JPS63230581A - Manufacture of clay porous body with open fine pores - Google Patents
Manufacture of clay porous body with open fine poresInfo
- Publication number
- JPS63230581A JPS63230581A JP62062184A JP6218487A JPS63230581A JP S63230581 A JPS63230581 A JP S63230581A JP 62062184 A JP62062184 A JP 62062184A JP 6218487 A JP6218487 A JP 6218487A JP S63230581 A JPS63230581 A JP S63230581A
- Authority
- JP
- Japan
- Prior art keywords
- clay
- porous body
- sol
- freezing
- mixture
- 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
- 239000004927 clay Substances 0.000 title claims description 51
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011148 porous material Substances 0.000 title description 14
- 238000007710 freezing Methods 0.000 claims description 23
- 230000008014 freezing Effects 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 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 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 229920006328 Styrofoam Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 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 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- -1 sabonite Chemical compound 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 239000008261 styrofoam Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は開放型微細空孔の粘土多孔体の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing an open microporous clay porous body.
粘土多孔体は吸着能、触媒能、あるいは包接能等を有す
るものとして用いられる。The clay porous material is used as having adsorption ability, catalytic ability, or inclusion ability.
従来技術
従来の粘土多孔体の製造方法としては、粘土ゾルに発泡
剤を混入し、起泡させて多孔体を製造する方法が行われ
ている。しかし、この方法では粘土以外の化学物質が混
入するばかりでなく、空孔は閉じた球状のものとなり、
かつ50/7111φ以下の微細な均一の空孔を高い空
隙率で導入することは困難であった。従って吸着能、触
媒能、包接能の優れた多孔体となし得なかった。BACKGROUND ART A conventional method for producing a porous clay body is to mix a foaming agent into a clay sol and foam it to produce a porous body. However, with this method, not only do chemicals other than clay get mixed in, but the pores become closed and spherical.
In addition, it was difficult to introduce fine uniform pores with a diameter of 50/7111φ or less at a high porosity. Therefore, a porous body with excellent adsorption ability, catalytic ability, and inclusion ability could not be obtained.
発明の目的
本発明は従来法の欠点を解消すべくなされたもので、そ
の目的は、空孔が開放的で、50μ■φ以下の微細な空
孔を均一に含有する粘土多孔体を容易に得られる方法を
提供するにある。Purpose of the Invention The present invention was made to solve the drawbacks of the conventional method, and its purpose is to easily produce a clay porous body with open pores and uniformly containing fine pores of 50μ■φ or less. We are here to provide you with a method.
発明の構成
本発明者は前記目的を達成すべく鋭意研究の結果、粘土
と水との混合物を凍結させ、氷を融解することなく真空
乾燥する方法について研究を重ねたところ、混合物の粘
土含有率と凍結速度との関係を一定条件下で行うと、混
合物からの氷晶核の発生が、個々の氷晶の肥大化よりも
優先し得られ、開放型の均一な微細構造となし得られる
ことを究明し得た。この知見に基づいて本発明を完成し
た。Structure of the Invention As a result of intensive research to achieve the above object, the present inventor conducted repeated research on a method of freezing a mixture of clay and water and vacuum drying it without melting the ice, and found that the clay content of the mixture By examining the relationship between ice crystals and freezing rate under certain conditions, the generation of ice crystal nuclei from the mixture takes precedence over the enlargement of individual ice crystals, resulting in an open, uniform microstructure. We were able to find out. The present invention was completed based on this knowledge.
本発明の要旨は
天然または合成の粘土と水との混合物を凍結後、氷を融
解することなく真空乾燥して粘土多孔体を製造するに際
し、粘土と水との混合物の粘土含有率(C)と凍結速度
(F)をIogF≧−0.IC−0.7(但し、Cは重
量百分率、Fはn+17secの単位とする)の条件の
下で凍結することを特徴とする開放型微細空孔の粘土多
孔体の製造方法にある。The gist of the present invention is to freeze a mixture of natural or synthetic clay and water and then vacuum dry it without melting the ice to produce a clay porous body. and freezing rate (F) when IogF≧−0. A method for producing an open microporous clay porous body characterized by freezing under conditions of IC-0.7 (where C is a weight percentage and F is a unit of n+17 seconds).
本発明の方法に用いる粘土としては天然例えばモンモリ
ロナイト、サボナイト、バイデライト。Clays used in the method of the invention include natural clays such as montmorillonite, sabonite, and beidellite.
カオリナイト、アロフェン、ベントナイト等、または合
成粘土であってもよい。It may be kaolinite, allophane, bentonite, etc., or synthetic clay.
粘土と水との混合物の粘土含有率(C)と凍結温度は、
1ogF≧−〇、IC−0.7(但しC,Fは前記と同
じものを表わす、以下同じ)の条件下であることが必要
である。 1ogPが−0.IC−0.7未満であると
、微細な氷晶に加えてレンズ状の大型な氷結晶が混在す
るようになり、氷結晶を昇華消失させた後は微細な空孔
とレンズ状の大きな空孔が混在する多孔体となる。凍結
速度を更に小さくするとレンズ状の大きな空孔のみが発
達したものとなる。The clay content (C) and freezing temperature of the mixture of clay and water are:
It is necessary that the conditions are 1ogF≧-〇, IC-0.7 (C and F represent the same as above, and the same applies hereinafter). 1ogP is -0. If the IC value is less than 0.7, large lens-shaped ice crystals will be present in addition to fine ice crystals, and after the ice crystals sublimate and disappear, there will be minute holes and large lens-shaped vacancies. It becomes a porous body with a mixture of pores. When the freezing rate is further reduced, only large lens-shaped holes develop.
そのことは次のような理由によるものと考えられる。This is considered to be due to the following reasons.
粘土ゾルが冷却され、水分子が氷となって析出する際に
、新たな氷晶核を形成するか、あるいは既存の氷晶核の
表面に移動してその結晶を肥大化するかは、ゾル中の水
分子の易動度によって決定され、その易動度は粘土ゾル
の濃度(C)、ゾルの冷却速度に支配され、粘土ゾルの
濃度が高ければ小さく、ゾルの冷却速度が大きければ小
さくなる。When the clay sol cools and water molecules precipitate as ice, it is up to the sol to decide whether to form new ice crystal nuclei or migrate to the surface of existing ice crystal nuclei and enlarge the crystals. The mobility is determined by the mobility of water molecules in the clay sol, and the mobility is controlled by the concentration of the clay sol (C) and the cooling rate of the sol. Become.
本発明の条件1ogF≧−0.IC−0.7の範囲では
氷結晶が肥大化するよりも新たに氷晶核が発生して均一
な粒径の微小氷晶が得られ、これをはずれると氷結晶の
肥大化と新たな氷晶核の形成が同時に行われ大きくはず
れると氷結晶の肥大化のみが行われるものと考えられる
。Conditions of the present invention: 1ogF≧−0. In the range of IC-0.7, new ice crystal nuclei are generated and micro ice crystals with a uniform particle size are obtained rather than the ice crystals becoming enlarged, and beyond this range, the ice crystals become enlarged and new ice is formed. It is thought that if crystal nuclei are formed at the same time and deviate greatly, only the ice crystals will enlarge.
粘土と水との混合物の凍結に用いる冷却体との接触を面
状線状点状に変化させると、接触部から概ね垂直に氷晶
粒を整列させた形状のものとなる。When the contact with the cooling body used to freeze a mixture of clay and water is changed to a planar, linear, or dotted shape, ice crystal grains are arranged approximately perpendicularly from the contact portion.
凍結後、真空乾燥器に入れ、氷晶を昇華消失させると、
一定の微細空孔を持った粘土多孔体が得る部分が生じ、
開放型のものとなり、通気性である。After freezing, place it in a vacuum dryer to sublimate and eliminate the ice crystals.
A part of the clay porous body with certain micropores is obtained,
It is open type and breathable.
得られる粘土多孔体は1000℃まで加熱しても、その
組織は破かいされず、若干の収縮が生ずるだけである。Even when the obtained porous clay body is heated to 1000° C., its structure is not broken and only a slight shrinkage occurs.
実施例1゜
山形県左沢産の天然ベントナイトを水ひし、2イオンを
Na”に置換し、乾燥して原料粉末とした。Example 1 Natural bentonite from Sazawa, Yamagata Prefecture was strained with water, two ions were replaced with Na'', and the mixture was dried to obtain a raw material powder.
この原料粉末を純水と混合して5.10および20%の
粘土ゾルを作った。This raw material powder was mixed with pure water to make 5.10% and 20% clay sols.
各ゾルを容器に入れ、予め液体窒素を用いて冷却してお
いた金属塊を接触させた。両者の接触面積を調節して、
ゾルの凍結速度(凍結ゾル体積/凍結に要した時間、
a+1/5ec)を変化させ、5%粘土ゾルの場合は2
Xl0−’ml/see、 10%粘土ゾルの場合は
1.3 Xl0−’及び2.5 X 10−”ml/s
ec、20%粘゛土ゾルの場合は2X10−’、 3
X10−”、 8XlO−’及び3 X 10−’m
l/secのそれぞれの凍結速度で凍結し、真空乾燥器
内で氷晶を昇華消失させた。これにより微細な空孔(5
0μ−以下、凍結速度が早い場合は10μφ)を有する
粘土多孔体を得た。空隙率は粘土ゾル濃度の逆比であっ
てそれぞれ95%、90%。Each sol was placed in a container and brought into contact with a metal block that had been cooled in advance using liquid nitrogen. Adjust the contact area between the two,
Sol freezing rate (frozen sol volume/time required for freezing,
a+1/5ec), and in the case of 5% clay sol, 2
Xl0-'ml/see, 1.3 Xl0-' and 2.5 X 10-'ml/s for 10% clay sol
ec, 2X10-' for 20% clay sol, 3
X10-'', 8X1O-' and 3 X10-'m
Freezing was carried out at respective freezing rates of 1/sec, and ice crystals were sublimated and disappeared in a vacuum dryer. This results in fine pores (5
A clay porous body having a diameter of 0μ or less (10μφ if the freezing rate is fast) was obtained. The porosity is the inverse ratio of the clay sol concentration, which is 95% and 90%, respectively.
80%であった。走査型電子顕微鏡で観察したところ、
空孔は一部隣接空孔と貫通し開放型であった。It was 80%. When observed with a scanning electron microscope,
Some of the holes penetrated through adjacent holes and were open.
得られた粘土多孔体を800℃で30分間加熱したとこ
ろ、組織、形状には殆ど変化なく、体積が若干収縮した
だけであった。When the obtained porous clay body was heated at 800° C. for 30 minutes, there was almost no change in the structure or shape, and the volume only slightly contracted.
実施例2゜
水熱合成法により合成されたNa”の層間イオンを有す
るNa型サポナイト粉末を純水と混合して、10%ゾル
とした。このゾルを注射器様の治具を用いて、予め液体
窒素で冷却しておいた金属塊の表面に連続的に噴出し、
I Xl0−’ml/secの凍結速度で凍結し、実施
例1と同様に真空乾燥処理を行った。Example 2 Na-type saponite powder having interlayer ions of Na'' synthesized by hydrothermal synthesis was mixed with pure water to make a 10% sol. This sol was injected in advance using a syringe-like jig. It is continuously ejected onto the surface of a metal block that has been cooled with liquid nitrogen.
It was frozen at a freezing rate of IXl0-'ml/sec, and vacuum-dried in the same manner as in Example 1.
その結果、10μmφの均一な微小空孔を有する長尺の
うどん状形態の粘土多孔体が得られた。加熱処理を実施
例1と同様に行ったが、その結果は実施例1と同様であ
った。As a result, a long, udon-shaped porous clay body having uniform micropores of 10 μmφ was obtained. The heat treatment was performed in the same manner as in Example 1, and the results were the same as in Example 1.
比較例1゜
実施例1と同じベントナイトゾル(粘土含有率5%)を
用い、これをアクリル樹脂製容器に入れ、銅製の針を底
部から垂直に挿入し、咳針の他端を液体窒素に浸し、液
体窒素の液面高さを調節して粘土ゾルの凍結速度を5
X 10−3〜2 X 10−”ml/secになるよ
うにした。5%粘土ゾルを用いて、本発明の目的とする
開放型微細空孔を有する粘土多孔体を得るためには、凍
結速度は8 X 10−”ml/sec以上でなければ
ならない。凍結後、真空乾燥器内で昇華させ粘土多孔体
を一部た。Comparative Example 1゜Using the same bentonite sol (clay content 5%) as in Example 1, it was placed in an acrylic resin container, a copper needle was inserted vertically from the bottom, and the other end of the cough needle was immersed in liquid nitrogen. Soak the clay sol and adjust the liquid nitrogen level to increase the freezing speed of the clay sol to 5.
X 10-3 to 2 The speed must be greater than or equal to 8 x 10-'' ml/sec. After freezing, the clay porous material was partially sublimated in a vacuum dryer.
得られた粘土多孔体は幅<100μI長さ数寵のレンズ
状の空孔が整列したもので、針を中心にしてガスタービ
ンの羽のように放射状の形状に形成した。これを800
℃で30分間加熱したが、その組織は殆ど変化せず、若
干の体積収縮が見られたのみであった。The resulting clay porous body had lens-shaped pores with a width of <100 μI and a length of several centimeters aligned, and was formed in a radial shape like the blades of a gas turbine with the needle as the center. This is 800
Although it was heated at ℃ for 30 minutes, the structure hardly changed and only a slight volume shrinkage was observed.
比較例2゜
水熱合成法により合成されたNa+を層間イオンとした
Na型モンモリロナイト粉末を純水に混合して粘土含有
率5%のゾルとした。該ゾルを底部を平坦に磨いたガラ
ス製容器に入れ、底部のみを銅または真鍮の金属塊に接
触させ、他の部分は発泡スチロール材を用いて断熱した
。金属塊を液体窒素に浸し、その浸液量を変化させてゾ
ルの凍結速度が5×lO弓〜2 X 10−”a+1/
secになるように調節しながら冷却し凍結させた。こ
れを真空乾燥器内で氷を昇華させ粘土多孔体を得た。得
られた粘土多孔体は幅0.1w長さ数寵のレンズ状の空
孔が冷却面に垂直に整列した組織を有するものであった
。Comparative Example 2 A Na-type montmorillonite powder synthesized by a hydrothermal synthesis method and containing Na+ as an interlayer ion was mixed with pure water to form a sol with a clay content of 5%. The sol was placed in a glass container with a polished flat bottom, and only the bottom was in contact with a copper or brass metal block, and the other parts were insulated using styrofoam material. By immersing a metal block in liquid nitrogen and varying the amount of immersion liquid, the freezing rate of the sol is 5 x 10~2 x 10-"a+1/
The mixture was cooled and frozen while controlling the temperature to sec. The ice was sublimed in a vacuum dryer to obtain a porous clay body. The resulting clay porous body had a structure in which lens-shaped holes with a width of 0.1w and a length of several centimeters were aligned perpendicularly to the cooling surface.
発明の効果 本発明の方法によると次のような優れた効果を有する。Effect of the invention The method of the present invention has the following excellent effects.
1)、50μmφ以下の均一な微細空孔を存する粘土多
孔体が容易に得られる。1) A clay porous body containing uniform micropores with a diameter of 50 μm or less can be easily obtained.
2)、微細空孔は発泡体を使用する従来法におけるよう
な閉じたものでなく、隣接する空孔と一部貫通した開放
的なものとなる。2) The micropores are not closed as in the conventional method using foam, but are open, partially penetrating adjacent pores.
3)、空隙率も粘土ゾル濃度と、凍結速度の調整により
多孔体め使用目的に合わせて、50〜99.9%と自由
に選択して生成し得られる。3) The porosity can be freely selected from 50 to 99.9% depending on the intended use of the porous body by adjusting the clay sol concentration and freezing rate.
4)、凍結に際し、冷却体との接触状態を変化させるこ
とにより、粘土多孔体中の空孔の配列を容易に変化させ
ることができる。4) During freezing, the arrangement of pores in the clay porous body can be easily changed by changing the contact state with the cooling body.
従って、得られる粘土多孔体を吸着剤、触媒等の用途に
応じたものと容易になし得る。Therefore, the resulting clay porous material can be easily made into a material suitable for use as an adsorbent, catalyst, etc.
j−゛−′−−2゛5
特許出願人 科学技術庁無機材質研究所長瀬 高
信 門 ゛
手続補正書
昭和62年6月2 日
特許庁長官 黒 1)明 雄 殿
1、事件の表示
昭和62年特許願第62184号
2、発明の名称
開放型微細空孔の粘土多孔体の製造方法3、補正をする
者
事件との関係 特許出願人
5、補正により増加する発明の数 なし6、補正の対象
明細書の特許請求の範囲及び発明の詳細な説明の欄7、
補正の内容
別紙
(1) 特許請求の範囲を次の通り訂正する。j−゛−′−−2゛5 Patent applicant Takashi Nagase, Institute of Inorganic Materials, Science and Technology Agency
Shinmon ゛Procedural Amendment June 2, 1988 Commissioner of the Patent Office Black 1) Mr. Akio 1, Indication of the case 1988 Patent Application No. 62184 2, Title of the invention Open-type microporous clay porous material Manufacturing method 3, Relationship with the case of the person making the amendment Patent applicant 5, Number of inventions increased by the amendment None 6, Scope of claims and detailed description of the invention in the specification to be amended 7,
Attachment to the contents of the amendment (1) The scope of the claims is amended as follows.
「天然または合成の粘土と水との混合物を凍結後、氷を
融解することなく莢腹旦て粘土多孔体を製造するに際し
、粘土と水との混合物の粘土含有率(C)と凍結速度(
F)を、logF= −0.IC−0.7(但し、Cは
重量百分率、Fはl11/secの単位とする)の条件
の下で凍結することを特徴とする開放型微細空孔の粘土
多孔体の製造方法。」(2)明細書第2頁15行、及び
第3頁3行「真空」を削除する。゛
(3)同第4真終行「真空乾燥器」の前に「例えば」を
挿入する。``When producing a porous clay material immediately after freezing a mixture of natural or synthetic clay and water, the clay content (C) of the mixture of clay and water and the freezing rate (
F), logF=-0. A method for producing an open-type microporous clay porous body, characterized by freezing under conditions of IC-0.7 (where C is a weight percentage and F is a unit of 111/sec). (2) Delete ``Vacuum'' on page 2, line 15, and page 3, line 3 of the specification.゛(3) Insert "for example" in front of "vacuum dryer" in the fourth true last line of the same sentence.
゛(4)同第5頁第1行「せると、」を「せるか、ある
いは乾燥冷気体にさらすと」に修正する。゛(4) In the first line of page 5, ``to cause'' should be amended to ``to cause, or to expose to dry cold gas.''
Claims (1)
解することなく真空乾燥して粘土多孔体を製造するに際
し、粘土と水との混合物の粘土含有率(C)と凍結速度
(F)を、logF≧−0.1C−0.7(但し、Cは
重量百分率、Fはml/secの単位とする)の条件の
下で凍結することを特徴とする開放型微細空孔の粘土多
孔体の製造方法。When producing a clay porous body by freezing a mixture of natural or synthetic clay and water and then vacuum drying it without melting the ice, the clay content (C) and freezing rate (F) of the mixture of clay and water are determined. ) is frozen under the conditions of logF≧-0.1C-0.7 (where C is a weight percentage and F is a unit of ml/sec). Method for producing porous body.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62062184A JPS63230581A (en) | 1987-03-17 | 1987-03-17 | Manufacture of clay porous body with open fine pores |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62062184A JPS63230581A (en) | 1987-03-17 | 1987-03-17 | Manufacture of clay porous body with open fine pores |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63230581A true JPS63230581A (en) | 1988-09-27 |
JPH0417913B2 JPH0417913B2 (en) | 1992-03-26 |
Family
ID=13192793
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62062184A Granted JPS63230581A (en) | 1987-03-17 | 1987-03-17 | Manufacture of clay porous body with open fine pores |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS63230581A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6376421B2 (en) | 1998-03-26 | 2002-04-23 | The Dow Chemical Company | Ion exchanged aluminum-magnesium silicate or fluorinated magnesium silicate aerogels and catalyst supports therefrom |
EP1245549A2 (en) | 2001-03-28 | 2002-10-02 | Asahi Glass Company Ltd. | Process for preparing silicate porous product |
WO2010087169A1 (en) * | 2009-01-30 | 2010-08-05 | 独立行政法人産業技術総合研究所 | Porous clay material and method for producing same |
-
1987
- 1987-03-17 JP JP62062184A patent/JPS63230581A/en active Granted
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6376421B2 (en) | 1998-03-26 | 2002-04-23 | The Dow Chemical Company | Ion exchanged aluminum-magnesium silicate or fluorinated magnesium silicate aerogels and catalyst supports therefrom |
EP1245549A2 (en) | 2001-03-28 | 2002-10-02 | Asahi Glass Company Ltd. | Process for preparing silicate porous product |
EP1245549A3 (en) * | 2001-03-28 | 2004-02-04 | Asahi Glass Company Ltd. | Process for preparing silicate porous product |
WO2010087169A1 (en) * | 2009-01-30 | 2010-08-05 | 独立行政法人産業技術総合研究所 | Porous clay material and method for producing same |
Also Published As
Publication number | Publication date |
---|---|
JPH0417913B2 (en) | 1992-03-26 |
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