve adsorbent blends |
| JP2004143035A (en) * | 2002-08-30 | 2004-05-20 | Tokuyama Corp | Crystalline inorganic porous material and its producing method |
| EP1394113B1 (en) * | 2002-08-30 | 2009-04-29 | Tokuyama Corporation | Crystalline inorganic porous material |
| JP5016442B2 (en) * | 2007-10-23 | 2012-09-05 | 共同印刷株式会社 | Method for producing adsorbent-containing molded body and adsorbent-containing molded body |
| DE102008046155B4 (en) | 2008-03-03 | 2017-01-26 | Chemiewerk Bad Köstritz GmbH | Process for producing an adsorbent granulate |
| EP2527296B1 (en) | 2011-05-25 | 2021-07-07 | Chemiewerk Bad Köstritz GmbH | Adhesive-free zeolithic granulate with faujasite structure and method for producing such an adhesive-free zeolithic granulate and use of same |
| DE102012020217A1 (en) | 2012-10-15 | 2014-04-17 | Chemiewerk Bad Köstritz GmbH | Binder-free compact zeolitic moldings and process for their preparation |
| JP2016179467A (en) * | 2015-03-24 | 2016-10-13 | 東ソー株式会社 | Dehydrator of gas |
| JP7145020B2 (en) * | 2018-09-26 | 2022-09-30 | 水澤化学工業株式会社 | purification material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58124539A (en) * | 1982-01-19 | 1983-07-25 | Toray Ind Inc | Adsorbent for separating gas |
| JPS59156954A (en) * | 1983-02-28 | 1984-09-06 | 三井造船株式会社 | Manufacture of porous ceramics |
| JPS6186476A (en) * | 1984-10-04 | 1986-05-01 | 東陶機器株式会社 | Manufacture of porous ceramic |
-
1986
- 1986-06-03 JP JP61127208A patent/JPH0674136B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694476A (en) * | 2017-07-25 | 2018-02-16 | 江苏远鸿新材料科技有限公司 | A kind of moulding manufacture method of high intensity ball-type drier |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62283812A (en) | 1987-12-09 |
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