JPH068172B2 - Aggregate of slit-like or honeycomb-like structure of aluminum hydroxide or aluminum oxide and its manufacturing method - Google Patents
Aggregate of slit-like or honeycomb-like structure of aluminum hydroxide or aluminum oxide and its manufacturing methodInfo
- Publication number
- JPH068172B2 JPH068172B2 JP61165302A JP16530286A JPH068172B2 JP H068172 B2 JPH068172 B2 JP H068172B2 JP 61165302 A JP61165302 A JP 61165302A JP 16530286 A JP16530286 A JP 16530286A JP H068172 B2 JPH068172 B2 JP H068172B2
- Authority
- JP
- Japan
- Prior art keywords
- aggregate
- honeycomb
- slit
- aluminum hydroxide
- aluminum oxide
- 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.)
- Expired - Lifetime
Links
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 title claims description 19
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000003463 adsorbent Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
- C01F7/36—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts from organic aluminium salts
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、薄板状に集合し特定の規則的空孔を有する水
酸化アルミニウムあるいは酸化アルミニウムの新規なス
リット状又はハニカム様の集合体、及びその製造方法に
関し、吸着剤、触媒、化粧料用粉体等の用途に使用し得
る新規なアルミナ粒（粒）状体を提供することを目的と
する。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention relates to a novel slit-shaped or honeycomb-shaped aggregate of aluminum hydroxide or aluminum oxide aggregated in a thin plate shape and having specific regular pores, and With respect to the production method thereof, it is an object of the present invention to provide a novel alumina granular material that can be used for applications such as an adsorbent, a catalyst, and a powder for cosmetics.
従来、アルミナもしくはその水和物は、その吸着能等を
利用して粉末、塊状、破砕状、錠剤等の形で吸着剤、乾
燥剤、触媒等として各工業に広汎に使用されており、更
に耐火物、顔料担体、医薬、化粧料等にも広く用いられ
ている。アルミナ水和物を脱水して得られるいわゆる活
性アルミナは細孔構造を有し、この細孔構造は吸着活性
や触媒活性のために重要なものであるが、通常気孔率0.
4〜0.7、見掛比重0.8〜２程度で、平均孔径は40〜100Å
であり、細孔は不規則にあいている。Conventionally, alumina or its hydrate has been widely used in each industry as an adsorbent, a desiccant, a catalyst, etc. in the form of powder, lump, crush, tablet, etc. by utilizing its adsorption ability and the like. It is also widely used in refractories, pigment carriers, medicines, cosmetics and the like. So-called activated alumina obtained by dehydrating alumina hydrate has a pore structure, and this pore structure is important for adsorption activity and catalytic activity, but usually has a porosity of 0.
4 to 0.7, apparent specific gravity of 0.8 to 2 and average pore size of 40 to 100Å
And the pores are irregular.
水酸化アルミニウムあるいは酸化アルミニウムを吸着
剤、触媒等として利用するには、その比表面積が大きい
方が効率が高い。しかしながら、水酸化アルミニウムあ
るいは酸化アルミニウムを微粒化すると、微粒子は密に
充填され、吸着剤、触媒を必要とする物質の流通透過性
は低下し、迅速な作業を期待する場合には不向きな形状
と言える。そこで、例えばハニカム様の形状に成型し、
流通透過性を向上させる方法が行われているが、現在得
られているものは、その壁厚が0.1mm以上、その空孔の
直径１mm以上と大きな形状であり、接触効率が低下して
しまう。そこで接触面積が高く、被吸着物あるいは触媒
を必要とする物質の流通透過を迅速にして接触効率を高
めるには、水酸化アルミニウムあるいは酸化アルミニウ
ムの形状がハニカム様又はスリット状で、その比表面積
が広がるように壁厚、空孔の幅が狭いものが好ましいこ
とが推測されるが、その様な形状の集合体、あるいはそ
の製造方法は従来全く知られていない。In order to use aluminum hydroxide or aluminum oxide as an adsorbent, a catalyst, etc., the larger the specific surface area, the higher the efficiency. However, when aluminum hydroxide or aluminum oxide is atomized, the particles are densely packed, and the flow permeability of substances that require adsorbents and catalysts is reduced, making them unsuitable for rapid work. I can say. So, for example, mold it into a honeycomb-like shape,
Although the method of improving the flow permeability has been carried out, what is currently obtained is that the wall thickness is 0.1 mm or more and the diameter of the pores is 1 mm or more, which is a large shape, and the contact efficiency is reduced. . Therefore, the contact area is high, and in order to speed up the flow and permeation of the substance to be adsorbed or the substance requiring the catalyst to enhance the contact efficiency, the shape of aluminum hydroxide or aluminum oxide is honeycomb-like or slit-like, and its specific surface area is It is presumed that it is preferable that the wall thickness and the width of the pores are narrow so as to widen, but an aggregate having such a shape or a manufacturing method thereof has not been known at all.
そこで本発明者らは、ゾルーゲル法による水酸化アルミ
ニウム微粒子の調製について研究を重ねるうち、水酸化
アルミニウムゾル又はゲルの一定条件下の凍結乾燥によ
り、特定の規則的空孔を有するアルミナ水和物凝集体を
製し得ること、そして更にこれを焼成することにより対
応するアルミナ凝集体を製し得ることを見出した。Therefore, while the inventors of the present invention have conducted extensive research on the preparation of aluminum hydroxide fine particles by the sol-gel method, by freeze-drying the aluminum hydroxide sol or gel under certain conditions, an alumina hydrate coagulation having specific regular pores is obtained. It has been found that the aggregates can be made, and by further calcining them, the corresponding alumina agglomerates can be made.
本発明によれば壁厚が0.01μｍ〜15μｍ、空孔の幅乃至
平均直径が１μｍ〜50μｍで、深さが10μｍ以上の、ハ
ニカム様又はスリット状の集合体が提供される。According to the present invention, there is provided a honeycomb-like or slit-like aggregate having a wall thickness of 0.01 μm to 15 μm, pore widths or average diameters of 1 μm to 50 μm, and a depth of 10 μm or more.
即ち本発明は、下記の(1)及び（又は）(2)の構造を有
し、次の一般式（Ｉ）で示される、水酸化アルミニウム
あるいは酸化アルミニウムのスリット状又はハニカム様
構造の集合体に係わるものである。That is, the present invention has the structure of the following (1) and (or) (2), the aggregate of aluminum hydroxide or aluminum oxide slit-like or honeycomb-like structure represented by the following general formula (I) Related to.
Al2O3・nH2O （Ｉ） （ｎは０〜3.5） (1) 平均厚みが0.01μｍ〜15μｍの複数の薄壁板Ａが
１μｍ〜50μｍの間隔で概ね等方向に重なり、その空隙
は所々薄壁板Ａとほぼ同じ厚みの薄壁板Ｂにより仕切ら
れているスリット状構造 (2) 平均厚みが0.01μｍ〜15μｍの薄壁部分とそれに
囲まれる平均直径１μｍ〜50μｍの空孔からなるハニカ
ム様構造 また本発明は上記新規集合体の製造方法として、Al2O3
としての濃度が0.1〜20重量％で、そのpHが１〜７であ
る水酸化アルミニウムあるいは酸化アルミニウムの水中
分散液を、−４℃〜−200℃で凍結した後、凍結状態の
まま水分を蒸発させることにより集合体を形成させる
か、あるいは更にその集合体を焼成することを特徴とす
る水酸化アルミニウムあるいは酸化アルミニウムのスリ
ット状又はハニカム様構造の集合体の製造方法を提供す
るものである。Al 2 O 3 · nH 2 O (I) (n is 0 to 3.5) (1) A plurality of thin wall plates A having an average thickness of 0.01 μm to 15 μm are superposed in a substantially equal direction at intervals of 1 μm to 50 μm, and the voids are formed. Is a slit-like structure that is partitioned in some places by a thin wall plate B having almost the same thickness as the thin wall plate A. (2) From a thin wall part with an average thickness of 0.01 μm to 15 μm and holes surrounded by it with an average diameter of 1 μm to 50 μm The honeycomb-like structure according to the present invention is also provided as a method for producing the above-mentioned novel aggregate, wherein Al 2 O 3
Of 0.1 to 20% by weight and pH of 1 to 7 in water of aluminum hydroxide or aluminum oxide is frozen at -4 ° C to -200 ° C, and water is evaporated in the frozen state. The present invention provides a method for producing an aggregate of aluminum hydroxide or aluminum oxide having a slit-like or honeycomb-like structure, which comprises forming an aggregate by firing or by further firing the aggregate.
本発明の製造方法の好ましい実施態様によれば、Al2O3
としての濃度が0.1〜20重量％でそのpHが１〜７である
上記式（Ｉ）で示される水酸化アルミニウムあるいは酸
化アルミニウムの水中分散液を、一方向から２cm/hr以
上の速度で−４℃〜−200℃に凍結し、その状態のまま
水分を蒸発させることにより集合体を形成させる。ま
た、必要に応じてその集合体を焼成することによって焼
成集合体を形成されることにより、目的とするスリット
状あるいは（及び）ハニカム様の集合体が得られる。According to a preferred embodiment of the production method of the present invention, Al 2 O 3
A dispersion of aluminum hydroxide or aluminum oxide of formula (I) in water having a concentration of 0.1 to 20% by weight and a pH of 1 to 7 at a rate of 2 cm / hr or more from one direction-4 Freeze to ℃ ~ -200 ℃, to evaporate the water in that state to form an aggregate. If desired, the aggregate is fired to form a fired aggregate, whereby a desired slit-shaped or / and honeycomb-like aggregate is obtained.
本発明の集合体は、好ましくは凝集粒（粉）状体として
得られるが、その大きさは塊状物から、粒状体、粉状体
まで所望の形状とすることができる。即ち、凍結乾燥し
て取り出した塊状アルミナ水和物、あるいは更に焼成を
した塊状アルミナ（水和物）を粉砕することにより本発
明の集合体の特徴とするスリット状あるいはハニカム様
凝集構造を保持したまま最低約30μｍまでの所望粒度の
ものとすることができる。The aggregate of the present invention is preferably obtained as agglomerated particles (powder), but the size thereof can be any desired shape, from lumps to granules and powders. That is, the aggregated alumina hydrate that was freeze-dried and taken out, or the aggregated alumina hydrate that was further fired was pulverized to retain the slit-like or honeycomb-like agglomerated structure that is the feature of the aggregate of the present invention. The desired particle size can be as low as about 30 μm.
かかる本発明粒子の構造的特徴は、上記の如く孔径0.1
μｍ〜15μｍで規則的なハニカム様細孔及び／又はスリ
ット状間孔を有する構造からなるアルミナ（水和物）凝
集体である。The structural feature of the particles of the present invention is that the pore size is 0.1 as described above.
It is an alumina (hydrate) aggregate having a structure having regular honeycomb-like pores and / or slit-shaped interstitial pores of μm to 15 μm.
上記（Ｉ）式中、１モルのAl2O3に対する水分子のモル
数であるｎは０〜3.5（100℃で24時間乾燥した後の値）
であるが、就中モル数ｎが1.6〜2.0のものが製造時の水
溶液中での高い分散性の点から好ましい。このような、
Al2O3１モルに対して1.6〜2.0モルの水分子を持つ水酸
化アルミニウムにベーマイトがある。本発明の製造方法
に於いて水酸化アルミニウム又は酸化アルミニウムの高
い水中分散液を得るには、例えば塩酸、硝酸、酢酸等の
酸水溶液を加え、pHを７以下にするが、特に高い分散性
を得るためにはpHを４以下に調整することが好ましい。
水酸化アルミニウム又は酸化アルミニウムの水溶液中の
濃度は、Al2O3としての重量濃度が0.1〜20重量％であ
る。0.1重量％以下では連続したスリット又はハニカム
の薄壁が得られず、一方20重量％以上であると、薄壁の
厚みが15μｍよりも大きくなってしまい好ましくない。
この時得られる分散液の状態はゾル状あるいはゲル状が
好ましい。この分散液はシリンダー状の管に注入された
後、−４℃〜−200℃の冷媒に入れられ凍結される。こ
の時の冷媒としては、例えばドライアイス／アセトン
液、液体チッ素、氷／水液等が使用し得る。この分散液
の凍結において、シリンダー状管は底方向へ媒体中に定
速度でおろされること、即ち一方向凍結法が、スリット
状又はハニカム様構造中の空孔を定方向に深くするため
に好ましく、その注入速度、即ち凍結速度は２cm/hr以
上が特に好ましい。この後凍結物は凍結状態で水分の蒸
発が行われるが、これは例えば真空下において水分を吸
引することにより行われる。この時の真空度は１Torr以
下が好ましい。この水分蒸発により目的とするスリット
状あるいはハニカム様の構造が得られる。この時作られ
た構造体は室温以上の温度で焼成してもよく、これによ
って例えばδ−アルミナ、θ−アルミナ、α−アルミナ
等に変化させ得る。In the above formula (I), n, which is the number of moles of water molecules with respect to 1 mole of Al 2 O 3 , is 0 to 3.5 (value after drying at 100 ° C. for 24 hours).
However, those having a molar number n of 1.6 to 2.0 are preferable from the viewpoint of high dispersibility in an aqueous solution at the time of production. like this,
There is boehmite in aluminum hydroxide having 1.6 to 2.0 moles of water molecules with respect to 1 mole of Al 2 O 3 . In order to obtain an aqueous dispersion of aluminum hydroxide or aluminum oxide having a high content in the production method of the present invention, an aqueous acid solution such as hydrochloric acid, nitric acid or acetic acid is added to bring the pH to 7 or less. In order to obtain it, it is preferable to adjust the pH to 4 or less.
The concentration of aluminum hydroxide or aluminum oxide in the aqueous solution is 0.1 to 20% by weight as Al 2 O 3 . If it is 0.1% by weight or less, continuous slits or honeycomb thin walls cannot be obtained, while if it is 20% by weight or more, the thickness of the thin walls becomes larger than 15 μm, which is not preferable.
The state of the dispersion liquid obtained at this time is preferably sol or gel. This dispersion is poured into a cylindrical tube and then put into a refrigerant at -4 ° C to -200 ° C to be frozen. As the refrigerant at this time, for example, dry ice / acetone liquid, liquid nitrogen, ice / water liquid, or the like can be used. In freezing this dispersion, the cylindrical tube is lowered in the medium at a constant velocity in the bottom direction, that is, the one-way freezing method is preferable in order to deepen the pores in the slit-shaped or honeycomb-like structure in the fixed direction. The injection rate, that is, the freezing rate is particularly preferably 2 cm / hr or more. After this, the frozen product undergoes evaporation of water in a frozen state, which is carried out by sucking water under vacuum, for example. The vacuum degree at this time is preferably 1 Torr or less. By this evaporation of water, the desired slit-like or honeycomb-like structure is obtained. The structure produced at this time may be fired at a temperature of room temperature or higher, whereby it can be changed to, for example, δ-alumina, θ-alumina, α-alumina or the like.
本発明の新規なアルミナ又はその水和物の粒乃至粉状体
は、その規則的な空孔構造のゆえに、吸着剤等として用
いた場合に接触効率がよく、粉体として化粧料等に用い
たときはすべりがよく、優れた感触の粉体であって、種
々の用途に優れた性能を発揮し得る。INDUSTRIAL APPLICABILITY The novel alumina or its hydrate granules or powders of the present invention have good contact efficiency when used as an adsorbent or the like because of its regular pore structure, and are used as a powder for cosmetics and the like. It is a powder that is slippery when touched and has an excellent feel, and can exhibit excellent performance in various applications.
次に本発明による水酸化アルミニウムあるいは酸化アル
ミニウムのスリット状あるいはハニカム様構造体を製造
する実施例について本発明を詳しく説明するが、本発明
はこれらの実施例に限定されるものではない。Next, the present invention will be described in detail with reference to examples for producing a slit-shaped or honeycomb-like structure of aluminum hydroxide or aluminum oxide according to the present invention, but the present invention is not limited to these examples.
実施例１ アルミニウムイソプロポキサイド〔Al(i-C3H7O3〕（東
京化成製）を使用し、この原料１モルに対して再蒸留水
100モルを加え、温度90℃で3500rpmの速度で撹拌しなが
ら、加水分解を行った。この溶液に1Nの塩酸を加え、pH
を４に調製した。この溶液に蒸留水を加え、Al2O3の濃
度を１重量％にした後、直径１cm、深さ５cmのプラスチ
ック製のシリンダー状管を注入し、この管をアセトンと
ドライアイスからなる−78℃の冷媒中に５cm/hrの速度
で降下させ、分散液を下から上に向け一方向に凍結させ
た。凍結物はシリンダー状の管中のまま凍結状態を保
ち、高真空下(0.05Torr)で２日間乾燥した。この凍結乾
燥で薄壁の厚さ0.1μｍ、空孔の幅５μｍ、深さ最大５c
mのスリット状の構造が得られた。この構造体の走査型
電子顕微鏡写真（日本電子製 JSM-840）を第１図に示
す。この構造体の結晶構造は粉末Ｘ線回折法（理学電機
工業製ガイガーフレックス、 D-S型 CuKα線）による同
定によれば擬ベーマイトであった。Example 1 Aluminum isopropoxide [Al (iC 3 H 7 O 3 ] (manufactured by Tokyo Kasei) was used, and redistilled water was used for 1 mol of this raw material.
100 mol was added, and hydrolysis was performed while stirring at a temperature of 90 ° C. and a speed of 3500 rpm. 1N hydrochloric acid was added to this solution to adjust the pH.
Was adjusted to 4. Distilled water was added to this solution to adjust the concentration of Al 2 O 3 to 1% by weight, and then a plastic cylindrical tube having a diameter of 1 cm and a depth of 5 cm was injected, and the tube was composed of acetone and dry ice. The dispersion liquid was dropped into the refrigerant at a temperature of 5 ° C. at a speed of 5 cm / hr, and the dispersion liquid was frozen in one direction from bottom to top. The frozen product was kept frozen in a cylindrical tube and dried under high vacuum (0.05 Torr) for 2 days. This freeze-drying has a thin wall thickness of 0.1 μm, pore width of 5 μm, and maximum depth of 5 c.
A slit-like structure of m was obtained. A scanning electron micrograph (JSM-840 manufactured by JEOL Ltd.) of this structure is shown in FIG. The crystal structure of this structure was pseudo-boehmite according to the identification by the powder X-ray diffraction method (Geiger flex manufactured by Rigaku Denki Kogyo, DS type CuKα ray).
実施例２ 実施例１に於いて、加水分解後の分散液を濃縮すること
によってAl2O3としての濃度を12重量％にした後、同様
にして凍結及び水分蒸発を行って製造すると、壁の厚み
0.5μｍ、空孔の直径５μｍ、深さ最大３cmのハニカム
様構造が得られた。この構造体の走査型顕微鏡写真を第
２図に示す。Example 2 In Example 1, the concentration of Al 2 O 3 was adjusted to 12% by weight by concentrating the hydrolyzed dispersion, and then frozen and evaporated in the same manner to produce a wall. Thickness of
A honeycomb-like structure having a diameter of 0.5 μm, a pore diameter of 5 μm and a maximum depth of 3 cm was obtained. A scanning micrograph of this structure is shown in FIG.
実施例３ 0.5mol/濃度のAlCl3・6H2O溶液400mlに1.25mol/NaO
H溶液400mlを加えて白色の水酸化アルミニウムの沈澱を
作る。次いでこの沈澱を母液と共にそのまま80℃に加熱
し、90分間その状態を保持して解膠すると、無色透明な
ゾルとなる（ゾルのpHは4.02）。このゾルを直径１cm、
深さ５cmのプラスチック製のシリンダー状管に注ぎ、実
施例１と同様にして凍結乾燥すると、薄壁の厚さ0.2μ
ｍ、空孔の幅５μｍ、深さ最大５cmのスリット状の構造
が得られた。Example 3 1.25 mol / NaO in 400 ml of 0.5 mol / concentration AlCl 3 .6H 2 O solution
400 ml of H solution are added to make a white aluminum hydroxide precipitate. Next, this precipitate is heated together with the mother liquor to 80 ° C. as it is, and the state is maintained for 90 minutes to deflocculate to obtain a colorless and transparent sol (pH of sol is 4.02). This sol has a diameter of 1 cm,
When it was poured into a plastic cylindrical tube having a depth of 5 cm and freeze-dried in the same manner as in Example 1, the thin wall thickness was 0.2 μm.
m, the width of the pores was 5 μm, and the maximum depth was 5 cm.
実施例４ 実施例１の方法でAl2O3の濃度を12重量％の分散液を調
製した後、冷媒として液体チッ素を用いて凍結し水分蒸
発を行うと、壁の厚み0.5μｍ、空孔の幅３μｍ、深さ
最大３cmのハニカム様構造が得られた。Example 4 A dispersion having an Al 2 O 3 concentration of 12% by weight was prepared by the method of Example 1 and then frozen using liquid nitrogen as a refrigerant to evaporate water, whereby a wall thickness of 0.5 μm and an empty space were obtained. A honeycomb-like structure having a pore width of 3 μm and a maximum depth of 3 cm was obtained.
実施例５ 実施例１の方法でAl2O3の濃度12重量％の分散液を調製
した後、直径３cm、深さ５cmのプラスチック製のシリン
ダー状管に注入し、以下同様の操作で凍結乾燥したとこ
ろ、薄壁の厚さ0.5μｍ、空孔の幅３μｍ、深さ最大５c
mのハニカム様構造及びスリット状構造の混合構造が得
られた。Example 5 A dispersion of Al 2 O 3 having a concentration of 12% by weight was prepared by the method of Example 1, and then poured into a plastic cylindrical tube having a diameter of 3 cm and a depth of 5 cm, and then freeze-dried by the same operation. As a result, the thickness of the thin wall was 0.5 μm, the width of the holes was 3 μm, and the maximum depth was 5 c.
A mixed structure of m-like honeycomb-like structure and slit-like structure was obtained.
実施例６ 実施例１の方法で製造したスリット状構造体を１分間に
１℃の昇温速度で550℃まで加熱したところ、スリット
状の構造は変わらず、組成はδ−Al2O3に変化した。Example 6 When the slit-shaped structure manufactured by the method of Example 1 was heated to 550 ° C. at a temperature rising rate of 1 ° C. for 1 minute, the slit-shaped structure remained unchanged and the composition changed to δ-Al 2 O 3 . changed.
実施例７ 実施例２の方向で製造したハニカム様の構造体を１分間
に１℃の昇温速度で1200℃まで加熱したところ、ハニカ
ム様の構造は変わらず、組成はα−Al2O3に変化した。Example 7 When the honeycomb-like structure manufactured in the direction of Example 2 was heated to 1200 ° C. at a heating rate of 1 ° C. for 1 minute, the honeycomb-like structure was not changed and the composition was α-Al 2 O 3. Changed to.
第１図は実施例１で得られた本発明のスリット状集合体
の結晶構造の走査型顕微鏡写真（倍率；400）、第２図
は実施例２で得られた本発明のハニカム様集合体の結晶
構造の走査型顕微鏡写真（倍率；400）である。FIG. 1 is a scanning micrograph (magnification: 400) of the crystal structure of the slit-shaped aggregate of the present invention obtained in Example 1, and FIG. 2 is the honeycomb-like aggregate of the present invention obtained in Example 2. 3 is a scanning micrograph (magnification: 400) of the crystal structure of
Claims (5)
次の一般式（Ｉ）で示される、水酸化アルミニウムある
いは酸化アルミニウムのスリット状又はハニカム様構造
の集合体。 Al2O3・nH2O （Ｉ） （ｎは０〜3.5） (1) 平均厚みが0.01μｍ〜15μｍの複数の薄壁板Ａが
１μｍ〜50μｍの間隔で概ね等方向に重なり、その空隙
は所々薄壁板Ａとほぼ同じ厚みの薄壁板Ｂにより仕切ら
れているスリット状構造 (2) 平均厚みが0.01μｍ〜15μｍの薄壁部分とそれに
囲まれる平均直径１μｍ〜50μｍの空孔からなるハニカ
ム様構造1. A structure having the following (1) and / or (2),
A slit-shaped or honeycomb-like aggregate of aluminum hydroxide or aluminum oxide represented by the following general formula (I). Al 2 O 3 · nH 2 O (I) (n is 0 to 3.5) (1) A plurality of thin wall plates A having an average thickness of 0.01 μm to 15 μm are superposed in a substantially equal direction at intervals of 1 μm to 50 μm, and the voids are formed. Is a slit-like structure that is partitioned in some places by a thin wall plate B having almost the same thickness as the thin wall plate A. (2) From a thin wall part with an average thickness of 0.01 μm to 15 μm and holes surrounded by it with an average diameter of 1 μm to 50 μm Honeycomb-like structure
記載の集合体。2. The aggregate according to claim 1, wherein the aggregate is granular.
のpHが１〜７である水酸化アルミニウムあるいは酸化ア
ルミニウムの水中分散液を、−４℃〜−200℃で凍結し
た後、凍結状態のまま水分を蒸発させることにより集合
体を形成させるか、あるいは更にその集合体を焼成する
ことを特徴とする水酸化アルミニウムあるいは酸化アル
ミニウムのスリット状又はハニカム様構造の集合体の製
造方法。3. An aqueous dispersion of aluminum hydroxide or aluminum oxide having a concentration of Al 2 O 3 of 0.1 to 20% by weight and a pH of 1 to 7 is frozen at -4 ° C to -200 ° C. After that, the aggregate is formed by evaporating the water in the frozen state, or the aggregate is fired, and the aggregate of aluminum hydroxide or aluminum oxide having a slit-like or honeycomb-like structure is produced. Method.
請求の範囲第３項記載の製造方法。4. The production method according to claim 3, wherein the freezing is one-way freezing.
範囲第４項記載の製造方法。5. The production method according to claim 4, wherein the freezing rate is 2.0 cm / hr or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61165302A JPH068172B2 (en) | 1986-07-14 | 1986-07-14 | Aggregate of slit-like or honeycomb-like structure of aluminum hydroxide or aluminum oxide and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61165302A JPH068172B2 (en) | 1986-07-14 | 1986-07-14 | Aggregate of slit-like or honeycomb-like structure of aluminum hydroxide or aluminum oxide and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6321219A JPS6321219A (en) | 1988-01-28 |
| JPH068172B2 true JPH068172B2 (en) | 1994-02-02 |
Family
ID=15809749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61165302A Expired - Lifetime JPH068172B2 (en) | 1986-07-14 | 1986-07-14 | Aggregate of slit-like or honeycomb-like structure of aluminum hydroxide or aluminum oxide and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH068172B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4245360A1 (en) | 2022-03-16 | 2023-09-20 | Ushio Denki Kabushiki Kaisha | Ultraviolet light irradiation device |
| EP4252785A1 (en) | 2022-03-30 | 2023-10-04 | Ushio Denki Kabushiki Kaisha | Ultraviolet irradiation device |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312791A (en) * | 1992-08-21 | 1994-05-17 | Saint Gobain/Norton Industrial Ceramics Corp. | Process for the preparation of ceramic flakes, fibers, and grains from ceramic sols |
| WO2006041170A1 (en) * | 2004-10-15 | 2006-04-20 | Ngk Insulators, Ltd. | Method for producing porous structure |
| JP5055520B2 (en) * | 2006-02-24 | 2012-10-24 | 独立行政法人産業技術総合研究所 | Porous structure and method for producing the same |
| ES2716223T3 (en) * | 2007-03-12 | 2019-06-11 | Kuraray Co | Production method of a porous ceramic material |
| FR2984882A1 (en) * | 2011-12-23 | 2013-06-28 | Saint Gobain Ct Recherches | PROCESS FOR PRODUCING A MESOPOROUS PRODUCT |
-
1986
- 1986-07-14 JP JP61165302A patent/JPH068172B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4245360A1 (en) | 2022-03-16 | 2023-09-20 | Ushio Denki Kabushiki Kaisha | Ultraviolet light irradiation device |
| EP4252785A1 (en) | 2022-03-30 | 2023-10-04 | Ushio Denki Kabushiki Kaisha | Ultraviolet irradiation device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6321219A (en) | 1988-01-28 |
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