JPS6321219A - Slit or honeycomb aggregate of aluminum hydroxide or aluminum oxide and its production - Google Patents
Slit or honeycomb aggregate of aluminum hydroxide or aluminum oxide and its productionInfo
- Publication number
- JPS6321219A JPS6321219A JP61165302A JP16530286A JPS6321219A JP S6321219 A JPS6321219 A JP S6321219A JP 61165302 A JP61165302 A JP 61165302A JP 16530286 A JP16530286 A JP 16530286A JP S6321219 A JPS6321219 A JP S6321219A
- Authority
- JP
- Japan
- Prior art keywords
- aggregate
- slit
- aluminum hydroxide
- honeycomb
- 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.)
- Granted
Links
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 title claims abstract description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000007710 freezing Methods 0.000 claims abstract description 11
- 230000008014 freezing Effects 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 5
- 238000004220 aggregation Methods 0.000 claims 1
- 230000002776 aggregation Effects 0.000 claims 1
- 239000011800 void material Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 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
- 238000001704 evaporation Methods 0.000 description 4
- 239000007788 liquid 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 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
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 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
- 239000000126 substance Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 208000010513 Stupor Diseases 0.000 description 1
- 239000002156 adsorbate 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
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011819 refractory material Substances 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
Abstract
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（粉）状体を提供することを目的と
する。Detailed Description of the Invention [Industrial Application Field] The present invention provides a novel slit-like or honeycomb-like aggregate of aluminum hydroxide or aluminum oxide that is assembled into a thin plate shape and has specific regular pores, and Regarding the manufacturing method, the object of the present invention is to provide a novel alumina granule (powder) that can be used as an adsorbent, a catalyst, a powder for cosmetics, and the like.
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。Conventionally, alumina or its hydrates have been widely used in various industries as adsorbents, desiccants, catalysts, etc. in the form of powders, lumps, crushed forms, tablets, etc., taking advantage of their adsorption ability. It is also widely used in refractories, pigment carriers, medicines, cosmetics, etc.
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４０〜１
００人であり、細孔は不規則においている。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 the porosity is usually 0.4 to 0.
．． 7. Apparent specific gravity is about 0.8-2, average pore diameter is 40-1
00, and the pores are irregularly arranged.
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−ヒ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。When using aluminum hydroxide or aluminum oxide as an adsorbent, catalyst, etc., the efficiency is higher when the specific surface area is larger. However, when aluminum hydroxide or aluminum oxide is atomized, the particles become densely packed, which reduces the permeability of substances that require adsorbents and catalysts, resulting in a shape that is unsuitable when rapid work is expected. I can say it. Therefore, methods have been used to improve the flow permeability by forming the honeycomb into a honeycomb-like shape, but the ones currently available have a wall thickness of 0.1 mm or more and a pore diameter of 1 mm. This is a large shape, and the contact efficiency decreases. Therefore, in order to increase the contact efficiency by quickly circulating and permeating substances that have a high contact area and require adsorbates or catalysts, the shape of aluminum hydroxide or aluminum oxide should be honeycomb-like or slit-like, and the specific surface area should be It is presumed that it is preferable to have a narrow wall thickness and a narrow pore width so as to spread out, but an aggregate of such a shape or a manufacturing method thereof is not known at all.
そこで本発明者らは、ゾル−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永和物凝集体を
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 conducting research on the preparation of aluminum hydroxide fine particles by the sol-gel method, the present inventors discovered that by freeze-drying aluminum hydroxide sol or gel under certain conditions, alumina permanent particles having specific regular pores were obtained. It has been found that it is possible to produce aggregates, and that by firing the aggregates, corresponding alumina aggregates can be produced.
本発明によれば壁厚が０．０１μＩｌｌ〜１５μｍ、空
孔の幅乃至平均直径が１μ１１〜５０μｍで、深さが１
０μｍ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, the wall thickness is 0.01μIll to 15μm, the width or average diameter of the pores is 1μ11 to 50μm, and the depth is 1μIll to 15μm.
A honeycomb-like or slit-like aggregate of 0 μm or more is provided.
即ち本発明は、下記の（１）及び（又は）（２）の構造
を有し、次の一般弐Ｎ）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 following structures (1) and (or) (2), and is an aggregate of slit-like or honeycomb-like structures of aluminum hydroxide or aluminum oxide, which is represented by the following general 2N). It is related.
＾１２０３・ｎ１Ｌｔｏ （１）（ｎはＯ
〜３．５）
（１１平均厚みが０．０１μＩ１１〜１５μｍ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、ＡＩｔ
ｏ３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。^1203・n1Lto (1) (n is O
~3.5) (11 A plurality of thin wall plates A having an average thickness of 0.01μI11 to 15μm are overlapped in approximately the same direction at intervals of 1μM to 50μm, and the gaps are formed in places by thin walls having approximately the same thickness as the thin wall plates A. Board B
(2) A honeycomb-like structure consisting of a thin wall portion with an average thickness of 0.01 μm to 15 μm and pores with an average diameter of 1 μm to 50 μm surrounded by the slit-like structure partitioned by (2) The present invention also relates to the production of the above novel aggregate. As a method, AIt
An aqueous dispersion of aluminum hydroxide or aluminum oxide with a concentration of 0.1 to 20% by weight as O3 and a pH of 1 to 7 is frozen at -4°C to -200°C and then left in a 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, characterized by forming an aggregate by evaporating water or further firing the aggregate. be.
本発明の製造方法の好ましい実施態様によれば、Ａｌｚ
（ｈ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（１）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
２ ｃｍ／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。According to a preferred embodiment of the production method of the present invention, Alz
(The concentration as h is 0.1 to 20% by weight and the pH is 1.
An aqueous dispersion of aluminum hydroxide or aluminum oxide represented by the above formula (1), which is Aggregates are formed by evaporating water.
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せることにより、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。In addition, by firing the aggregate to form a fired aggregate, if necessary, the desired slit-like or/and honeycomb-like aggregate can be 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 made into any desired shape from agglomerates to granules and powders. That is, the slit-like or honeycomb-like agglomerated structure characteristic of the aggregate of the present invention is maintained by crushing the block alumina hydrate obtained by freeze-drying or the block alumina (hydrate) obtained by further firing. The desired particle size can be as small 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．
ＩＩＩｍ ”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 characteristics of the particles of the present invention include, as described above, a pore size of 0.
IIIm “15 μm regular honeycomb-like pores and/or
Or, it is an alumina (hydrate) aggregate having a structure having slit-like pores.
上記（Ｉ）式中、１モルのＡｈＯｓに対する水分子のモ
ル数であるｎはＯ〜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、Δ１２０３１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、ｐｎを
７以下にするが、特に高い分散性を得るためにはｐｔ＋
を４以下に調整することが好ましい。In the above formula (I), n, which is the number of moles of water molecules per 1 mole of AhOs, is 0 to 3.5 (value after drying at 100°C for 24 hours), especially when the number of moles n is 1. 6-2.0
It is preferable from the viewpoint of high dispersibility in an aqueous solution during production. Such, 1.6 to Δ12031 mole
Boehmite is an aluminum hydroxide with 2.0 moles of water molecules. In the production method of the present invention, in order to obtain an aqueous dispersion of aluminum hydroxide or aluminum oxide, for example, an aqueous acid solution such as hydrochloric acid, nitric acid, or acetic acid is added to adjust the pn to 7 or less. To get pt+
is preferably adjusted to 4 or less.
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、ＡＩｔＯ：ｒ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、−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２ ｃｍ／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ｌ Ｔｏｒｒ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。The concentration of aluminum hydroxide or aluminum oxide in the aqueous solution is the weight concentration as AItO:r of 0.1 to 20.
Weight%. If it is less than 0.1% by weight, continuous slits or thin walls of the honeycomb cannot be obtained, and if it is more than 20% by weight, the thickness of the thin walls will become greater than 15 μm, which is not preferable. The state of the dispersion obtained at this time is preferably a sol or a gel. After this dispersion is injected into a cylindrical tube, it is placed in a refrigerant at -4°C to -200°C and frozen. As the refrigerant at this time, for example, dry ice/acetone liquid, liquid nitrogen, ice/water liquid, etc. can be used. In freezing this dispersion, the cylindrical tube is lowered into the medium at a constant rate toward the bottom, i.e., the unidirectional freezing method is preferred in order to deepen the pores in the slit-like or honeycomb-like structure in a fixed direction. The injection rate, ie, the freezing rate, is particularly preferably 2 cm/hr or more. Thereafter, moisture is evaporated from the frozen product in a frozen state, for example, by suctioning the moisture under vacuum. The degree of vacuum at this time is preferably 1 Torr or less. The desired slit-like or honeycomb-like structure is obtained by this water evaporation. The structure produced at this time may be fired at a temperature higher than room temperature, whereby it can be converted into, for example, δ-alumina, θ-alumina, α-alumina, and 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。Due to its regular pore structure, the novel alumina or its hydrate particles or powder of the present invention have good contact efficiency when used as an adsorbent, etc., and can be used as a powder in cosmetics, etc. When mixed, it is a powder that is slippery and has an excellent feel, and can exhibit excellent performance in a variety of 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の詳細な説明するが、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 of manufacturing a slit-like 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
（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’Ｃで３５００ｒｐｍ
の速度で攪拌しながら、加水分解を行った。Example 1 Using aluminum isopropoxide (manufactured by Tokyo Kasei), 100 mol of redistilled water was added to 1 mol of this raw material, and the mixture was heated at 3500 rpm at a temperature of 90'C.
Hydrolysis was carried out while stirring at a speed of .
この溶液にＩＮの塩酸を加え、ｐｎを４に調製した。IN hydrochloric acid was added to this solution to adjust pn to 4.
この溶液に蒸留水を加え、ＡＩｔＯ３の濃度を１重量％
にした後、直径ＩＣＩ１１％深さ５０Ｉ１１のプラスチ
ック製のシリンダー状管に注入し、この管をアセトンと
ドライアイスからなる一７８℃の冷媒中に５ ｃｍ／ｈ
ｒの速度で降下させ、分散液を下から上に向は一方向に
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０．１μｍ１空孔の幅
５μｍ、深さ最大５ｃｎ＋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Ｊ
ＳＭ−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−５型、ＣｕＫα線）による同定によれば擬ベーマ
イトであった。Distilled water was added to this solution to bring the concentration of AItO3 to 1% by weight.
After cooling, the tube was injected into a plastic cylindrical tube with a diameter of ICI 11% and a depth of 50I11, and the tube was heated at 5 cm/h in a refrigerant of acetone and dry ice at -78℃.
The dispersion was unidirectionally frozen from bottom to top. The frozen product was kept frozen in a cylindrical tube and dried for 2 days under high vacuum (0.05 Torr). By this freeze-drying, a slit-like structure with a thin wall thickness of 0.1 μm, 1 pore width of 5 μm, and a maximum depth of 5 cn+ was obtained. Scanning electron micrograph of this structure (JEOL J
SM-840) is shown in FIG. The crystal structure of this structure was identified as pseudo-boehmite by powder X-ray diffraction method (Geigerflex manufactured by Rigaku Denki Kogyo, D-5 type, CuKα radiation).
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ＡｈＯ８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, after the concentration of AhO8 was made 12% by weight by concentrating the dispersion after hydrolysis,
When produced in the same manner by freezing and water evaporation, a honeycomb-like structure with a wall thickness 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／ １２ ’４度のＡｌＣｌ３ ・６８２
０溶液４００ｍ１に１．２５ｍｏｌ／ ｌ１ＮａＯＨ溶
液４００ｍ１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ｐｏ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０．２μｍ、空孔の幅５μｍ、深さ最大５ｃ
ｆｆｌのスリット状の構造が得られた。Example 3 0.5 mol/12'4 degree AlCl3 ・682
Add 400 ml of 1.25 mol/l1 NaOH solution to 400 ml of 0 solution to form a white precipitate of aluminum hydroxide. Next, this precipitate is heated as it is to 80° C. together with the mother liquor, and the state is maintained for 90 minutes to deflocculate, resulting in a colorless and transparent sol (po of the sol is 4.02). This sol was poured into a plastic cylindrical tube with a diameter of 1 cm and a depth of 5 cm, and freeze-dried in the same manner as in Example 1.
Thin wall thickness 0.2μm, hole width 5μm, maximum depth 5c
A slit-like structure of ffl was obtained.
実施例４
実施例１の方法で＾１，０３の濃度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 After preparing a dispersion of ^1,03 with a concentration of 12% by weight using the method of Example 1, it was frozen using liquid nitrogen as a refrigerant and water evaporated. Hole width 3μm
, a honeycomb-like structure with a maximum depth of 3 cm was obtained.
実施例５
実施例１の方法で＾１２０３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、以下間、 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５ｃｍのノ＼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 After preparing a dispersion of ^1203 at a concentration of 12% by weight using the method of Example 1, it was poured into a plastic cylindrical tube with a diameter of 3 cm and a depth of 5 cm, and freeze-dried in the following manner. As a result, a mixed structure of a nicum-like structure and a slit-like structure with a thin wall thickness of 0.5 μm, a hole width of 3 μm, and a maximum depth of 5 cm was obtained.
実施例６
実施例１の方法で製造したスリ・ノド状構造体を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−八へｔ０３に変化
した。Example 6 When the slit-shaped structure produced by the method of Example 1 was heated to 550°C at a heating rate of 1°C per minute, the slit-like structure remained unchanged and the composition changed to δ-8 to t03. It changed to
実施例７
実施例２の方法で製造したノ＼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−八へ２０３に
変化した。Example 7 When the No\Nicum-like structure produced by the method of Example 2 was heated to 1200°C at a heating rate of 1°C per minute,
The honeycomb-like structure remained unchanged, but the composition changed to α-8 to 203.
第１図は実施例１で得られた本発明のスリ・ノド状集合
体の走査型顕微鏡写真（倍率ｉ ４００）、第２図は実
施例２で得られた本発明のノ＼ニカム様集合体の走査型
顕微鏡写真（倍率； ４００）である。
第 １ 図
第 ２ 図
ス呆≦奪基ａ４
一９謬昏■仏
一−′″洋謙闇醪利洟蝕
、−，４だコら渾七−を岬１
〜寥り一表際融ｄ
〜−−−鴻ミ（田頃迦
８婦・′−３，２．２−う、う
１Ｐ
ｔ＝夕ニ梠贋夕
手続主甫”ｉＴＦ書（方式）
昭和６１年１０月１３日FIG. 1 is a scanning micrograph (magnification i 400) of the pickpocket-like aggregate of the present invention obtained in Example 1, and FIG. This is a scanning micrograph (magnification: 400) of the body. 1st figure 2nd figure Sudama≦Kaiki a4 19th stupor■Buddha 1-'''Western Ken's Darkness, Liquor Eclipse,-,4. ～---Koumi (Tagoroka 8fu・'-3,2.2-U,U1P t=Yuuni 梠补认评甫”iTF document (method) October 13, 1985
Claims (1)
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。 Ａｌ＿２Ｏ＿３・ｎＨ＿２Ｏ（ 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 ２ 集合体が粒状である特許請求の範囲第１項記載の集
合体。 ３ Ａｌ＿２Ｏ＿３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。 ４ 凍結が一方向凍結法による凍結である特許請求の範
囲第３項記載の製造方法。 ５ 凍結速度が２．０ｃｍ／ｈｒ以上である特許請求の
範囲第４項記載の製造方法。[Scope of Claims] 1 A slit-like or honeycomb-like structure of aluminum hydroxide or aluminum oxide, which has the following structures (1) and (or) (2) and is represented by the following general formula (I). Aggregation. Al_2O_3・nH_2O(I) (n is 0 to 3.5) (1) A plurality of thin wall plates A with an average thickness of 0.01 μm to 15 μm are overlapped in approximately the same direction at intervals of 1 μm to 50 μm,
The void has a slit-like structure that is partitioned in places by thin-walled plates B, which have approximately the same thickness as thin-walled plates A. Honeycomb-like structure composed of pores 2. The aggregate according to claim 1, wherein the aggregate is granular. 3 Concentration as Al_2O_3 is 0.1 to 20% by weight
Then, an aqueous dispersion of aluminum hydroxide or aluminum oxide with a pH of 1 to 7 is frozen at -4°C to -200°C, and then water is evaporated in the frozen state to form aggregates. A method for producing an aggregate of aluminum hydroxide or aluminum oxide having a slit-like or honeycomb-like structure, the method comprising: or further firing the aggregate. 4. The manufacturing method according to claim 3, wherein the freezing is performed by a unidirectional freezing method. 5. The manufacturing 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 true JPS6321219A (en) | 1988-01-28 |
| JPH068172B2 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279095A (en) * | 1992-08-21 | 1994-10-04 | Saint Gobain Norton Ind Ceramics Corp | Method for manufacture of ceramic substance and product thereof |
| WO2006041170A1 (en) * | 2004-10-15 | 2006-04-20 | Ngk Insulators, Ltd. | Method for producing porous structure |
| JP2007223856A (en) * | 2006-02-24 | 2007-09-06 | National Institute Of Advanced Industrial & Technology | Porous structure and its manufacturing method |
| US8524128B2 (en) | 2007-03-12 | 2013-09-03 | Kuraray Co., Ltd. | Method for production of porous ceramic material |
| JP2015508378A (en) * | 2011-12-23 | 2015-03-19 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Process for producing mesoporous products |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023135750A (en) | 2022-03-16 | 2023-09-29 | ウシオ電機株式会社 | Ultraviolet light irradiation device |
| JP2023147372A (en) | 2022-03-30 | 2023-10-13 | ウシオ電機株式会社 | Ultraviolet light irradiation device |
-
1986
- 1986-07-14 JP JP61165302A patent/JPH068172B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279095A (en) * | 1992-08-21 | 1994-10-04 | Saint Gobain Norton Ind Ceramics Corp | Method for manufacture of ceramic substance and product thereof |
| WO2006041170A1 (en) * | 2004-10-15 | 2006-04-20 | Ngk Insulators, Ltd. | Method for producing porous structure |
| JPWO2006041170A1 (en) * | 2004-10-15 | 2008-05-22 | 日本碍子株式会社 | Method for producing porous structure |
| JP5098333B2 (en) * | 2004-10-15 | 2012-12-12 | 日本碍子株式会社 | Method for producing porous structure |
| JP2007223856A (en) * | 2006-02-24 | 2007-09-06 | National Institute Of Advanced Industrial & Technology | Porous structure and its manufacturing method |
| US8524128B2 (en) | 2007-03-12 | 2013-09-03 | Kuraray Co., Ltd. | Method for production of porous ceramic material |
| JP5313872B2 (en) * | 2007-03-12 | 2013-10-09 | 株式会社クラレ | Method for producing porous ceramic material |
| JP2015508378A (en) * | 2011-12-23 | 2015-03-19 | サン−ゴバン サントル ド レシェルシュ エ デテュド ユーロペアン | Process for producing mesoporous products |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH068172B2 (en) | 1994-02-02 |
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