JPS62283812A - Zeolite molded body and its production - Google Patents
Zeolite molded body and its productionInfo
- Publication number
- JPS62283812A JPS62283812A JP12720886A JP12720886A JPS62283812A JP S62283812 A JPS62283812 A JP S62283812A JP 12720886 A JP12720886 A JP 12720886A JP 12720886 A JP12720886 A JP 12720886A JP S62283812 A JPS62283812 A JP S62283812A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- weight
- molded body
- parts
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 81
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 77
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000000835 fiber Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002734 clay mineral Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920003169 water-soluble polymer Polymers 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 229910021647 smectite Inorganic materials 0.000 abstract description 3
- -1 zeolite anhydride Chemical class 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229910052680 mordenite Inorganic materials 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【発明の詳細な説明】
３、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。Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a zeolite molded body 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、１ｓｏ−ブタンとｎ−ブタ
ンとの分離、ＰＳＡ Ｃプレッシャー・スイング°ア
トソープション（Ｐｒｅｓｓｕｒｅ ＳｗｉｎｇＡｄｓ
ｏｒｐｔｉｏｎ） ）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 molded bodies contain H2O in natural gas,
Removal of CO2, H2S, mercaptan, dehydration/drying of organic solvents, various industrial gases, etc., separation of 1so-butane and n-butane, PSA Pressure Swing Ads
Because of its functional adsorptive properties, it is widely used in various industrial fields, such as the separation of oxygen and nitrogen in the air by the 3.3-5.3.3.3.3.3.3 method, and catalysts in oil refining and petrochemical industries.
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 the performance of such zeolite molded bodies differs depending on the molding technique used, even if the characteristics of the zeolite powder itself are the same.
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 been made regarding methods for producing zeolite molded bodies.
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（′、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−！３
８７２号公報、特公昭３５−７８９号公報、特公昭３９
−２１８２１号公報、特公昭４Ｂ−３２５７２号公報、
特公昭４８−２７３７４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４７−８７８９
５号公報、有機質結合剤を使用するもの；例えば特開昭
４８−３９３！３９号公報、特開昭４９−４０３２１号
公報、特公昭５０−９７４８号公報、特開昭５０−１２
０４８７号公報、特開昭５４−６９５９８号公報、特開
昭５４−２１８３２号公報等が代表的にあげられる。Zeolite molded bodies can be roughly divided into those that use a binder and those that do not ('), but in the former, those that use clay minerals as a binder; for example, those that use a clay mineral as a binder; for example,
Publication No. 872, Special Publication No. 35-789, Special Publication No. 39 of Showa
-21821 Publication, Special Publication No. 4B-32572,
Japanese Patent Publication No. 48-27374 is representative, and those using an inorganic binder other than clay minerals: For example, Japanese Patent Publication No. 42-90, Japanese Patent Publication No. 48-37513,
Special Publication No. 44-14092, Special Publication No. 47-8789
5, using an organic binder; for example, JP-A-48-393!39, JP-A-49-40321, JP-A-50-9748, JP-A-50-12
Representative publications include JP-A No. 0487, JP-A-54-69598, and JP-A-54-21832.
〔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粒度特性
、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％（湿温重量基準）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, when a zeolite molded body is specified by the particle size characteristics of the zeolite crystals and the molding method, 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 experiments conducted by the present inventors, the permissible moisture range is surprisingly narrow, and the moisture content of the kneaded product (excluding crystal water) is about 17 to 23
% by weight (wet weight basis), and the macropore volume in this range can only be adjusted in the range of approximately 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 macropore volume as much as possible in a molded article because it improves performance, but there is a limit because this property is inconsistent with 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。Especially recently, with the development of adsorption separation technology using the PSA method,
Zeolite adsorbents have come to be used for this purpose, and in this case, the adsorption speed of zeolites and molded bodies has attracted attention 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 with a large macropore volume while maintaining 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 improvements in order to solve the basic problems in zeolite molded bodies containing binders 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、バルブ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 the Problems] The present inventors have conducted intensive research in view of the above-mentioned conventional technology, and have found that when a zeolite molded body using clay mineral as a binder is molded in combination with valve short fibers, The present invention was completed based on the finding that the strength of the molded product can be sufficiently maintained and the macropore volume of the molded product can be 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７０〜８５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（ｍＪ／ｇ）／ミクロ
孔容積（ｍｊ’／ｇ）の比が１〜４．５で、かつマクロ
孔容積が０．３〜０．７ｍｐ／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, a zeolite molded body containing zeolite in an amount of 70 to 85% by weight based on anhydride, the molded body has a ratio of macropore volume (mJ/g)/micropore volume (mj' Provided is a zeolite molded body characterized by having continuous pores with a ratio of 1 to 4.5 and a macropore volume of 0.3 to 0.7 mp/g.
また、本発明によれば、第２に、平均粒子径１〜５ｇｍ
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１０００座国以下のパ
ルプ短繊維ｌ〜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
成型および乾繰して得られる成形体を５００〜７００℃
における焼成により有Ｊａ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。According to the present invention, secondly, the average particle size is 1 to 5 g.
100 parts by weight of zeolite powder (anhydrous equivalent) consists of 5 to 30 parts by weight of clay mineral powder, 1 to 35 parts by weight of short pulp fibers with a fiber length of 1000 or less, and 0 to 3 parts by weight of an organic water-soluble polymer substance. The mixture is granulated and dried in the presence of an appropriate amount of water, and the resulting molded product is heated to 500 to 700°C.
Provided is a method for producing a zeolite molded body, characterized in that the Ja component is burned out by firing in the step of calcination, thereby imparting continuous macropores to the molded body.
［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。[Function] The zeolite powder in the present invention is not particularly limited as long as it is a crystalline aluminosilicate with a unique three-dimensional structure and has the characteristics of a so-called molecular sieve, and may be either 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
イド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かあ（ヂられ、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。These zeolites include high-silica zeolites such as zeolite A, zeolite, olide X, zeolite Y, mordenite, and ZSM-5. is better.
かかるゼオライト粉末は平均粒子径１〜５ｇｍ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しなり易く、実用性に
欠けるからである。Such zeolite powder preferably has an average particle size in the range of 1 to 5 gm, and preferably has a particle size distribution as sharp as possible. This is because substances outside this range tend to be difficult to synthesize or have poor adsorption properties, and are therefore impractical.
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, the above zeolite powder has cation exchange properties, and even if it is a substituted zeolite in which all or part of the sodium ions of the basic zeolite, sodium aluminosilicate, are ion-exchanged with other metal ions. Of course, there is no problem, and substituted zeolites are often used as necessary. Typical examples of cations that can be substituted include H., Li., K., and Ca''.
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７０〜８５重量％含有するもの
であって、マクロ孔容ｆｆｌ（ｍｉ’／ｇ）／ミクロ孔
容積（ｆｆｌβ／ｇ）の比が１〜４．５で、かつマクロ
孔容積が０．３〜０．７ｍＡ＋／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 70 to 85% by weight of the above-mentioned zeolite based on anhydride, and has a macropore volume ffl (mi'/g)/micropore volume (fflβ/g). It is characterized by having continuous pores with a ratio of 1 to 4.5 and a macropore volume of 0.3 to 0.7 mA+/g.
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。Note that 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 molded body, and each is given by the test method described later.
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, almost all other ingredients include clay minerals as a binder.
マクロ孔容積（ｍｆ！／ｇ）／ミクロ孔容積（ｍｉ’／
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 (mf!/g)/micropore volume (mi'/
By setting the ratio of g) in the range of 1 to 4.5, a molded article with a high adsorption rate and high strength can be obtained. If this ratio is less than 1, the adsorption performance is poor, and if it exceeds 4.5, the strength of the molded product is low, which is not preferred.
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
て従来よりもマクロ孔容積が太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, the zeolite molded body according to the present invention has continuous pores and a larger macropore volume than conventional ones while maintaining sufficient molding strength, and therefore has excellent gas adsorption speed. It has the following.
次に、本発明にがかるゼオライト成形体は、平均粒子径
１〜５ｐｍ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１０００μ
ｍ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 molded body according to the present invention contains 5 to 30 parts by weight of clay mineral powder per 100 parts by weight of zeolite powder (anhydride equivalent) with an average particle diameter of 1 to 5 pm, and a fiber length of 1000 μm.
A molded body obtained by granulating and drying a mixture consisting of 1 to 35 parts by weight of short pulp fibers of 50 m or less and 0 to 3 parts by weight of an organic water-soluble polymer substance in the presence of an appropriate amount of water.
It can be produced by burning out the organic components by firing at ~700°C, thereby imparting continuous macropores to the molded body.
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屈、カオ
リン系、パリゴルスカイト、ヘクトライトあるいはセビ
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 examples of clay minerals include fine powders of one or more clay minerals such as smectite, kaolin, palygorskite, hectorite, or seviolite.
更にパルプ類ＲＭＪとしては、繊維長が１０角の以上で
１■以下であることが必要であり、好ましくは１０〜１
００ｇｍ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, for pulp RMJ, it is necessary that the fiber length is 10 squares or more and 1 square or less, preferably 10 to 1
00gm amorphous pulp is preferred. If the fiber length is outside this range, the formed body will have insufficient continuous pores after firing, or even if there are continuous pores, the molding strength will be insufficient.
Alternatively, the powder tends to be mixed ununiformly, making it unsuitable for achieving the desired properties of the molded product.
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 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 dry strength of the molded product and also has the effect of preventing dust generation when the blended raw materials are transported by air during the granulation process. This is because, depending on the blending and molding operations, it is possible to do without this auxiliary raw material, so it is not necessarily used as an essential raw material.
かかる出発原料は、ゼオライト粉末を無水物換算で１０
０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賀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。The starting material is zeolite powder in an amount of 10% on anhydride basis.
0 to 30 parts by weight of clay mineral powder, 1 to 35 parts by weight of short pulp fibers, and 0 to 3 parts by weight of water-soluble polymer material are mixed, and the desired amount of water is added to this and kneaded. do.
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。With composition ratios other than the above, it is difficult to obtain a desired formed body that satisfies both strength and 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。Kneading and granulation of a raw material blend in the presence of water are already obvious in this field, and in the present invention, it may be carried out by any desired means without particular limitation.
このことば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１−１０ｍ＋ａの範囲のものがよい。The same applies to the shape of the granulated product; in most cases, the size of the granulated product is preferably in the range of 1 to 10 m+a, depending 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酎
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 forming the granules, a drying step is required in order to give the granules the strength necessary to sufficiently dissolve them in the subsequent firing step. This usually ranges from 0.5 to 2 hours at 100-120°C.
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 500-700°C, preferably 550-650°C
The granulated product is fired for 1 to 3 hours, preferably 1.5 to 2.5 hours to substantially burn off the organic matter present, as well as dehydrate the zeolite water to activate it and impart strength to the molded product.
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バルブ短
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
。Through this process, the valve short fibers that are uniformly dispersed and intertwined with each other and mixed with the granules during kneading and granulation burn and disappear, and their skeletons form continuous pores, resulting in molding. 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 molded body can be used as a product as it is, but it can also be classified as necessary and returned to an appropriate previous process after being crushed if the product has a particle size other than desired.
実施例Ｉ
ＮａＡ型ゼオライト粉末（１０，９８Ｎａ２０・Ａｉ’
２０３・１．９８Ｓｉ０２・３．９Ｈ２０） １２５重
量部、カオリン系粘土１５重量部、繊維長１０〜１００
μｍの非晶質バルブ短繊維（山場国策パルプ製、パルプ
フロラクト１）５重量部を混合後、水４０重量部を加え
てニーダ−で２０分混練する。次いで押出造粒ａ（不二
パウダル株製）を用いて、ダイス１３．３５Ｉｌ！ｌ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℃１２時間乾燥後、６００℃１２時間焼成
して直径３■のゼオライト成形体ペレットを得た。Example I NaA type zeolite powder (10,98Na20・Ai'
203.1.98Si02.3.9H20) 125 parts by weight, 15 parts by weight of kaolin clay, fiber length 10-100
After mixing 5 parts by weight of amorphous bulb short fibers (manufactured by Yamaba Kokusaku Pulp, Pulp Floract 1), 40 parts by weight of water was added and kneaded in a kneader for 20 minutes. Next, using extrusion granulation a (manufactured by Fuji Paudal Co., Ltd.), a die of 13.35Il! 1 was set and extrusion molded to obtain a cylindrical molded product. The obtained molded product was dried at 110°C for 12 hours and then calcined at 600°C for 12 hours to obtain zeolite molded pellets with a diameter of 3 cm.
実施例２
実施例１で用いたＮａＡ型ゼオライト粉末２５Ｏｉ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時間攪拌しながらカルシウムイオン交換を行う。Example 2 250i parts of the NaA type zeolite powder used in Example 1 was dispersed in 2000 parts by weight of water, 160 parts by weight of calcium chloride (dihydrate) was dissolved in this zeolite slurry, and calcium chloride was dissolved while stirring for 10 hours. Perform ion exchange.
イオン交換後、Ｔｐ過水洗して＋２０’ｃ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。After ion exchange, the product was washed with Tp water, dried at +20'C for 3 hours, and pulverized to obtain 246 parts by weight of CaA type zeolite.
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Ｃａ
Ａ型ゼオライ） １２３重量部、α化澱粉（松谷化学工
業■製マツ／リンＣ）り２重量部、力士リン系粘土１０
重量部、モンモリロライト系粘土１０重量部、繊維長ｌ
Ｏ〜１００ 牌ｍの非晶質、バルブ短繊維（山場国策パ
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。As a result of analyzing this dried product, the Ca ion exchange rate was 74%.
It was confirmed that the zeolite was type 5A zeolite. This Ca
A-type zeolite) 123 parts by weight, pregelatinized starch (Matsu/Rin C manufactured by Matsutani Chemical Co., Ltd.) 2 parts by weight, sumo wrestler phosphorus clay 10
Parts by weight, 10 parts by weight of montmorillolite clay, fiber length l
After mixing 10 parts by weight of O to 100 m long amorphous bulb short fibers (KC Flock W-50 (S) manufactured by Yamaba Kokusaku Pulp), 42 parts by weight of water was added and kneaded for 20 minutes in a kneader.
次いで押出造粒機（第二パウダルＨ５ｕ）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＋１０℃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, using an extrusion granulator (second powder H5u), a die diameter of 1.5 mm was set, and extrusion molding was performed to obtain a cylindrical molded product. After drying the obtained molded product at +10℃ for 2 hours,
C. for 2 hours to obtain zeolite molded pellets with a diameter of 1.5 mm.
実施例３
ＮａＸ ）ｊｌｌセライト粉末（Ｎａ２ＣＩＡｆｚ０３
・２．５Ｓｉ０２ ・ｎＨ２Ｏ） １２８重量部（含水
率２２％）、モンモリロナイト系粘±（クニミネ工業■
製りニゲルＶＡ）１５重量部、カオリン系粘土１０重量
部、繊維長１０〜１００ ｐ、ｍの非晶質パルプ短繊維
（山場国策パルプ製、パルプフロラクト５）２０重量部
を、混合後、水４６重量部を加えて、ニーダ−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３ ｍ＋１１）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℃１３０分間焼成しＮａＸ型ゼオライトペレット
を得た。Example 3 NaX)jll celite powder (Na2CIAfz03
・2.5Si02 ・nH2O) 128 parts by weight (water content 22%), montmorillonite-based viscosity (Kunimine Kogyo ■
After mixing 15 parts by weight of Nigel VA), 10 parts by weight of kaolin clay, and 20 parts by weight of amorphous pulp short fibers with a fiber length of 10 to 100 p (manufactured by Yamaba Kokusaku Pulp, Pulp Floract 5), Add 46 parts by weight of water and knead in a kneader for 20 minutes. Next, extrusion molding was performed using an extrusion granulator (manufactured by Fuji Paudal Co., Ltd.) with a die (diameter 3 m + 11) set. After drying the obtained cylindrical molded product at 110°C for 2 hours,
It was calcined at 750°C for 130 minutes to obtain NaX type zeolite pellets.
実施例４
Ｎａモルデナイト粉末（Ｎａ２ＣＩＡｉ’２０３４０Ｓ
ｉ０２・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１ａｒｐ１１１’）で、水を噴霧しながら転勤造粒を
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℃１１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 (Na2CIAi'20340S
After mixing 114 parts by weight (water content: 12%) of i02.nH2O, 30 parts by weight of kaolin clay, and 30 parts by weight of the same short pulp fibers as in Example 1, a dish-type granulator (diameter 70 cm, number of revolutions 1 arp 111') was mixed. Then, transfer granulation was performed while spraying water. The amount of water added was 35 parts by weight. The obtained granules were dried at 110°C for 2 hours and then fired at 700°C for 11 hours 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■製ゼオライト１
５０ ） １０５重量部、スメクタイト属粘土（クニミ
ネ工業■製りニゲルＶＡ） ２０重量部、実施例２と同
じバルブ短繊維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、転勤造粒を行なった。水添加量は
３４重量部であった。得られた造粒物を１１０’Ｃで２
時間乾燥後、７００℃１１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 Natural mordenite powder (zeolite 1 manufactured by Kunimine Kogyo ■)
50) After mixing 105 parts by weight of smectite clay (Niger VA manufactured by Kunimine Industries), and 10 parts by weight of the same valve short fiber as in Example 2, pregelatinized starch (Matsuya Matsunorin CM manufactured by Kagaku Kogyo Co., Ltd.) 4%
Transfer granulation was performed while spraying the solution. The amount of water added was 34 parts by weight. The obtained granules were heated at 110'C for 2
After drying for an hour, it was fired at 700°C for 11 hours to obtain a spherical porous natural mordenite molded product.
比較例１
実施例２においてパルプ短ｍ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−で２０分混
練後、押出造粒機を用いて（第二パウダルー製）ダイス
径３０＋１１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１
１０℃、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, without adding pulp short fibers, Na-A
After mixing 125 parts by weight of type zeolite powder and 15 parts by weight of kaolin clay, 40 parts by weight of water was added and kneaded for 20 minutes in a kneader. Using an extrusion granulator (manufactured by Daini Powderoo), a die diameter of 30+11 was set. , and extrusion molding was carried out in the same manner as in Example 2 to obtain a cylindrical molded product. The obtained molded product is 1
After drying at 10° C. for 2 hours, it was calcined at 600° C. for 2 hours to obtain zeolite molded pellets with a diameter of 3 mm.
く評価方法〉
（１）ゼオライト粉末の粒度測定
コールタ−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。(1) Measurement of particle size of zeolite powder Particle size was 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 zeolite powders before molding, such as NaA type zeolite, CaA type zeolite, NaX type zeolite, and mordenite, were stored in a constant temperature and humidity chamber at a temperature of 25°C and a relative humidity of 60% for 5 days. After the moisture absorption treatment, it was fired at 800°C, and the pore volume was determined from the volume of adsorbed water using 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Ｔ）！−２０３型で
１００個の試料を測定しその平均値を求めた。(3) Compression breaking strength Tablet breaking strength measuring device manufactured by Toyama Sangyo Co., Ltd. T)! 100 samples were measured using the -203 model, and the average value was determined.
（４）マクロ孔容積の測定
成形体試料１．０ｇを採取し、水銀圧入式ボロシ） −
’）−Ｃｊｙ７タクｏ−ム社製、ＡＵＴＯ５ＣＡＭ−３
３）で１０〜２３００Ｋｇ／ｃ１１１２まで加圧し、細
孔半径で約３２〜０．００３２ ｐ−ｍまでの全マクロ
孔容積を測定した。(4) Measurement of macropore volume 1.0 g of the molded body sample was taken and mercury intrusion type rag) -
') - Cjy7 manufactured by Tacom, AUTO5CAM-3
In step 3), the pressure was increased to 10 to 2300 Kg/c1112, and the total macropore volume from about 32 to 0.0032 p-m in terms of pore radius was measured.
く物性測定結果〉 第１表に示すとおり。Physical property measurement results> As shown in Table 1.
第 １ 表
［発明の効果］
本発明によれば、０．３〜０．７ｍＡ＋／ｇという大き
なマクロ孔容積と充分な成形強度をもっゼオライト成形
体を容易に得ることができる。Table 1 [Effects of the Invention] According to the present invention, a zeolite molded body having a large macropore volume of 0.3 to 0.7 mA+/g and sufficient molding strength can be easily obtained.
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 molded body has a high gas adsorption rate, it can be effectively used as an adsorbent or catalyst in various industrial fields as well as the PSA method.
Claims (5)
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) A zeolite molded body containing 70 to 95% by weight of zeolite based on anhydride, the molded body having a ratio of macropore volume (ml/g)/micropore volume (ml/g) of 1.
~4.5, and the macropore volume is 0.3 to 0.7 ml/
A zeolite molded body characterized by having continuous pores of g.
ら選ばれた少なくとも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) Claim 1, wherein the zeolite powder is at least one A-type, Y-type, X-type, or mordenite-type zeolite powder selected from H, Li, K, Na, or Ca. Zeolite molded body.
、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 article according to claim 1, wherein the molded article is a spherical, oval, or rod-shaped molded article having a maximum diameter in the range of 1 to 10 mm.
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) 5 to 30 parts by weight of clay mineral powder per 100 parts by weight of zeolite powder with an average particle size of 1 to 5 μm (calculated as anhydride),
A molded body obtained by granulation molding and drying a mixture consisting of 1 to 35 parts by weight of short pulp fibers with a fiber length of 1000 μm or less and 0 to 3 parts by weight of an organic water-soluble polymer substance in the presence of an appropriate amount of water. A method for producing a zeolite molded body, which comprises burning out organic components by firing at 700°C to impart continuous macropores to the molded body.
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) The method for producing a zeolite molded article according to claim 4, wherein the short pulp fibers are amorphous short pulp fibers having a fiber length in the range of 10 to 100 μm.
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 true JPS62283812A (en) | 1987-12-09 |
| JPH0674136B2 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 (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297282A (en) * | 1987-05-29 | 1988-12-05 | Showa Senpu Kk | Production of zeolite compact |
| US5462693A (en) * | 1991-12-12 | 1995-10-31 | Nippon Chemical Industrial Co., Ltd. | Air purifying agent and a process for producing same |
| EP0888802A2 (en) * | 1997-06-06 | 1999-01-07 | Haralambos Spyridis | Porous air filtering and refining material |
| JPH11246215A (en) * | 1998-03-04 | 1999-09-14 | Tosoh Corp | Low silica x-zeolite bead compact and its production |
| JP2004143035A (en) * | 2002-08-30 | 2004-05-20 | Tokuyama Corp | Crystalline inorganic porous material and its producing method |
| JP2005515876A (en) * | 2002-01-22 | 2005-06-02 | ゼオケム・エルエルシー | Method for producing molecular sieve adsorbent blend |
| US7267812B2 (en) * | 2002-08-30 | 2007-09-11 | Tokuyama Coporation | Crystalline inorganic porous material and production process therefor |
| JP2009101294A (en) * | 2007-10-23 | 2009-05-14 | Kyodo Printing Co Ltd | Method for manufacturing molded body containing adsorbent and molded body containing adsorbent |
| DE102008046155A1 (en) | 2008-03-03 | 2009-09-10 | Chemiewerk Bad Köstritz GmbH | Adsorbent granules and process for its preparation |
| EP2527296A2 (en) | 2011-05-25 | 2012-11-28 | 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 |
| JP2020049423A (en) * | 2018-09-26 | 2020-04-02 | 水澤化学工業株式会社 | Purification material |
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| CN107694476B (en) * | 2017-07-25 | 2020-07-10 | 江苏远鸿新材料科技有限公司 | Forming and manufacturing method of high-strength spherical drying agent |
Citations (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
Patent Citations (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 |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63297282A (en) * | 1987-05-29 | 1988-12-05 | Showa Senpu Kk | Production of zeolite compact |
| US5462693A (en) * | 1991-12-12 | 1995-10-31 | Nippon Chemical Industrial Co., Ltd. | Air purifying agent and a process for producing same |
| EP0888802A2 (en) * | 1997-06-06 | 1999-01-07 | Haralambos Spyridis | Porous air filtering and refining material |
| EP0888802A3 (en) * | 1997-06-06 | 1999-06-16 | Haralambos Spyridis | Porous air filtering and refining material |
| JPH11246215A (en) * | 1998-03-04 | 1999-09-14 | Tosoh Corp | Low silica x-zeolite bead compact and its production |
| JP2005515876A (en) * | 2002-01-22 | 2005-06-02 | ゼオケム・エルエルシー | Method for producing molecular sieve adsorbent blend |
| JP2004143035A (en) * | 2002-08-30 | 2004-05-20 | Tokuyama Corp | Crystalline inorganic porous material and its producing method |
| US7267812B2 (en) * | 2002-08-30 | 2007-09-11 | Tokuyama Coporation | Crystalline inorganic porous material and production process therefor |
| JP2009101294A (en) * | 2007-10-23 | 2009-05-14 | Kyodo Printing Co Ltd | Method for manufacturing molded body containing adsorbent and molded body containing adsorbent |
| DE102008046155A1 (en) | 2008-03-03 | 2009-09-10 | Chemiewerk Bad Köstritz GmbH | Adsorbent granules and process for its preparation |
| US9682361B2 (en) | 2008-03-03 | 2017-06-20 | Chemiewerk Bad Kostritz Gmbh | Adsorbent granulate and method for the manufacture thereof |
| EP2527296A2 (en) | 2011-05-25 | 2012-11-28 | 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 |
| DE102012010109A1 (en) | 2011-05-25 | 2012-11-29 | Chemiewerk Bad Köstritz GmbH | Binder-free zeolitic granules with faujasite structure and process for the preparation of such binder-free zeolitic granules together with use |
| DE102012020217A1 (en) | 2012-10-15 | 2014-04-17 | Chemiewerk Bad Köstritz GmbH | Binder-free compact zeolitic moldings and process for their preparation |
| WO2014060246A1 (en) | 2012-10-15 | 2014-04-24 | Chemiewerk Bad Köstritz GmbH | Binder-free compact zeolite preforms and method for the production thereof |
| JP2016179467A (en) * | 2015-03-24 | 2016-10-13 | 東ソー株式会社 | Dehydrator of gas |
| JP2021000633A (en) * | 2015-03-24 | 2021-01-07 | 東ソー株式会社 | Gas dehydrator |
| JP2020049423A (en) * | 2018-09-26 | 2020-04-02 | 水澤化学工業株式会社 | Purification material |
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| Publication number | Publication date |
|---|---|
| JPH0674136B2 (en) | 1994-09-21 |
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