JP2000203829A - Porous activated alumina and its production - Google Patents
Porous activated alumina and its productionInfo
- Publication number
- JP2000203829A JP2000203829A JP11007542A JP754299A JP2000203829A JP 2000203829 A JP2000203829 A JP 2000203829A JP 11007542 A JP11007542 A JP 11007542A JP 754299 A JP754299 A JP 754299A JP 2000203829 A JP2000203829 A JP 2000203829A
- Authority
- JP
- Japan
- Prior art keywords
- activated alumina
- aqueous solution
- pore diameter
- alumina
- distribution curve
- 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.)
- Pending
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 93
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 50
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 11
- -1 aluminum compound Chemical class 0.000 claims abstract description 8
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 101150035983 str1 gene Proteins 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000010304 firing Methods 0.000 description 36
- 239000000499 gel Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 102100033040 Carbonic anhydrase 12 Human genes 0.000 description 1
- 101000867855 Homo sapiens Carbonic anhydrase 12 Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- LCQXXBOSCBRNNT-UHFFFAOYSA-K ammonium aluminium sulfate Chemical compound [NH4+].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCQXXBOSCBRNNT-UHFFFAOYSA-K 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は活性アルミナ及びそ
の製造方法に関し、更に詳細には内部に多数の細孔が形
成された多孔質の活性アルミナ、及び活性アルミナの細
孔径を調整し得る活性アルミナの製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an activated alumina and a method for producing the same, and more particularly, to a porous activated alumina having a large number of pores formed therein, and an activated alumina capable of adjusting the pore diameter of the activated alumina. And a method for producing the same.
【０００２】[0002]
【従来の技術】アルミナは、耐熱性が高く、化学的安定
性、耐薬品性に優れており、種々の工業用途に用いられ
ている。特に内部に多数の細孔が形成された多孔質の活
性アルミナは、大きな比表面積が形成されるため、各種
の気体・液体を吸着する吸着能を有し、触媒の担体、フ
ィルタ、吸着剤、或いは乾燥剤等の多くの分野に利用さ
れている。かかる活性アルミナは、従来、水酸化アルミ
ニウム（バイヤライト、ベーマイト、ギブサイト等）、
アルミニウムアルコキシド、アンモニウムミョウバン等
の原料を焼成することによって製造されている。2. Description of the Related Art Alumina has high heat resistance, excellent chemical stability and chemical resistance, and is used for various industrial applications. In particular, porous activated alumina having a large number of pores formed therein has a large specific surface area, and therefore has an adsorption ability to adsorb various gases and liquids, and a catalyst carrier, a filter, an adsorbent, Alternatively, it is used in many fields such as desiccants. Conventionally, such activated aluminas include aluminum hydroxide (such as bayerite, boehmite, and gibbsite),
It is manufactured by firing raw materials such as aluminum alkoxide and ammonium alum.
【０００３】[0003]
【発明が解決しようとする課題】ところで、前述した種
々の分野において活性アルミナを用いる場合には、吸着
または分離する気体等の分子に適合した、細孔径、細孔
容積等の活性アルミナを用いる必要がある。このため、
従来では、活性アルミナの製造方法において、母塩結
晶、前駆体、或いは製造条件を変えることによって、比
表面積を調整した活性アルミナを得ることはできる。し
かし、従来の製法によって得られた活性アルミナは、そ
の細孔径の分布曲線はブロードであったり、細孔の分布
曲線が２つ又はそれ以上のピークを持つ等、細孔径を精
密に制御することは困難である。そこで、本発明の課題
は、細孔径の分布曲線が単一で、かつ、５〜３０ｎｍの
範囲で任意に細孔径を制御した活性アルミナを提供する
こと、及び細孔径等の細孔特性を調整し得る活性アルミ
ナの製造方法を提供することにある。In the case where activated alumina is used in the various fields mentioned above, it is necessary to use activated alumina having a pore diameter and a pore volume suitable for molecules of gas or the like to be adsorbed or separated. There is. For this reason,
Conventionally, in a method for producing activated alumina, it is possible to obtain activated alumina whose specific surface area is adjusted by changing a mother salt crystal, a precursor, or production conditions. However, the activated alumina obtained by the conventional manufacturing method has a pore diameter distribution curve that is broad, and the pore distribution curve has two or more peaks. It is difficult. Therefore, an object of the present invention is to provide an activated alumina having a single pore diameter distribution curve and having an arbitrary controlled pore diameter in the range of 5 to 30 nm, and adjusting pore properties such as the pore diameter. It is an object of the present invention to provide a method for producing activated alumina.
【０００４】[0004]
【課題を解決するための手段】本発明者は、前記課題を
解決すべく検討を重ねた結果、塩基性塩化アルミニウム
水溶液に陽イオン性界面活性剤であるアルキルトリメチ
ルアンモニウムクロライドを添加した水溶液を水熱処理
し、得られた水溶液をゲル化した後、ゲル化物を焼成す
ることによって活性アルミナを得るとともに活性アルミ
ナに形成された細孔の分布は単一の分布を示すこと、お
よび添加する有機化合物の種類やゲル化物の焼成温度を
変更することによって、得られる活性アルミナの細孔径
を変更できることを見出し、本発明に到達した。すなわ
ち本発明は、内部に多数の細孔が形成された多孔質の活
性アルミナにおいて、該活性アルミナに形成された細孔
径の分布曲線が、単一ピークの分布曲線であって、前記
分布曲線がピークとなる細孔径が５ｎｍ以上、３０ｎｍ
以下であることを特徴とする活性アルミナにある。ま
た、本発明は、アルミニウム化合物を焼成して内部に多
数の細孔が形成された多孔質活性アルミナを製造する際
に、該アルミニウム化合物として用いた塩基性塩化アル
ミニウム水溶液に水溶性の有機化合物を添加した後、水
熱処理し、次いで、得られた塩基性塩化アルミニウム水
溶液をゲル化し、得られたゲル化物を、前記ゲル化物中
に残留する前記水溶性有機化合物の熱分解温度以上の温
度で焼成して活性アルミナとすることを特徴とする活性
アルミナの製造方法にある。Means for Solving the Problems As a result of repeated studies to solve the above-mentioned problems, the present inventor has found that an aqueous solution obtained by adding an alkyltrimethylammonium chloride, which is a cationic surfactant, to a basic aluminum chloride aqueous solution is added to water. After the heat treatment, the resulting aqueous solution is gelled, and the gelled material is calcined to obtain activated alumina, and that the distribution of pores formed in activated alumina shows a single distribution, and that the organic compound to be added is The inventors have found that the pore diameter of the obtained activated alumina can be changed by changing the kind and the firing temperature of the gelled product, and have reached the present invention. That is, the present invention provides a porous activated alumina having a large number of pores formed therein, wherein the distribution curve of the pore diameter formed in the activated alumina is a single-peak distribution curve, and the distribution curve is The peak pore diameter is 5 nm or more, 30 nm
Activated alumina characterized by the following. Further, the present invention, when producing a porous activated alumina having a large number of pores formed therein by calcining an aluminum compound, a water-soluble organic compound is added to the basic aluminum chloride aqueous solution used as the aluminum compound. After the addition, hydrothermal treatment is performed, and then the obtained basic aluminum chloride aqueous solution is gelled, and the obtained gelled substance is calcined at a temperature not lower than the thermal decomposition temperature of the water-soluble organic compound remaining in the gelled substance. To produce activated alumina.
【０００５】本発明に係わる活性アルミナは、その細孔
径の分布曲線が、単一ピークの分布曲線であって、この
分布曲線がピークとなる細孔径が５ｎｍ以上、３０ｎｍ
以下となるものである。また、本発明に係わる活性アル
ミナの製造方法によれば、透光性を有したシート状、フ
レーク状、顆粒状、および粉末状の活性アルミナを得る
ことができる。しかも、本発明の製造方法では添加する
水溶性有機化合物の種類や添加量を変更すること、又は
得られたゲル化物の焼成温度を変更することによって、
得られる活性アルミナの細孔径などの細孔特性を容易に
制御することができる。In the activated alumina according to the present invention, the pore diameter distribution curve is a single peak distribution curve, and the pore diameter at which this distribution curve peaks is 5 nm or more and 30 nm or less.
It is as follows. Further, according to the method for producing activated alumina according to the present invention, translucent sheet, flake, granular, and powdered activated alumina can be obtained. Moreover, in the production method of the present invention, by changing the type and amount of the water-soluble organic compound to be added, or by changing the firing temperature of the obtained gelled product,
The pore characteristics such as the pore diameter of the obtained activated alumina can be easily controlled.
【０００６】[0006]
【発明実施の形態】本発明に係わる活性アルミナに形成
された細孔径の分布曲線は、単一ピークの分布曲線であ
る。この分布曲線は、そのピークとなる細孔径が５ｎｍ
以上、３０ｎｍ以下であり、この範囲内でピークとなる
細孔径を任意に変化させることができる。本発明に係わ
る微細で均斉な細孔が形成された活性アルミナから成る
シート、フレーク状粒子、顆粒状粒子、又は粉末状粒子
は、実質的に透光性を呈するものである。ここで「実質
的に透光性を有する」とは、活性アルミナのシート、フ
レーク、顆粒、粉末を、肉眼又は光学顕微鏡で観察した
とき、実質的に透光性を示すことをいい、具体的には図
３に示したような透過率曲線を与えることをいう。かか
る活性アルミナは、結晶形がγアルミナ又はθアルミナ
であることが好ましい。ここで、高圧ナトリウムランプ
等に用いられている発光管は、透光性アルミナとしての
αアルミナによって形成されているが、αアルミナ発光
管は緻密な焼結体であるため、本発明に係わる多孔質の
活性アルミナとは別異のものである。この様に、微細で
均斉な細孔が形成されている本発明に係わる活性アルミ
ナにおいて、その比表面積は５０〜３００ｍ２／ｇの範
囲にあり、細孔容積は０．１〜１．０ｃｍ３／ｇの範囲
にある。この比表面積の値は、液体窒素温度下の試料に
窒素ガスを吸着させ、その吸着量と窒素ガス分子の占有
面積から比表面積を測定するBET法によって求めたもの
であり、また、細孔容積の値は、窒素ガス吸着によって
求めた細孔直径１．７〜３００ｎｍの細孔範囲のもので
ある。BEST MODE FOR CARRYING OUT THE INVENTION The distribution curve of the pore diameter formed in the activated alumina according to the present invention is a single peak distribution curve. This distribution curve has a peak pore diameter of 5 nm.
As described above, the diameter is 30 nm or less, and the pore diameter serving as a peak within this range can be arbitrarily changed. The sheet, flake-like particles, granule-like particles, or powder-like particles of activated alumina having fine and uniform pores according to the present invention exhibit substantially light-transmitting properties. Here, "substantially translucent" means that activated alumina sheets, flakes, granules, and powders are substantially translucent when observed with the naked eye or an optical microscope. Means giving a transmittance curve as shown in FIG. Such activated alumina preferably has a crystal form of γ-alumina or θ-alumina. Here, the arc tube used for a high-pressure sodium lamp or the like is formed of α-alumina as a translucent alumina. However, since the α-alumina arc tube is a dense sintered body, It is distinct from high quality activated alumina. As described above, in the activated alumina according to the present invention in which fine and uniform pores are formed, the specific surface area is in the range of 50 to 300 m 2 / g, and the pore volume is 0.1 to 1.0 cm 3. / G. The value of this specific surface area was obtained by a BET method in which nitrogen gas was adsorbed on a sample under the temperature of liquid nitrogen and the specific surface area was measured from the amount of adsorption and the occupied area of nitrogen gas molecules. Is in the range of pores having pore diameters of 1.7 to 300 nm determined by nitrogen gas adsorption.
【０００７】本発明に係わる活性アルミナは、原料とし
て用いた塩基性塩化アルミニウム水溶液に水溶性の有機
化合物を添加した後、水熱処理し、次いで、得られた塩
基性塩化アルミニウム水溶液をゲル化し、得られたゲル
化物を、前記ゲル化物中に残留する前記水溶性有機化合
物の熱分解温度以上の温度で焼成することによって得る
ことができる。ここで、原料として用いる塩基性塩化ア
ルミニウム水溶液としては、ＯＨ／Ａｌモル比が２〜
２．７の範囲にある塩基性塩化アルミニウム水溶液、具
体的には下記〔化２〕に示す塩基性塩化アルミニウム水
溶液が好適である。The activated alumina according to the present invention is obtained by adding a water-soluble organic compound to a basic aluminum chloride aqueous solution used as a raw material, subjecting it to a hydrothermal treatment, and then gelling the resulting basic aluminum chloride aqueous solution. The obtained gelled product can be obtained by firing at a temperature not lower than the thermal decomposition temperature of the water-soluble organic compound remaining in the gelled product. Here, the basic aluminum chloride aqueous solution used as a raw material has an OH / Al molar ratio of 2 to 2.
A basic aluminum chloride aqueous solution in the range of 2.7, specifically, a basic aluminum chloride aqueous solution shown in the following [Chemical Formula 2] is preferable.
【化２】Ａｌ（ＯＨ）ＸＣｌ３−Ｘ・ｎＨ２Ｏ 但し、２．０≦Ｘ≦２．７ また、塩基性塩化アルミニウム水溶液に添加する水溶性
の有機化合物は、水溶性であり、焼成時には熱分解して
消失し得る有機化合物である。このため、水溶性を有し
ない有機化合物、或いは焼成後に残存する金属が含有さ
れている有機化合物は不適当である。本発明において用
いることができる水溶性の有機化合物としては、具体的
には、界面活性剤、ポリエチレングリコール、ポリビニ
ルアルコール、エチレングリコール、ポリアクリルアミ
ド、寒天等を挙げることができる。この界面活性剤とし
ては、第４級アンモニウム塩、具体的には、ドデシルト
リメチルアンモニウムクロライド，ヘキサデシルトリメ
チルアンモニウムクロライド，オクタデシルトリメチル
アンモニウムクロライドおよびベンジルアルキルジメチ
ルアンモニウムクロライド等を挙げることができる。か
かる水溶性の有機化合物のうち、界面活性剤、ポリエチ
レングリコール、ポリビニルアルコールを好適に用いる
ことができる。これら有機化合物の１種又は２種以上
を、塩基性塩化アルミニウム水溶液に添加することがで
き、その添加量は、塩基性塩化アルミニウム水溶液中の
アルミニウム成分を酸化アルミニウム（Al203）に換算
した換算量に対し、１０重量％以上、特に好ましくは１
０〜１２０重量％とすることが好ましい。Embedded image Al (OH) X Cl 3-X · nH 2 O where 2.0 ≦ X ≦ 2.7 Further, the water-soluble organic compound added to the basic aluminum chloride aqueous solution is water-soluble, Organic compounds that can be eliminated by thermal decomposition during firing. Therefore, an organic compound having no water solubility or an organic compound containing a metal remaining after firing is inappropriate. Specific examples of the water-soluble organic compound that can be used in the present invention include a surfactant, polyethylene glycol, polyvinyl alcohol, ethylene glycol, polyacrylamide, and agar. Examples of the surfactant include quaternary ammonium salts, specifically, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, and benzylalkyldimethylammonium chloride. Among such water-soluble organic compounds, a surfactant, polyethylene glycol, and polyvinyl alcohol can be suitably used. One or more of these organic compounds, may be added to a basic aluminum chloride aqueous solution, the amount added, the aluminum component of the basic in aluminum chloride aqueous solution in terms of aluminum oxide (Al 2 0 3) 10% by weight or more, particularly preferably 1% by weight,
The content is preferably set to 0 to 120% by weight.
【０００８】本発明では、かかる水溶性の有機化合物を
添加した塩基性塩化アルミニウム水溶液を水熱処理す
る。水熱処理温度は、１１０〜１７０℃（特に好ましく
は１２０〜１６０℃）とすることが好ましい。次いで、
得られた塩基性塩化アルミニウムをゲル化する。このゲ
ル化温度は、室温〜７０℃とすることが好ましい。次い
で、得られたゲル化物を焼成する。この焼成の際に、塩
基性塩化アルミニウムや添加した有機化合物を熱分解し
つつ所定の焼成温度まで昇温し、所定の焼成温度で所定
時間保持することによって活性アルミナを得ることがで
きる。かかる焼成条件としては、焼成温度までの昇温速
度を３０〜５００℃／Ｈｒとし、焼成温度を６００〜１
２００℃（特に好ましくは６５０〜１１５０℃）とする
ことが好ましい。なお、１２５０℃以上の温度で焼成す
ると活性の乏しいαアルミナに相転移し、比表面積、細
孔容積が減少するとともに透光性が消失する。この様に
して得られた活性アルミナは、実質的に透光性を呈する
ものであり、用途に合わせてシート状、顆粒状、粉末状
にすることができる。それらの細孔径分布は、その形状
に係わらず、単一の分布曲線となる。In the present invention, a basic aluminum chloride aqueous solution to which such a water-soluble organic compound is added is subjected to hydrothermal treatment. The hydrothermal treatment temperature is preferably 110 to 170 ° C (particularly preferably 120 to 160 ° C). Then
The obtained basic aluminum chloride is gelled. The gelation temperature is preferably between room temperature and 70 ° C. Next, the obtained gel is fired. In this firing, activated alumina can be obtained by elevating the temperature to a predetermined firing temperature while thermally decomposing the basic aluminum chloride and the added organic compound and maintaining the temperature at the predetermined firing temperature for a predetermined time. As the firing conditions, the heating rate up to the firing temperature is 30 to 500 ° C./Hr, and the firing temperature is 600 to 1
The temperature is preferably 200 ° C (particularly preferably 650 to 1150 ° C). When calcined at a temperature of 1250 ° C. or more, phase transition to α-alumina having poor activity occurs, the specific surface area and the pore volume decrease, and the light transmittance disappears. The activated alumina thus obtained exhibits substantially translucency, and can be formed into a sheet, granule, or powder according to the use. Their pore size distribution is a single distribution curve regardless of its shape.
【０００９】本発明に係わる製造方法によって、微細で
かつ均斉な細孔が形成された活性アルミナを得ることが
できる理由は、以下のように推察される。すなわち、活
性アルミナに形成される細孔は、生成した結晶粒子間の
間隙に起因し、結晶粒子の大きさとその分布とが細孔径
を決定する。このため、細孔径の分布曲線を単一ピーク
とするためには、結晶粒子の大きさとその分布を均斉化
する必要がある。この様に、結晶粒子の大きさとその分
布を均斉化するためには、焼成に供する前駆体であるゲ
ル化物のゲル構造を均質とすることが重要である。すな
わち、ゲル化物の構造に欠陥や不均質箇所が存在する場
合、ゲル化物を焼成して得られる活性アルミナにゲル化
物の不均質性が反映され、得られる活性アルミナの構造
が不均質となるからである。この点、本発明において
は、塩基性塩化アルミニウム水溶液に水溶性の有機化合
物を添加することによって、有機分子と多核ヒドロキソ
アルミニウム錯体との化学的相互作用が生じ、さらに、
水熱処理を行うことによって化学的相互作用がより強固
なものとなる。この化学的相互作用に由来して均質なゲ
ル化物を形成できる。本発明では、上述したように、均
質なゲル化物を焼成工程に供するため、焼成工程におい
て、微細構造の均質性が高められた活性アルミナを得る
ことができる。The reason why activated alumina having fine and uniform pores formed by the production method according to the present invention can be obtained as follows. That is, the pores formed in the activated alumina are caused by the gaps between the generated crystal grains, and the size and distribution of the crystal grains determine the pore diameter. Therefore, in order to make the distribution curve of the pore diameter a single peak, it is necessary to equalize the size of the crystal particles and their distribution. As described above, in order to equalize the size and distribution of crystal grains, it is important to make the gel structure of the gelled product, which is the precursor to be fired, uniform. In other words, if there are defects or inhomogeneous parts in the structure of the gelled material, the heterogeneity of the gelled material is reflected in the activated alumina obtained by firing the gelled material, and the structure of the obtained activated alumina becomes heterogeneous. It is. In this regard, in the present invention, by adding a water-soluble organic compound to a basic aluminum chloride aqueous solution, a chemical interaction between an organic molecule and a polynuclear hydroxoaluminum complex occurs.
By performing the hydrothermal treatment, the chemical interaction becomes stronger. A homogeneous gel can be formed from this chemical interaction. In the present invention, as described above, since the homogeneous gelled material is subjected to the firing step, it is possible to obtain activated alumina with improved microstructure homogeneity in the firing step.
【００１０】本発明においては、添加する水溶性有機化
合物の種類、または焼成温度を変更することによって、
得られる活性アルミナの細孔径や比表面積等を調整する
ことができる。ここで、水溶性有機化合物の添加量を同
一とし、その種類を変更した場合、活性アルミナの細孔
径分布を単一に保持しつつ、細孔径などを変更すること
ができる。また、同一のゲル化物を用い、焼成温度を変
更した場合、活性アルミナの細孔径分布を単一に保持し
つつ、細孔径などを変更することができる。本発明にお
いて得られる活性アルミナは、大きな細孔容積を有して
いるため、この細孔内に酸化チタン、白金等の各種の物
質を担持させることができる。担持方法としては、例え
ば、硫酸チタニルなどのチタン塩溶液又はチタニアコロ
イドを活性アルミナの細孔内に含浸させ、得られた試料
を焼成することにより、活性アルミナ細孔内に酸化チタ
ンを生成させる方法などが挙げられる。以上、述べてき
た本発明に係わる製造方法では、焼成後に得られる活性
アルミナの形態は、シート状、フレーク状、顆粒状とな
る。なお、シート状、フレーク状の活性アルミナの厚さ
は、ゲル化物の厚さを変化させることにより、任意に変
えることができる。In the present invention, by changing the kind of the water-soluble organic compound to be added or the calcination temperature,
The pore size and specific surface area of the obtained activated alumina can be adjusted. Here, when the amount of the water-soluble organic compound to be added is the same and the type thereof is changed, the pore size and the like can be changed while maintaining the pore size distribution of activated alumina singly. In addition, when the same gelled material is used and the firing temperature is changed, the pore size and the like can be changed while maintaining the pore size distribution of activated alumina singly. Since the activated alumina obtained in the present invention has a large pore volume, various substances such as titanium oxide and platinum can be supported in these pores. As a supporting method, for example, a method in which a titanium salt solution such as titanyl sulfate or a titania colloid is impregnated in the pores of activated alumina, and the obtained sample is fired to generate titanium oxide in the activated alumina pores. And the like. In the production method according to the present invention described above, the form of activated alumina obtained after firing is a sheet, flake, or granule. The thickness of the sheet-like or flake-like activated alumina can be arbitrarily changed by changing the thickness of the gelled material.
【００１１】[0011]
【実施例】以下、実施例によって本発明を更に詳細に説
明する。ここで活性アルミナの構造解析はＸ線回折（Ｃ
ｕＫα）を用いて行い、その比表面積は前述したBET法
により測定し、細孔容積は窒素ガス吸着によって求めた
細孔直径１．７〜３００ｎｍの細孔範囲の値である。ま
た、細孔径分布は、液体窒素温度下の試料について、窒
素ガスによる吸着等温線を測定し、得られた測定値を用
いてＢＪＨ法により算出した。The present invention will be described in more detail with reference to the following examples. Here, the structural analysis of activated alumina was performed by X-ray diffraction (C
The specific surface area is measured by the above-mentioned BET method, and the pore volume is a value in the range of pores having a pore diameter of 1.7 to 300 nm obtained by nitrogen gas adsorption. The pore size distribution was calculated by a BJH method using a sample at a liquid nitrogen temperature by measuring an adsorption isotherm with a nitrogen gas and using the obtained measured value.
【００１２】（実施例１）ＯＨ／Ａｌ比が２．５であ
り、酸化アルミニウム（Al203)に換算した換算濃度が
２．０重量％相当のアルミニウム成分を含む塩基性塩化
アルミニウム水溶液に、その酸化アルミニウム（Al203)
換算濃度に対し、陽イオン性界面活性剤であるヘキサデ
シルトリメチルアンモニウムクロライド（[C16H33N(C
H3)3]Cl）を８０重量％添加した。次いでこの水溶液を
オートクレーブに入れ、撹拌しながら１５０℃で１時間
水熱処理を行った。得られた水溶液を５０℃で乾燥して
ゲル化させゲル化物を得た後、ゲル化物を１００℃／Ｈ
ｒの昇温速度で７００℃の焼成温度まで昇温し、更に７
００℃の焼成温度で１時間保持した。得られた焼成物に
ついてＸ線回折を行った結果、図１のＡに示すようにγ
アルミナであった。そのγアルミナの細孔径分布曲線を
測定した結果、図２に示す単一ピークの細孔径分布曲線
Ａとなった。細孔径分布曲線のピーク位置は８．５ｎｍ
であった。また、比表面積は２２１ｍ ２／ｇ、細孔容積
は０．４１ｃｍ３／ｇであった。(Example 1) OH / Al ratio is 2.5
Aluminum oxide (AlTwo0Three)
Basic chloride containing 2.0% by weight of aluminum component
Add the aluminum oxide (AlTwo0Three)
Hexadene, a cationic surfactant,
Siltrimethylammonium chloride ([C16H33N (C
HThree)Three] Cl) was added at 80% by weight. Then this aqueous solution
Put in an autoclave and stir at 150 ° C for 1 hour
Hydrothermal treatment was performed. The obtained aqueous solution is dried at 50 ° C.
After gelation to obtain a gelled material, the gelled material is heated at 100 ° C./H
at a heating rate of 700 r to a firing temperature of 700 ° C.
It was kept at a firing temperature of 00 ° C. for one hour. To the resulting fired product
As a result of performing X-ray diffraction on
It was alumina. The pore size distribution curve of γ-alumina
As a result of the measurement, the pore diameter distribution curve of a single peak shown in FIG.
A. The peak position of the pore size distribution curve is 8.5 nm.
Met. The specific surface area is 221m 2/ G, pore volume
Is 0.41cm3/ G.
【００１３】同一のゲル化物を１００℃／Ｈｒの昇温速
度で８５０℃の焼成温度まで昇温し、更に８５０℃の焼
成温度で１時間保持した。得られた焼成物についてＸ線
回折を行った結果、γアルミナであった。そのγアルミ
ナの細孔径分布曲線を測定した結果、図２に示す単一の
ピークの細孔径分布曲線Ｂとなった。細孔径分布曲線の
ピーク位置は１６ｎｍであった。また、比表面積は１７
５ｍ２／ｇ、細孔容積は０．８０ｃｍ３／ｇであった。The same gelled product was heated at a heating rate of 100 ° C./Hr to a firing temperature of 850 ° C., and further kept at a firing temperature of 850 ° C. for 1 hour. The obtained fired product was subjected to X-ray diffraction and found to be γ-alumina. As a result of measuring the pore diameter distribution curve of the γ-alumina, a single peak pore diameter distribution curve B shown in FIG. 2 was obtained. The peak position of the pore size distribution curve was 16 nm. The specific surface area is 17
5 m 2 / g, and the pore volume was 0.80 cm 3 / g.
【００１４】同一のゲル化物を１００℃／Ｈｒの昇温速
度で１１００℃の焼成温度まで昇温し、更に１１００℃
の焼成温度で１時間保持した。得られた焼成物について
Ｘ線回折を行った結果、図１のＢに示すようにθアルミ
ナであった。そのθアルミナの細孔径分布曲線を測定し
た結果、図２に示す単一のピークの細孔径分布曲線Ｃと
なった。細孔径分布曲線のピーク位置は２５ｎｍであっ
た。また、比表面積は７７ｍ２／ｇ、細孔容積は０．５
４ｃｍ３／ｇであった。The same gel is heated at a heating rate of 100 ° C./Hr to a firing temperature of 1100 ° C., and further heated at 1100 ° C.
At the firing temperature of 1 hour. The obtained fired product was subjected to X-ray diffraction. As a result, it was found to be θ alumina as shown in FIG. 1B. As a result of measuring the pore diameter distribution curve of the θ-alumina, a single peak pore diameter distribution curve C shown in FIG. 2 was obtained. The peak position of the pore size distribution curve was 25 nm. The specific surface area is 77 m 2 / g and the pore volume is 0.5
It was 4 cm 3 / g.
【００１５】８５０℃で焼成して得られた厚さ８０μｍ
のγアルミナの透過率曲線を図３のＡに示す。また、１
１００℃で焼成して得られた厚さ８０μｍのθアルミナ
の透過率曲線を図３のＢに示す。いずれの焼成物も可視
光領域において光線透過性があることが認められる。な
お、いずれの温度で処理した焼成物も肉眼により透光性
が確認できた。A thickness of 80 μm obtained by firing at 850 ° C.
FIG. 3A shows the transmittance curve of γ-alumina. Also, 1
FIG. 3B shows a transmittance curve of θ-alumina having a thickness of 80 μm obtained by firing at 100 ° C. It is recognized that all of the fired products have light transmittance in the visible light region. In addition, the translucency of the baked product treated at any temperature could be confirmed with the naked eye.
【００１６】（実施例２）ＯＨ／Ａｌ比が２．５であ
り、酸化アルミニウム（Al203)に換算した換算濃度が
２．０重量％相当のアルミニウム成分を含む塩基性塩化
アルミニウム水溶液に、その酸化アルミニウム（Al203)
換算濃度に対し、分子量４００のポリエチレングリコー
ル（以下、ＰＥＧ４００と称する）を８０重量％添加し
た。次いでこの水溶液をオートクレーブに入れ、撹拌し
ながら１５０℃で１時間水熱処理を行った。得られた水
溶液を５０℃で乾燥してゲル化させゲル化物を得た後、
ゲル化物を１００℃／Ｈｒの昇温速度で７００℃の焼成
温度まで昇温し、更に７００℃の焼成温度で１時間保持
した。得られた焼成物についてＸ線回折を行った結果、
γアルミナであった。そのγアルミナの細孔径分布曲線
を測定した結果、単一のピークの細孔径分布曲線とな
り、細孔分布曲線のピーク位置は６．２ｎｍであった。
また、比表面積は２２１ｍ２／ｇ、細孔容積は０．４１
ｃｍ３／ｇであった。EXAMPLE 2 A basic aluminum chloride aqueous solution containing an aluminum component having an OH / Al ratio of 2.5 and an equivalent concentration of 2.0% by weight in terms of aluminum oxide (Al 2 O 3 ) was prepared. , Its aluminum oxide (Al 2 O 3 )
80% by weight of polyethylene glycol having a molecular weight of 400 (hereinafter referred to as PEG400) was added to the reduced concentration. Next, this aqueous solution was placed in an autoclave, and subjected to hydrothermal treatment at 150 ° C. for 1 hour while stirring. After drying the obtained aqueous solution at 50 ° C. to form a gel, a gel is obtained.
The gelled product was heated at a heating rate of 100 ° C./Hr to a firing temperature of 700 ° C., and further kept at a firing temperature of 700 ° C. for 1 hour. As a result of performing X-ray diffraction on the obtained fired product,
It was gamma alumina. As a result of measuring the pore diameter distribution curve of the γ-alumina, the pore diameter distribution curve was a single peak, and the peak position of the pore distribution curve was 6.2 nm.
The specific surface area is 221 m 2 / g, and the pore volume is 0.41.
cm 3 / g.
【００１７】同一のゲル化物を１００℃／Ｈｒの昇温速
度で８５０℃の焼成温度まで昇温し、更に８５０℃の焼
成温度で１時間保持した。得られた焼成物についてＸ線
回折を行った結果、γアルミナであった。そのγアルミ
ナの細孔径分布曲線を測定した結果、単一のピークの細
孔径分布曲線となり、細孔径分布曲線のピーク位置は１
１ｎｍであった。また、比表面積は１６３ｍ２／ｇ、細
孔容積は０．４９ｃｍ ３／ｇであった。なお、いずれの
温度で処理した焼成物も実施例１と同等の透光性を示し
た。The same gel is heated at a rate of 100 ° C./Hr.
Temperature to a firing temperature of 850 ° C, and then a firing temperature of 850 ° C.
It was kept at the forming temperature for 1 hour. X-ray about the obtained fired product
As a result of diffraction, it was γ-alumina. Its gamma aluminum
As a result of measuring the pore size distribution curve of
It becomes a pore size distribution curve, and the peak position of the pore size distribution curve is 1
1 nm. The specific surface area is 163m2/ G, fine
The pore volume is 0.49cm 3/ G. In addition, any
The fired product treated at the temperature also shows the same light transmittance as in Example 1.
Was.
【００１８】（実施例３）ＯＨ／Ａｌ比が２．２であ
り、酸化アルミニウム（Al203)に換算した換算濃度が
４．０重量％相当のアルミニウム成分を含む塩基性塩化
アルミニウム水溶液に、その酸化アルミニウム（Al203)
換算濃度に対し、ヘキサデシルトリメチルアンモニウム
クロライド（[C16H33N(CH3)3]Cl）を５０重量％添加し
た。次いでこの水溶液をオートクレーブに入れ、撹拌し
ながら１４０℃で１時間水熱処理を行った。得られた水
溶液を６０℃で乾燥してゲル化させゲル化物を得た後、
ゲル化物を１００℃／Ｈｒの昇温速度で８５０℃の焼成
温度まで昇温し、更に８５０℃の焼成温度で１時間保持
した。得られた焼成物についてＸ線回折を行った結果、
γアルミナであった。そのγアルミナの細孔径分布曲線
を測定した結果、単一のピークの細孔径分布曲線とな
り、細孔径分布曲線のピーク位置は８．６ｎｍであっ
た。また、比表面積は２０３ｍ２／ｇ、細孔容積は０．
５９ｃｍ３／ｇであった。なお、焼成物は実施例１と同
等の透光性を示した。[0018] (Example 3) and OH / Al ratio of 2.2, a basic aluminum chloride aqueous solution containing the conversion was reduced concentration of 4.0 wt% equivalent aluminum component in an aluminum oxide (Al 2 0 3) , Its aluminum oxide (Al 2 O 3 )
50% by weight of hexadecyltrimethylammonium chloride ([C 16 H 33 N (CH 3 ) 3 ] Cl) was added to the reduced concentration. Next, this aqueous solution was placed in an autoclave, and subjected to hydrothermal treatment at 140 ° C. for 1 hour while stirring. After drying the obtained aqueous solution at 60 ° C. to form a gel, a gel is obtained.
The gelled product was heated to a firing temperature of 850 ° C. at a heating rate of 100 ° C./Hr, and further kept at a firing temperature of 850 ° C. for 1 hour. As a result of performing X-ray diffraction on the obtained fired product,
It was gamma alumina. As a result of measuring the pore diameter distribution curve of the γ-alumina, the pore diameter distribution curve was a single peak, and the peak position of the pore diameter distribution curve was 8.6 nm. The specific surface area was 203 m 2 / g, and the pore volume was 0.2.
It was 59 cm 3 / g. The fired product showed the same light transmittance as that of Example 1.
【００１９】（実施例４）ＯＨ／Ａｌ比が２．４であ
り、酸化アルミニウム（Al203)に換算した換算濃度が
２．０重量％相当のアルミニウム成分を含む塩基性塩化
アルミニウム水溶液に、その酸化アルミニウム（Al203)
換算濃度に対し、ドデシルトリメチルアンモニウムクロ
ライド（[C12H25N(CH3)3]Cl）を８０重量％添加した。
次いでこの水溶液をオートクレーブに入れ、撹拌しなが
ら１４０℃で１時間水熱処理を行った。得られた水溶液
を樹脂製の平らなバットに入れ、４０℃で乾燥してゲル
化させ、シート状のゲル化物を得た後、シート状ゲル化
物を５０℃／Ｈｒの昇温速度で８００℃の焼成温度まで
昇温し、更に８００℃の焼成温度で１時間保持した。厚
さ４０μｍのシート状の焼成物が得られた。得られた焼
成物についてＸ線回折を行った結果、γアルミナであっ
た。そのγアルミナの細孔径分布曲線を測定した結果、
単一のピークの細孔径分布曲線となり、細孔径分布曲線
のピーク位置は７．２ｎｍであった。また、比表面積は
２４０ｍ２／ｇ、細孔容積は０．５５ｃｍ３／ｇであっ
た。得られたシート状のγアルミナは、図４に示すよう
に透光性を示した。Example 4 A basic aluminum chloride aqueous solution containing an aluminum component having an OH / Al ratio of 2.4 and an equivalent concentration of 2.0% by weight in terms of aluminum oxide (Al 2 O 3 ) was prepared. , Its aluminum oxide (Al 2 O 3 )
To reduced concentration, dodecyl trimethyl ammonium chloride ([C 12 H 25 N ( CH 3) 3] Cl) was added 80 wt%.
Next, this aqueous solution was placed in an autoclave, and subjected to hydrothermal treatment at 140 ° C. for 1 hour while stirring. The obtained aqueous solution is put in a flat vat made of resin, dried at 40 ° C. and gelled, and a sheet-like gel is obtained. , And further maintained at a firing temperature of 800 ° C. for 1 hour. A sheet-like fired product having a thickness of 40 μm was obtained. The obtained fired product was subjected to X-ray diffraction and found to be γ-alumina. As a result of measuring the pore diameter distribution curve of the γ-alumina,
The pore diameter distribution curve had a single peak, and the peak position of the pore diameter distribution curve was 7.2 nm. The specific surface area was 240 m 2 / g, and the pore volume was 0.55 cm 3 / g. The obtained sheet-like γ-alumina showed a light-transmitting property as shown in FIG.
【００２０】（実施例５）実施例４で得られたシート状
のγアルミナを酸化チタン（TiO2）に換算した換算濃度
で１２重量％相当のチタン成分を含む硫酸チタニル水溶
液に入れた後、減圧処理を行い、γアルミナの細孔内に
硫酸チタニル水溶液を含浸させた。シート状γアルミナ
を硫酸チタニル水溶液から取り出し、４０℃で乾燥させ
た後、１００℃／Ｈｒの昇温速度で７００℃の焼成温度
まで昇温し、更に７００℃の焼成温度で１時間保持し
た。得られたシート状の焼成物は、光線透過率の減少は
あるが、透光性は保持した。焼成物についてＸ線回折を
行った結果、γアルミナの回折線と共にアナタース型の
酸化チタンの回折線が認められ、γアルミナ中に酸化チ
タンが生成したことが確認された。また、焼成物中の酸
化チタンの担持量は２重量％であった。Example 5 After the sheet-like γ-alumina obtained in Example 4 was placed in an aqueous solution of titanyl sulfate containing a titanium component equivalent to 12% by weight in terms of a concentration converted to titanium oxide (TiO 2 ), A reduced pressure treatment was performed to impregnate the pores of γ-alumina with an aqueous solution of titanyl sulfate. The sheet-like γ-alumina was taken out from the aqueous solution of titanyl sulfate, dried at 40 ° C, heated to a firing temperature of 700 ° C at a heating rate of 100 ° C / Hr, and kept at a firing temperature of 700 ° C for 1 hour. Although the obtained sheet-like fired product had a decrease in light transmittance, it maintained translucency. As a result of X-ray diffraction of the fired product, diffraction lines of anatase-type titanium oxide were recognized together with diffraction lines of γ-alumina, and it was confirmed that titanium oxide was generated in γ-alumina. The amount of titanium oxide carried in the fired product was 2% by weight.
【００２１】（比較例）水酸化アルミニウム（ギブサイ
ト）を２００℃／Ｈｒの昇温速度で１１００℃の焼成温
度まで昇温し、更に１１００℃の焼成温度で１時間保持
した。粉末状粒子からなるアルミナが得られた。得られ
た粉末状粒子のＸ線回折による構造解析によれば、結晶
形はκアルミナであった。得られたκアルミナは肉眼お
よび光学顕微鏡下での観察では透光性を示さなかった。(Comparative Example) Aluminum hydroxide (gibbsite) was heated at a heating rate of 200 ° C./Hr to a firing temperature of 1100 ° C., and further kept at a firing temperature of 1100 ° C. for 1 hour. An alumina consisting of powdery particles was obtained. According to the structural analysis by X-ray diffraction of the obtained powdery particles, the crystal form was κ alumina. The obtained κ-alumina did not show translucency under the naked eye and observation under a light microscope.
【００２２】[0022]
【発明の効果】本発明によれば、細孔径の分布曲線が単
一な透光性を有した活性アルミナを得ることができ、活
性アルミナの細孔径や比表面積等の細孔特性を容易に調
整することができる。このため、フィルタ、触媒担体、
吸着剤或いは乾燥剤等に本発明に係わる活性アルミナを
用いる際に、分離又は吸着又は反応する気体等の分子に
適合した細孔径や細孔容積等の活性アルミナを容易に供
給することができる。According to the present invention, activated alumina having a single translucent pore diameter distribution curve can be obtained, and the pore characteristics such as the pore diameter and specific surface area of the activated alumina can be easily adjusted. Can be adjusted. For this reason, filters, catalyst carriers,
When the activated alumina according to the present invention is used as an adsorbent or a desiccant, the activated alumina having a pore diameter and a pore volume suitable for molecules of a gas or the like to be separated or adsorbed or reacted can be easily supplied.
【図１】本発明に係わる活性アルミナについて、結晶形
の種々の例を説明するためのグラフＡおよびＢを示す。FIG. 1 shows graphs A and B for illustrating various examples of crystal forms for activated alumina according to the present invention.
【図２】本発明に係わる活性アルミナについて、細孔径
分布の種々の例を説明するためのグラフＡ〜Ｃを示す。FIG. 2 shows graphs A to C for explaining various examples of a pore diameter distribution of the activated alumina according to the present invention.
【図３】本発明に係わる活性アルミナの光線透過率の種
々の例を説明するためのグラフＡおよびＢを示す。3 shows graphs A and B for explaining various examples of the light transmittance of the activated alumina according to the present invention. FIG.
【図４】本発明に係わる活性アルミナの一例を説明する
ための写真である。FIG. 4 is a photograph for explaining an example of activated alumina according to the present invention.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G066 AA20B AA23B AB13D AB21D AC12D AC22D AE20D BA03 BA09 BA23 BA24 BA26 BA31 BA50 FA05 FA20 FA21 FA34 4G069 AA01 AA08 AA09 BA01A BA01B BA01C BA04B BA38 EA01Y EA08 EC02Y EC03Y EC06Y EC07Y FB08 FB33 FB34 4G076 AA02 AB04 AB05 AB06 BA12 BA39 BB08 BC02 BC07 BD02 CA02 CA08 CA12 CA28 DA01 DA30 FA04 FA06 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G066 AA20B AA23B AB13D AB21D AC12D AC22D AE20D BA03 BA09 BA23 BA24 BA26 BA31 BA50 FA05 FA20 FA21 FA34 4G069 AA01 AA08 AA09 BA01A BA01B BA01C BA04B BA38 EA01 EC03 EA08 EC03 EA08 EC08 AA02 AB04 AB05 AB06 BA12 BA39 BB08 BC02 BC07 BD02 CA02 CA08 CA12 CA28 DA01 DA30 FA04 FA06
Claims (8)
活性アルミナにおいて、該活性アルミナに形成された細
孔の分布曲線が、単一ピークの分布曲線であって、前記
分布曲線がピークとなる細孔径が５ｎｍ以上、３０ｎｍ
以下であることを特徴とする活性アルミナ。1. In a porous activated alumina having a large number of pores formed therein, a distribution curve of pores formed in the activated alumina is a single peak distribution curve, and the distribution curve is The peak pore diameter is 5 nm or more, 30 nm
Activated alumina characterized by the following.
末状の活性アルミナが、実質的に透光性を有する請求項
１記載の活性アルミナ。2. The activated alumina according to claim 1, wherein the activated alumina in the form of a sheet, flakes, granules or powder has substantially translucency.
である請求項１〜２記載の活性アルミナ。3. The activated alumina according to claim 1, wherein the crystal phase of the activated alumina is a γ phase or a θ phase.
数の細孔が形成された多孔質活性アルミナを製造する際
に、該アルミニウム化合物として用いた塩基性塩化アル
ミニウム水溶液に水溶性の有機化合物を添加した後、水
熱処理し、次いで、得られた塩基性塩化アルミニウム水
溶液をゲル化し、得られたゲル化物を、前記ゲル化物中
に残留する前記水溶性有機化合物の熱分解温度以上の温
度で焼成して活性アルミナとすることを特徴とする細孔
径を調整し得る活性アルミナの製造方法。4. When an aluminum compound is fired to produce a porous activated alumina having a large number of pores formed therein, a water-soluble organic compound is added to the basic aluminum chloride aqueous solution used as the aluminum compound. Then, hydrothermal treatment, then gel the obtained basic aluminum chloride aqueous solution, the obtained gelled product is calcined at a temperature equal to or higher than the thermal decomposition temperature of the water-soluble organic compound remaining in the gelled product. A method for producing activated alumina, wherein the pore diameter can be adjusted by using activated alumina.
下記〔化１〕に示す塩基性塩化アルミニウム水溶液を用
いる請求項４記載の細孔径を調整し得る活性アルミナの
製造方法。 【化１】Ａｌ（ＯＨ）ＸＣｌ３−Ｘ・ｎＨ２Ｏ 但し、２．０≦Ｘ≦２．７5. As a basic aluminum chloride aqueous solution,
The method for producing activated alumina capable of adjusting the pore diameter according to claim 4, wherein a basic aluminum chloride aqueous solution shown in the following [Chemical Formula 1] is used. ## STR1 ## Al (OH) X Cl 3- X.nH 2 O, provided that 2.0 ≦ X ≦ 2.7
剤、ポリエチレングリコール又はポリビニルアルコール
を用いる請求項４〜５のいずれか一項記載の細孔径を調
整し得る活性アルミナの製造方法。6. The method for producing activated alumina according to claim 4, wherein a surfactant, polyethylene glycol or polyvinyl alcohol is used as the water-soluble organic compound.
塩化アルミニウム水溶液中のアルミニウム成分を酸化ア
ルミニウム（Al2O3）に換算した換算量に対し、１０重
量％以上とする請求項４〜６のいずれか一項記載の細孔
径を調整し得る活性アルミナの製造方法。7. The addition amount of the water-soluble organic compound is at least 10% by weight based on the conversion amount of aluminum component in the basic aluminum chloride aqueous solution to aluminum oxide (Al 2 O 3 ). The method for producing activated alumina according to any one of claims 1 to 6, wherein the pore diameter can be adjusted.
℃とする請求項４〜７のいずれか一項記載の細孔径を調
整し得る活性アルミナの製造方法。8. The sintering temperature of the gelled product is from 600 to 1200.
The method for producing activated alumina capable of adjusting the pore diameter according to any one of claims 4 to 7, wherein the temperature is set to ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11007542A JP2000203829A (en) | 1999-01-14 | 1999-01-14 | Porous activated alumina and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11007542A JP2000203829A (en) | 1999-01-14 | 1999-01-14 | Porous activated alumina and its production |
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| Publication Number | Publication Date |
|---|---|
| JP2000203829A true JP2000203829A (en) | 2000-07-25 |
Family
ID=11668691
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| JP (1) | JP2000203829A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2823132A1 (en) * | 2001-04-04 | 2002-10-11 | Pro Catalyse | PROCESS FOR REMOVING METAL HALIDES FROM AN ORGANIC OR NON-ORGANIC EFFLUENT, LIQUID OR GASEOUS |
| JP2003026419A (en) * | 2001-07-12 | 2003-01-29 | Taimei Chemicals Co Ltd | METHOD FOR PREPARING alpha-ALUMINA |
-
1999
- 1999-01-14 JP JP11007542A patent/JP2000203829A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2823132A1 (en) * | 2001-04-04 | 2002-10-11 | Pro Catalyse | PROCESS FOR REMOVING METAL HALIDES FROM AN ORGANIC OR NON-ORGANIC EFFLUENT, LIQUID OR GASEOUS |
| WO2002081063A1 (en) * | 2001-04-04 | 2002-10-17 | Axens | Method for eliminating metal halides that are present in a liquid or gaseous, organic or non-organic effluent |
| US7252768B2 (en) | 2001-04-04 | 2007-08-07 | Axens | Method for eliminating metal halides that are present in a liquid or gaseous, organic or non-organic effluent |
| KR100880235B1 (en) | 2001-04-04 | 2009-01-28 | 악상스 | Method for eliminating metal halides that are present in a liquid or gaseous, organic or non-organic effluent |
| JP2003026419A (en) * | 2001-07-12 | 2003-01-29 | Taimei Chemicals Co Ltd | METHOD FOR PREPARING alpha-ALUMINA |
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