JP5260894B2 - Method for producing adsorbent-containing molded body and adsorbent-containing molded body - Google Patents
Method for producing adsorbent-containing molded body and adsorbent-containing molded body Download PDFInfo
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Abstract
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本発明は、吸着剤含有成形体の製造方法及び吸着剤含有成形体に関し、詳しくは、型を個々に使用しないで成形されるゼオライト高濃度含有の吸着剤含有成形体の製造方法及び該製造方法により得られた吸着剤含有成形体に関する。 The present invention relates to a method for producing an adsorbent-containing molded article and an adsorbent-containing molded article, and more specifically, a method for producing an adsorbent-containing molded article containing a high concentration of zeolite that is molded without individually using a mold, and the production method. Relates to an adsorbent-containing molded article obtained by the above.
従来、水分を含む気体成分を吸着させるためにゼオライトが使用されていたが、高湿度環境下では気体成分よりも水分を多く吸着する傾向にあるが、ゼオライトのマクロポアのサイズを特定の範囲とすることにより選択的にガスを分離したり、電子部品や電子製品内部で発生するアウトガスを吸着したり、冷蔵庫フロン冷媒の吸着、有機溶媒中の水分の除去、近年環境保護の観点からは発電所等の燃焼排気ガスからの二酸化炭素吸着分離の用途に広く用いられている。 Conventionally, zeolite has been used to adsorb gas components containing moisture, but it tends to adsorb more moisture than gas components in a high humidity environment, but the size of the macropores in the zeolite is in a specific range. To selectively separate gases, adsorb outgas generated inside electronic parts and electronic products, adsorb refrigerator refrigerants, remove moisture in organic solvents, power plants from the viewpoint of environmental protection in recent years It is widely used for the adsorption separation of carbon dioxide from combustion exhaust gas.
特許文献１には、金属アルコキシド溶液と合成ゼオライトとの混合溶液を加水分解して、多孔質ガラス中に合成ゼオライトを分散させ、しかる後乾燥させる吸着剤組成物の製造方法が開示されている。しかしながら、合成ゼオライト含有量は３０重量％以下と低含有量である。 Patent Document 1 discloses a method for producing an adsorbent composition in which a mixed solution of a metal alkoxide solution and a synthetic zeolite is hydrolyzed to disperse the synthetic zeolite in porous glass and then dried. However, the synthetic zeolite content is as low as 30% by weight or less.
特許文献２には、無機系バインダーの粘土とゼオライトをボールミルのような物理的力で混練し分散させ、２５０℃以上で焼成させたゼオライト多孔質体を開示している。 Patent Document 2 discloses a porous zeolite body in which an inorganic binder clay and zeolite are kneaded and dispersed by a physical force such as a ball mill and calcined at 250 ° C. or higher.
ゼオライト粉末の吸着力を維持したままの成形体を作るにはゼオライト粉末含有量を７０重量％以上にする必要がある。しかしながら、ゼオライト粉末は集結性が無いため高含有させる困難であった。また、ゼオライト９０重量％ビーズが製造されているが（例えば、特許文献３参照）、粘土系材料をバインダーとして混練し造粒機で製造しているのでビーズ形状のみであった。そのビーズ形状は、電子部品に組み込む微細形状からするとサイズ精度は劣るものであった。 In order to produce a compact with the adsorption power of the zeolite powder maintained, the zeolite powder content needs to be 70% by weight or more. However, it is difficult to make the zeolite powder highly contained because it has no aggregation property. Moreover, although 90 wt% zeolite beads are manufactured (see, for example, Patent Document 3), the beads are only in the shape of beads because they are kneaded using a clay-based material as a binder and manufactured by a granulator. The bead shape was inferior in size accuracy from the fine shape incorporated in the electronic component.
また、粘土系材料を用い成形体を個々に金型を使用して成形すると、型入れ、型抜き作業による成形品の欠け、破損が少なからず発生することは避けられず、微細形状を成形することは困難であった。 In addition, when moldings are individually molded using clay-based materials using molds, it is inevitable that molded parts will be chipped and broken due to mold insertion and die-cutting operations, and a fine shape is formed. It was difficult.
また、錠剤成形のような方法では、成形時に一次成形されたシート状のゼオライト材料を、更に二次成形で繰り返し加圧されるとゼオライトのマクロポアが潰れて吸着能力が低下することがある。 In a method such as tablet molding, if the sheet-shaped zeolite material that is primarily molded at the time of molding is further repeatedly pressed in the secondary molding, the macropores of the zeolite may be crushed and the adsorption capacity may be reduced.
そこで大規模な装置を使用せず、ゼオライト７０重量％以上の成形体を電子部品に組み込むことができるような微細でサイズ精度が良い微細形状を作れる製造方法が望まれていた。
本発明の目的は、吸着力を維持することができるようにゼオライトを７０重量％以上の高濃度に含有したゼオライト高含有成形体の吸着剤含有成形体の製造方法及び該製造方法により得られた吸着剤含有成形体を提供することである。 The object of the present invention was obtained by a method for producing an adsorbent-containing molded article of a zeolite-rich molded article containing zeolite in a high concentration of 70% by weight or more so that the adsorption power can be maintained, and the production method. It is to provide an adsorbent-containing shaped article.
本発明の別の目的は、サイズ精度が良好な微細形状を型を個々に使用しなくても成形方法が容易な吸着剤含有成形体の製造方法を提供することである。 Another object of the present invention is to provide a method for producing an adsorbent-containing molded article that can be easily molded without using individual molds having fine shapes with good size accuracy.
本発明に従って、水及びアルコールの一方又は両方からなる溶媒、無機系バインダー及びゼオライトを混合してゼオライト含有湿潤粘土を形成する工程と、
該ゼオライト含有湿潤粘土を湿潤粘土体に硬化させる工程と、
該湿潤粘土体を切断する工程と、
該切断した湿潤粘土体を乾燥させて乾燥粘土体を形成する工程と、
を有する吸着剤含有成形体の製造方法であって、
該湿潤粘土体の変形率が０％超過９５％以下であり、
該切断工程が一片の刃からなる刃物で湿潤粘土体を切断させる工程であり、
該乾燥粘土体のゼオライト含有率が７０〜９８重量％である、
ことを特徴とする吸着剤含有成形体の製造方法が提供される。
In accordance with the present invention, mixing a solvent comprising one or both of water and alcohol, an inorganic binder and zeolite to form a zeolite-containing wet clay;
Curing the zeolite-containing wet clay to a wet clay body;
Cutting the wet clay body;
Drying the cut wet clay body to form a dry clay body;
A method for producing an adsorbent-containing molded article having
The deformation rate of the wet clay body is 0% and 95% or less,
The cutting step is a step of cutting the wet clay body with a blade consisting of a single blade,
The dry clay body has a zeolite content of 70 to 98% by weight,
There is provided a method for producing an adsorbent-containing molded article characterized by the above.
また、本発明に従って、上記吸着剤含有成形体の製造方法により得られた吸着剤含有成形体が提供される。 Moreover, according to this invention, the adsorbent containing molded object obtained by the manufacturing method of the said adsorbent containing molded object is provided.
上述したように、本発明により、成形し易い、ゼオライトを７０重量％以上と高含有した成形体が混練機や造粒機等の装置、更には個々に型を使用しなくても得られるようになった。 As described above, according to the present invention, it is possible to obtain a molded body that is easy to be molded and contains a high amount of zeolite of 70% by weight or more without using an apparatus such as a kneader or a granulator, or individually using a mold. Became.
また、本発明ではゼオライトを使用しているので、得られた成形体は水分以外の有機ガスや臭気を高効率で吸着でき、様々な用途に応用可能である。 In addition, since zeolite is used in the present invention, the obtained molded body can adsorb organic gas and odor other than moisture with high efficiency and can be applied to various uses.
本発明の製造方法によって、吸着剤を個々に型を使用しないで成形できるので、型入れ・型抜き作業が無くなり製造工程が簡素化することができ、型抜きによる成形品の欠け、破損が減少し、高い生産性で微細形状の成形体が作製することが可能となった。 With the manufacturing method of the present invention, the adsorbent can be molded without using a mold individually, so that there is no need to mold and unmould, the manufacturing process can be simplified, and chipping and breakage of molded products due to die cutting are reduced. In addition, it is possible to produce a compact shaped body with high productivity.
以下に、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明で用いるゼオライトは、親水性ゼオライト、疎水性ゼオライトのどちらでも構わず、天然ゼオライト又は合成ゼオライトを出発原料として鉱酸等を用いた脱アルミニウム処理等によって調製する方法、或はシリカ源、アルミナ源、アルカリ源及び有機鉱化剤を混合し結晶化する直接合成法等により得られる。ゼオライトは、分子の大きさの違いによって物質を分離するのに用いられる多孔質の粒状物質であり、均一な細孔を有する構造であって、細孔の空洞に入る小さな分子を吸着して一種のふるいの作用を示すため、吸着可能な分子の種類はゼオライト種類によって決まる。有機成分等の気体成分を吸着する場合は、ゼオライトの細孔入口径が吸着される分子径よりも大きければよい。通常は、細孔入口が酸素８、１０又は１２員環のゼオライトであればよい。本発明では、特に水分より有機ガスや臭気成分を優先的に吸着するものが好ましい。 The zeolite used in the present invention may be either a hydrophilic zeolite or a hydrophobic zeolite, and is prepared by a dealumination treatment using a mineral acid or the like using a natural zeolite or a synthetic zeolite as a starting material, or a silica source, alumina It can be obtained by a direct synthesis method in which a source, an alkali source and an organic mineralizer are mixed and crystallized. Zeolite is a porous granular material used to separate substances according to the difference in molecular size, and has a structure with uniform pores. Therefore, the type of molecules that can be adsorbed depends on the type of zeolite. When adsorbing a gas component such as an organic component, the pore inlet diameter of the zeolite may be larger than the molecular diameter to be adsorbed. Usually, the pore inlet may be a zeolite having an oxygen 8, 10 or 12 membered ring. In the present invention, those that preferentially adsorb organic gas and odor components over moisture are preferred.
本発明で用いる無機系バインダーは、金属アルコキシド加水分解物、コロイダルシリカ、アルミナゾル、ポリシロキサン及び粘土系鉱物からなる群から選択される。中でも金属アルコキシド加水分解物が好ましく、金属種としてはＳｉ、Ａｌ、Ｔｉが特に好ましい。粘土系鉱物としては、カオリン、ベントナイド等が挙げられる。 The inorganic binder used in the present invention is selected from the group consisting of metal alkoxide hydrolysates, colloidal silica, alumina sol, polysiloxane, and clay minerals. Of these, metal alkoxide hydrolysates are preferable, and Si, Al, and Ti are particularly preferable as the metal species. Examples of clay minerals include kaolin and bentonide.
本発明で用いる溶媒は、水及びアルコールの一方又は両方であり、無機バインダーが粘土系鉱物の場合は水のみで構わず、金属アルコキシド加水分解物、コロイダルシリカ、アルミナゾル、ポリシロキサン等は水及びアルコールの両方を混合して用いることができる。溶媒としてアルコールを用いる場合、イソプロピルアルコールやブタノール等の揮発性の低いアルコール使用すると湿潤粘土の変化率がなかなか変化しないので、メタノールやエタノールの低級アルコールを使用することが好ましい。溶媒における水とアルコールの比率は、水の濃度が２０重量％以上であることが好ましい。溶媒の湿潤粘土体における含有量は３０〜５０重量％が好ましく、５０重量％超過となると一次乾燥時に体積収縮率が大きくもろくなり、成形体にヒビが入り易い。 The solvent used in the present invention is one or both of water and alcohol. When the inorganic binder is a clay mineral, water may be used. Metal alkoxide hydrolyzate, colloidal silica, alumina sol, polysiloxane and the like are water and alcohol. Both of these can be used in combination. When alcohol is used as the solvent, it is preferable to use a lower alcohol such as methanol or ethanol because the change rate of wet clay does not change easily when a low-volatile alcohol such as isopropyl alcohol or butanol is used. The ratio of water to alcohol in the solvent is preferably such that the water concentration is 20% by weight or more. The content of the solvent in the wet clay body is preferably 30 to 50% by weight, and if it exceeds 50% by weight, the volume shrinkage becomes brittle during primary drying, and the molded body tends to crack.
本発明で示す湿潤粘土・湿潤粘土体の粘土とは、一般的に用いられるゲル状態をも含む。 The clay of the wet clay / wet clay body shown in the present invention includes a commonly used gel state.
水及びアルコールの一方又は両方からなる溶媒、無機系バインダー及びゼオライトを混合するとゼオライト含有湿潤粘土の状態は以下の様に、湿潤粘土状に変化し始め、
（１）流動性が有る状態（平らな面に流すと形状保持ができない状態）・・・変化率９５％超過１００％以下
（２）流動性が殆ど無い〜無い状態（粘土状）・・・変化率１０％超過９５％以下
（３）流動性が無い状態（寒天状）・・・変形率０％超過１０％以下
時間を往うごとに順々に変化していく。
When a solvent composed of one or both of water and alcohol, an inorganic binder, and zeolite are mixed, the state of the zeolite-containing wet clay begins to change to a wet clay, as follows:
(1) State with fluidity (state in which shape cannot be maintained when flowed on a flat surface) ... Change rate over 95% and 100% or less (2) State with little or no fluidity (clay-like) ... Change rate 10% over 95% or less (3) State of no fluidity (agar-like) ... Deformation rate 0% over 10% or less It changes in order as time passes.
本発明では、生産性の点からは、以下の製法が好ましい。 In the present invention, the following production method is preferable from the viewpoint of productivity.
混合したものが流動性のあるうちに型に入れておき、流動性が殆ど無い〜無い状態、つまり変形率が０％超過９５％以下の湿潤粘土体、その後、湿潤粘土体を加圧し、シート状に形成する。上記加圧で湿潤粘土体が延ばされることで圧力が分散されゼオライトのマクロポアが潰れて吸着能力が低下することがなく、更に成形体をより高硬度化させることができる。湿潤粘土体の変形率が９５％超過と流動性が高い液体状では精度良く成形することが困難である。変形率は、静置時間を変化させることで本発明の範囲内にすることができる。 The mixed material is put in a mold while it is fluid, and there is almost no fluidity, that is, a wet clay body with a deformation rate exceeding 0% and 95% or less, and then the wet clay body is pressurized, To form. By extending the wet clay body by the above pressurization , the pressure is dispersed, the macropores of the zeolite are not crushed and the adsorption capacity is not lowered, and the molded body can be further hardened. If the wet clay body has a deformation rate exceeding 95% and is in a liquid state with high fluidity, it is difficult to mold with high accuracy. The deformation rate can be made within the scope of the present invention by changing the standing time.
得られた粘土状の流動性の無いシート状の湿潤粘土体は、一片の刃からなる刃物で切断される。このように、一片の刃からなる刃物で切断することで、湿潤粘土体の切断時の刃による応力がかかっても湿潤粘土体は塑性変形の範囲内で応力を分散させるのでサイズ精度が良好な微細形状を形成することができる。これに対し、３ｍｍ角以下の微細形状の湿潤粘土体を切断するために一片の刃からなる刃物を複数並べて同時に切断すると、刃と刃との間に挟まれる湿潤粘土体は上記一片の刃からなる刃物の切断時以上の応力がかかるのでサイズ精度に劣るものとなる。また、好ましくは湿潤粘土体を端部から切断することによりサイズ精度が良好になる。本発明における一片の刃からなる刃物としては、直線状の一枚の刃からなるものが好ましい。 The obtained clay-like non-fluid sheet-like wet clay body is cut with a blade consisting of a single blade. In this way, by cutting with a blade consisting of a single blade, the wet clay body disperses the stress within the range of plastic deformation even when stress is applied by the blade when cutting the wet clay body, so the size accuracy is good. A fine shape can be formed. On the other hand, when cutting a plurality of blades made of a single blade in order to cut a wet clay body having a fine shape of 3 mm square or less and simultaneously cutting the wet clay body, the wet clay body sandwiched between the blades is removed from the single blade. Since the stress more than at the time of cutting of the resulting cutter is applied, the size accuracy is inferior. Further, the size accuracy is preferably improved by cutting the wet clay body from the end. As the blade composed of a single blade in the present invention, a blade composed of a single straight blade is preferable.
シート状の湿潤粘土体を切断せず、後述の乾燥方法の後に切断しようとすると、乾燥粘土体が粉々に割れる等して、目的の形状を得ることは困難であり、乾燥粘土体にさせる形状が大きいと体積収縮が大きくなるためヒビが入ることがある。この様にシート状等の湿潤粘土体を切断することによって、短時間で大量の目的形状、特に微細形状の湿潤粘土体が得られ生産性を高められる。 If the sheet-shaped wet clay body is not cut, and if it is to be cut after the drying method described later, it is difficult to obtain the desired shape because the dry clay body breaks into pieces, etc. If the value is large, the volumetric shrinkage becomes large and cracks may occur. By cutting the wet clay body such as a sheet in this manner, a large amount of the target shape, particularly a fine shape wet clay body can be obtained in a short time, and the productivity can be improved.
本発明における変形率は、２３℃／５５％ＲＨの環境下で、
（１）湿潤粘土体を、直径１５ｍｍ×厚さ５ｍｍに成形したものを水平な面に置く、
（２）上記湿潤粘土体を直径１０ｍｍの円柱（素材：ＳＵＳ３０４ステンレス鋼）で２０Ｎの負荷を掛ける、
（３）負荷を解除した３秒後（解除後は他に負荷がかかるようなことをしなければ形状維持している）に湿潤粘土体の厚みを測定し、下記式より変形率を算出する；
変形率＝（負荷により凹んだ距離（ｍｍ）／５ｍｍ）×１００％
で示される。
The deformation rate in the present invention is 23 ° C./55% RH environment,
(1) A wet clay body molded to a diameter of 15 mm and a thickness of 5 mm is placed on a horizontal surface.
(2) Applying a load of 20 N to the wet clay body with a cylinder having a diameter of 10 mm (material: SUS304 stainless steel),
(3) The thickness of the wet clay body is measured 3 seconds after releasing the load (the shape is maintained if no other load is applied after the release), and the deformation rate is calculated from the following equation. ;
Deformation rate = (distance recessed by load (mm) / 5 mm) × 100%
Indicated by
湿潤粘土体が含む溶媒分が多いと一次乾燥時に体積収縮率が大きくもろくなり、成形体にヒビが入り易いので、湿潤粘土体の固形分濃度は３０重量％以上が好ましく、特には４５重量％〜８０重量％が好ましい。 When the wet clay body contains a large amount of solvent, the volume shrinkage ratio becomes large and brittle during primary drying, and the molded body is liable to crack. Therefore, the solid content concentration of the wet clay body is preferably 30% by weight or more, particularly 45% by weight. ~ 80 wt% is preferred.
本発明によって得られる成形体は、ゼオライト粉末の吸着力を維持したままの成形体を作るためゼオライトの含有量が７０〜９８重量％であることが必要で、吸着性の点からは好ましくは８０〜９５重量％である。本発明によるゼオライト含有率が高い、つまりバインダーが少ないので硬さを保持した成形体を作るのは難しく、微細形状を作製する際にもろさがないようにする必要がある。 The molded product obtained by the present invention needs to have a zeolite content of 70 to 98% by weight in order to produce a molded product while maintaining the adsorption power of the zeolite powder, and is preferably 80 from the viewpoint of adsorptivity. ~ 95 wt%. Since the zeolite content according to the present invention is high, that is, there are few binders, it is difficult to produce a molded product that retains hardness, and it is necessary to prevent brittleness when producing a fine shape.
そのため本発明では、ゼオライト含有の湿潤粘土体の乾燥方法として、粘土体の水分やアルコール分を揮発させるための一次乾燥を行い、無機系バインダーを焼結させるための二次乾燥を行うことが好ましい。一次乾燥においては、水分やアルコール分を揮発させるため室温（２３℃±２℃）以上であれば乾燥させることができ、特に２３℃〜１２０℃が好ましく、より好ましくは２３℃〜６０℃である。乾燥時間としては２分〜１０分が好ましい。二次乾燥において、乾燥粘土体は無機系バインダーが焼結していないため硬度が低いので１４０℃以上で乾燥させることが好ましく、より好ましくは２００℃〜６００℃であり、更に好ましくは３００℃〜５００℃である。乾燥時間としては１時間〜３時間が好ましい。 Therefore, in the present invention, as a method for drying a zeolite-containing wet clay body, it is preferable to perform primary drying for volatilizing the moisture and alcohol content of the clay body and secondary drying for sintering the inorganic binder. . In the primary drying, water and alcohol are volatilized, so that it can be dried at room temperature (23 ° C. ± 2 ° C.) or more, particularly preferably 23 ° C. to 120 ° C., more preferably 23 ° C. to 60 ° C. . The drying time is preferably 2 minutes to 10 minutes. In the secondary drying, the dried clay body has a low hardness because the inorganic binder is not sintered, and is preferably dried at 140 ° C or higher, more preferably 200 ° C to 600 ° C, and still more preferably 300 ° C to 500 ° C. The drying time is preferably 1 hour to 3 hours.
以下に、具体的な実施例を挙げて本発明をより詳細に説明するが、本発明はこれらの実施例により限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.
（実施例１）
カオリン系粘土 １３．７ｇ
疎水性ゼオライト（商品名：ＨｉＳｉＶ３０００、ユニオン昭和社製） ４６．１６ｇ
純水 ６０．４ｇ
上記の材料を室温（２３℃）で攪拌し、ゼオライト含有湿潤粘土を得た。ゼオライト含有湿潤粘土を５０×５０ｍｍの正方形の型に入れ、２３℃／５５％ＲＨの環境下で静置し、流動性が無い粘土状の湿潤粘土体（固形分濃度４８質量％）を作製した。同様に測定用に作製した湿潤粘土体の変形率は４０％であった。
Example 1
Kaolin clay 13.7g
Hydrophobic zeolite (trade name: HiSiV3000, manufactured by Union Showa) 46.16 g
60.4g of pure water
The above materials were stirred at room temperature (23 ° C.) to obtain zeolite-containing wet clay. Zeolite-containing wet clay was put into a 50 × 50 mm square mold and allowed to stand in an environment of 23 ° C./55% RH to produce a clay-like wet clay body (solid content concentration 48 mass%) having no fluidity. . Similarly, the deformation rate of the wet clay produced for measurement was 40%.
粘土状の湿潤粘土体を加圧し、厚さ３ｍｍのシート状の湿潤粘土体を得た。その後、直線状の長さ１００ｍｍの一枚の刃からなるカッターを用いてシート状の湿潤粘土体の端部から順に切断し、湿潤粘土体を３×３×３ｍｍに切断した後に、室温（２３℃）で１０分間一次乾燥させ、乾燥粘土体を作製した。 The clay-like wet clay body was pressurized to obtain a sheet-like wet clay body having a thickness of 3 mm. Then, using a cutter composed of a straight blade having a length of 100 mm, the sheet-like wet clay body is cut in order from the end, and the wet clay body is cut into 3 × 3 × 3 mm, and then room temperature (23 C.) for 10 minutes to produce a dried clay body.
次に、乾燥粘土体を電気炉で５００℃で１時間二次乾燥させることにより、ゼオライト含有率８０重量％の成形体が得られた。 Next, the dried clay body was subjected to secondary drying in an electric furnace at 500 ° C. for 1 hour to obtain a molded body having a zeolite content of 80% by weight.
得られたゼオライト成形体を下記の評価方法に従って評価を行った。結果を表１に示す。 The obtained zeolite compact was evaluated according to the following evaluation method. The results are shown in Table 1.
＜評価＞
「成形状態」
成形体のヒビ、欠け、収縮度合いを観察した。
<Evaluation>
"Molded state"
The molded body was observed for cracks, chipping and shrinkage.
「高さ精度(標準偏差σ)」
３×３×３ｍｍの成形体の高さ（厚み）を３ヶ所マイクロスコープで測定し、１つの成形体での高さ差（最大値−最小値）を算出する。この測定を２０個の成形体で行い標準偏差を算出する。
`` Height accuracy (standard deviation σ) ''
The height (thickness) of the 3 × 3 × 3 mm molded body is measured with three microscopes, and the height difference (maximum value−minimum value) of one molded body is calculated. This measurement is performed on 20 molded bodies, and the standard deviation is calculated.
（実施例２）
シランアルコキシド（ＴＥＯＳ） ２５ｇ
純水 ２３．５ｇ
メタノール ３７．６ｇ
２Ｎ塩酸 ７．０ｇ
疎水性ゼオライト（商品名：ＨｉＳｉＶ３０００） ４６．１６ｇ
上記の材料を用いて実施例１と同様にして流動性が無い粘土状の湿潤粘土体（固形分濃度４５質量％）を作製した。測定用に作製した湿潤粘土体の変形率は２０％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
(Example 2)
Silane alkoxide (TEOS) 25g
Pure water 23.5g
37.6g of methanol
2N hydrochloric acid 7.0g
Hydrophobic zeolite (trade name: HiSiV3000) 46.16 g
Using the above materials, a clay-like wet clay body having a fluidity (solid content concentration: 45% by mass) was prepared in the same manner as in Example 1. The deformation rate of the wet clay produced for measurement was 20%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（実施例３）
実施例１において、疎水性ゼオライトを１０４ｇ、純水を７５ｇに変更した以外は、同様にして流動性が無い粘土状の湿潤粘土体（固形分濃度６０質量％）を作製した。測定用に作製した湿潤粘土体の変形率は３５％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
(Example 3)
A clay-like wet clay body (solid content concentration 60 mass%) having no fluidity was produced in the same manner as in Example 1 except that the hydrophobic zeolite was changed to 104 g and the pure water was changed to 75 g. The deformation rate of the wet clay body prepared for measurement was 35%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（実施例４）
実施例２において、疎水性ゼオライトを１０４ｇに変更した以外は、同様にして流動性が無い粘土状の湿潤粘土体（固形分濃度５９質量％）を作製した。測定用に作製した湿潤粘土体の変形率は１５％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
Example 4
In Example 2, a clay-like wet clay body having a fluidity (solid content concentration: 59% by mass) was produced in the same manner except that the hydrophobic zeolite was changed to 104 g. The deformation rate of the wet clay produced for measurement was 15%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（実施例５）
カオリン系粘土 １３．７ｇ
親水性ゼオライト（３Ａ） ４６．１６ｇ
純水 ５０ｇ
メタノール １０ｇ
上記の材料を用いて実施例１と同様にして流動性が無い粘土状の湿潤粘土体（固形分濃度４８質量％）を作製した。測定用に作製した湿潤粘土体の変形率は４０％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
(Example 5)
Kaolin clay 13.7g
46.16 g of hydrophilic zeolite (3A)
50g of pure water
Methanol 10g
Using the above materials, a clay-like wet clay body (solid content concentration 48 mass%) having no fluidity was prepared in the same manner as in Example 1. The deformation rate of the wet clay produced for measurement was 40%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（実施例６）
シランアルコキシド（ＴＥＯＳ） ２５ｇ
純水 １３ｇ
メタノール ４８ｇ
２Ｎ塩酸 ７ｇ
親水性ゼオライト（３Ａ） ４６．１６ｇ
上記の材料を用いて実施例１と同様にして流動性が無い粘土状の湿潤粘土体（固形分濃度４５質量％）を作製した。測定用に作製した湿潤粘土体の変形率は２０％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
(Example 6)
Silane alkoxide (TEOS) 25g
13g of pure water
Methanol 48g
7g of 2N hydrochloric acid
46.16 g of hydrophilic zeolite (3A)
Using the above materials, a clay-like wet clay body having a fluidity (solid content concentration: 45% by mass) was prepared in the same manner as in Example 1. The deformation rate of the wet clay produced for measurement was 20%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（実施例７）
実施例１において、純水を１４６ｇに変更した以外は、同様にして流動性が殆ど無い粘土状の湿潤粘土体（固形分濃度２８質量％）を作製した。測定用に作製した湿潤粘土体の変形率は９０％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
(Example 7)
In Example 1, except that pure water was changed to 146 g, a clay-like wet clay body (solid content concentration 28% by mass) having almost no fluidity was produced in the same manner. The deformation rate of the wet clay body prepared for measurement was 90%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（実施例８）
実施例２において、純水を５０ｇ、メタノールを８１ｇに変更した以外は、同様にして流動性が殆ど無い粘土状の湿潤粘土体（固形分濃度２８質量％）を作製した。測定用に作製した湿潤粘土体の変形率は９０％であった。その後、実施例１と同様にして乾燥させ成形体を作製し、評価を行った。結果を表１に示す。
(Example 8)
In Example 2, a clay-like wet clay body (solid content concentration: 28% by mass) having almost no fluidity was prepared in the same manner except that 50 g of pure water and 81 g of methanol were changed. The deformation rate of the wet clay body prepared for measurement was 90%. Then, it was made to dry like Example 1 and the molded object was produced, and evaluation was performed. The results are shown in Table 1.
（比較例１）
実施例１と同じ材料を用い湿潤粘土体の変形率が９７％の状態でシート状に成形した。その後、直線状の長さ１００ｍｍの一枚の刃からなるカッターを用いてシート状の湿潤粘土体の端部から順に切断しようとしたが、流動性が有る状態では一定形状の成形は不可能であった。結果を表１に示す。
(Comparative Example 1)
Using the same material as in Example 1, the wet clay body was formed into a sheet shape with a deformation rate of 97%. After that, we tried to cut in order from the edge of the wet clay body in the form of a sheet using a cutter consisting of a single blade with a linear length of 100 mm. there were. The results are shown in Table 1.
（比較例２）
実施例１において、３ｍｍ間隔で直線状の長さ１００ｍｍのカッターを３枚並べた刃物を用いてシート状の湿潤粘土体を切断した以外は、同様にして成形体を作製し、評価を行った。結果を表１に示す。
(Comparative Example 2)
In Example 1, a molded body was prepared and evaluated in the same manner except that the sheet-like wet clay body was cut using a blade in which three linear cutters having a length of 100 mm were arranged at intervals of 3 mm. . The results are shown in Table 1.
（比較例３）
実施例２において、３ｍｍ間隔で直線状の長さ１００ｍｍのカッターを３枚並べた刃物を用いてシート状の湿潤粘土体を切断した以外は、同様にして成形体を作製し、評価を行った。結果を表１に示す。
(Comparative Example 3)
In Example 2, a molded body was prepared and evaluated in the same manner except that the sheet-like wet clay body was cut using a blade in which three linear cutters having a length of 100 mm were arranged at intervals of 3 mm. . The results are shown in Table 1.
比較例１の変形率が本発明の範囲外の流動性が有る状態では一定形状の成形は不可能であった。３ｍｍ角の微細形状を複数のカッターで同時に切断した比較例２及び３ではカッターとカッターの間に挟まれる湿潤粘土体に切断時に応力がかかり精度に劣るものであった。 When the deformation rate of Comparative Example 1 had fluidity outside the range of the present invention, it was impossible to form a fixed shape. In Comparative Examples 2 and 3 in which a 3 mm square fine shape was simultaneously cut with a plurality of cutters, the wet clay body sandwiched between the cutters was stressed during cutting, and the accuracy was poor.
本発明の製造方法によって、吸着剤含有成形が個々に型を使用することなく、高い生産性で用途に合わせた微細形状も高い精度で作製でき、吸着分野に広く用いることが可能である。 According to the production method of the present invention, the adsorbent-containing molding can be produced with high accuracy and with high accuracy without using a mold individually, and can be widely used in the adsorption field.
Claims (9)
該ゼオライト含有湿潤粘土を変形率が１５％以上９０％以下である湿潤粘土体に硬化させる工程と、
該湿潤粘土体をシート状に形成する工程と、
該シート状の湿潤粘土体を一片の刃からなる刃物を単独で用いて切断する工程と、
該切断した湿潤粘土体を乾燥させて、高さ精度（標準偏差σ）が０．００２〜０．０１５でゼオライト含有率が７０〜９８重量％である乾燥粘土体を形成する工程と、
を有する吸着剤含有成形体の製造方法。 Mixing a solvent composed of one or both of water and alcohol, an inorganic binder, and zeolite to form a zeolite-containing wet clay;
Curing the zeolite-containing wet clay to a wet clay body having a deformation rate of 15% or more and 90% or less ;
Forming the wet clay body into a sheet;
Cutting the sheet-like wet clay using a blade consisting of a single blade alone ;
Drying the cut wet clay body to form a dry clay body having a height accuracy (standard deviation σ) of 0.002 to 0.015 and a zeolite content of 70 to 98% by weight ;
Method for producing adsorbents containing shaped bodies that have a.
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