JPH07267632A - Production of porous gamma-alumina - Google Patents
Production of porous gamma-aluminaInfo
- Publication number
- JPH07267632A JPH07267632A JP6061349A JP6134994A JPH07267632A JP H07267632 A JPH07267632 A JP H07267632A JP 6061349 A JP6061349 A JP 6061349A JP 6134994 A JP6134994 A JP 6134994A JP H07267632 A JPH07267632 A JP H07267632A
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- heat
- treated
- phase
- temperature
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 22
- 239000011707 mineral Substances 0.000 claims abstract description 22
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 13
- 239000011029 spinel Substances 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 37
- 238000005191 phase separation Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229960002050 hydrofluoric acid Drugs 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 72
- 229910052622 kaolinite Inorganic materials 0.000 description 19
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 14
- 229910052621 halloysite Inorganic materials 0.000 description 14
- 238000009826 distribution Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910001583 allophane Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/04—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by dissolving-out added substances
Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、γ-アルミナ多孔体の製
造方法に関し、さらに詳しくは、耐熱性に優れ、高い比
表面積を有し、孔径分布がシャープであるようなγ-ア
ルミナ多孔体の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a γ-alumina porous body, and more specifically, to a γ-alumina porous body having excellent heat resistance, a high specific surface area, and a sharp pore size distribution. It relates to a manufacturing method.
【０００２】[0002]
【発明の技術的背景】近年、地球環境問題が盛んに議論
されているが、特に大都市近郊における大気汚染の大き
な原因として、自動車エンジンなどの内燃機関からの排
気ガスに含まれる有害物質が挙げられる。これらの内燃
機関から排出される排出ガス中の有害物質を低減させる
には、自動車エンジン等における燃料の燃焼効率をさら
に改善することが望ましい。このような要求に応えるに
は、過酷な条件下でも機能する触媒の開発が求められ
る。BACKGROUND OF THE INVENTION In recent years, global environmental problems have been actively discussed, and a major cause of air pollution, particularly in the suburbs of large cities, is harmful substances contained in exhaust gas from internal combustion engines such as automobile engines. To be In order to reduce harmful substances in the exhaust gas discharged from these internal combustion engines, it is desirable to further improve the combustion efficiency of fuel in automobile engines and the like. In order to meet such requirements, it is necessary to develop a catalyst that functions even under severe conditions.
【０００３】ところで、現在このような触媒としては、
Ｐｔ等を担持した不均一触媒が用いられており、その触
媒担体は、γ-アルミナである。しかし、一般的にγ-ア
ルミナは、１０００℃付近で安定相のα-アルミナへ相
転移し、その比表面積が著しく低下し、触媒担体として
の機能を失ってしまうとの問題点があった。Now, as such a catalyst,
A heterogeneous catalyst supporting Pt or the like is used, and the catalyst carrier is γ-alumina. However, in general, γ-alumina undergoes a phase transition to α-alumina which is a stable phase at around 1000 ° C., its specific surface area is remarkably reduced, and the function as a catalyst carrier is lost.
【０００４】このため、高温でも高い比表面積を維持で
きるような耐熱性に優れた触媒担体の開発が望まれてい
る。なお、これまでにγ-アルミナからα-アルミナへの
転移温度は、γ-アルミナに酸化物等を添加することに
より著しく変わることが知られており、特にγ-アルミ
ナにＳｉＯ2を添加すれば、転移温度を著しく上昇さ
せ、高温下でγ-アルミナの高い比表面積を維持しうる
ことが報告されている（文献：B.E.Yoldas(1976)“Ther
mal stabilization of an active alumina and effect
of dopants on the surface area ”J. Materials Scie
nce,11,465-470.）。Therefore, it is desired to develop a catalyst carrier having excellent heat resistance that can maintain a high specific surface area even at high temperatures. It has been known that the transition temperature from γ-alumina to α-alumina is significantly changed by adding an oxide or the like to γ-alumina, and especially when SiO 2 is added to γ-alumina. , It has been reported that the transition temperature can be remarkably increased and the high specific surface area of γ-alumina can be maintained at high temperature (Reference: BEYoldas (1976) “Ther.
mal stabilization of an active alumina and effect
of dopants on the surface area ”J. Materials Scie
nce, 11,465-470.).
【０００５】[0005]
【発明の目的】本発明は、上記のような従来技術に伴う
問題点を解決しようとするものであって、高い比表面積
を有し、孔径分布がシャープであり、しかも耐熱性に優
れるようなγ-アルミナ多孔体の製造方法を提供するこ
とを目的としている。SUMMARY OF THE INVENTION The present invention is intended to solve the above problems associated with the prior art, and has a high specific surface area, a sharp pore size distribution, and excellent heat resistance. It is an object of the present invention to provide a method for producing a γ-alumina porous body.
【０００６】[0006]
【発明の概要】本発明に係るγ-アルミナ多孔体の製造
方法は、カオリン鉱物および／またはアルミナ-シリカ
系の共沈ゲルを加熱して、スピネル相と非晶質シリカと
に相分離された熱処理物を調製し、次いで得られた熱処
理物をアルカリまたはフッ酸にて処理して非晶質シリカ
を溶出させることを特徴としている。SUMMARY OF THE INVENTION In the method for producing a γ-alumina porous material according to the present invention, a kaolin mineral and / or an alumina-silica coprecipitated gel is heated to cause phase separation into a spinel phase and an amorphous silica. It is characterized in that a heat-treated product is prepared and then the obtained heat-treated product is treated with alkali or hydrofluoric acid to elute amorphous silica.
【０００７】本発明の好ましい態様においては、上記カ
オリン鉱物を、９００〜１２００℃の温度で、１００時
間以下加熱して、スピネル相と非晶質シリカとに相分離
された熱処理物を調製し、次いで得られた熱処理物（焼
結体）をアルカリまたはフッ酸にて処理して非晶質シリ
カを溶出させることが望ましい。また、上記熱処理物を
２００℃以下の温度で、１分〜１００時間アルカリまた
はフッ酸にて処理することが望ましい。In a preferred embodiment of the present invention, the above kaolin mineral is heated at a temperature of 900 to 1200 ° C. for 100 hours or less to prepare a heat-treated product in which a spinel phase and amorphous silica are phase-separated, Next, it is desirable to treat the obtained heat-treated product (sintered body) with alkali or hydrofluoric acid to elute the amorphous silica. Further, it is desirable to treat the heat-treated product with alkali or hydrofluoric acid at a temperature of 200 ° C. or lower for 1 minute to 100 hours.
【０００８】このような本発明に係るγ-アルミナ多孔
体の製造方法によれば、高い比表面積を有し、孔径分布
がシャープであり、しかも耐熱性に優れるようなγ-ア
ルミナ多孔体が得られる。According to such a method for producing a γ-alumina porous material according to the present invention, a γ-alumina porous material having a high specific surface area, a sharp pore size distribution and excellent heat resistance is obtained. To be
【０００９】[0009]
【発明の具体的説明】以下、本発明に係るγ-アルミナ
多孔体の製造方法について具体的に説明する。 ［カオリン鉱物の相分離］本発明においては、カオリン
鉱物を加熱して、スピネル相と非晶質シリカとに相分離
された熱処理物を調製する。DETAILED DESCRIPTION OF THE INVENTION The method for producing a γ-alumina porous material according to the present invention will be specifically described below. [Phase Separation of Kaolin Mineral] In the present invention, the kaolin mineral is heated to prepare a heat-treated product in which the spinel phase and the amorphous silica are phase separated.
【００１０】カオリン鉱物は、一般式：ｎＳｉＯ2・Ａ
ｌ2Ｏ3・ｍＨ2Ｏで表わされるが、このようなカオリン
鉱物として、具体的には、例えば、カオリナイト（２Ｓ
ｉＯ2・Ａｌ2Ｏ3・２Ｈ2Ｏ）、ディッカイト（２ＳｉＯ
2・Ａｌ2Ｏ3・２Ｈ2Ｏ）、ナクライト（２ＳｉＯ2・Ａ
ｌ2Ｏ3・２Ｈ2Ｏ）、ハロイサイト（２ＳｉＯ2・Ａｌ2
Ｏ3・４Ｈ2Ｏ）、アロフェン（１〜２ＳｉＯ2・Ａｌ2Ｏ
3・５Ｈ2Ｏ）、イモゴライト（ＳｉＯ2・Ａｌ2Ｏ3・ｎ
Ｈ2Ｏ）等が挙げられる。Kaolin mineral has the general formula: nSiO 2 .A
It is represented by l 2 O 3 .mH 2 O. Specific examples of such kaolin minerals include kaolinite (2S
iO 2 · Al 2 O 3 · 2H 2 O), dickite (2SiO)
2・ Al 2 O 3・ 2H 2 O), Nacrite (2SiO 2・ A
l 2 O 3 · 2H 2 O), halloysite (2SiO 2 · Al 2
O 3 · 4H 2 O), allophane (1~2SiO 2 · Al 2 O
3 · 5H 2 O), imogolite (SiO 2 · Al 2 O 3 · n
H 2 O) and the like.
【００１１】なお、カオリナイトは、化学式：２ＳｉＯ
2・Ａｌ2Ｏ3・２Ｈ2Ｏで表わされる粘土鉱物で、その粒
子形状は、１μｍ程度の大きさの六角板状で、結晶構造
は、Ａｌ（Ｏ，ＯＨ）6八面体層とＳｉＯ2四面体層とが
１：１でサンドイッチした層構造となっている。このカ
オリナイトの結晶を構成している層間に水分子が一層入
り、数〜１０μｍ程度の管状結晶となったものがハロイ
サイトである。Kaolinite has the chemical formula: 2SiO
It is a clay mineral represented by 2 · Al 2 O 3 · 2H 2 O, its particle shape is a hexagonal plate with a size of about 1 μm, and its crystal structure is an Al (O, OH) 6 octahedron layer and SiO 2 It has a layered structure in which it is sandwiched 1: 1 with a tetrahedral layer. Halloysite is one in which water molecules are further introduced between the layers constituting the kaolinite crystal to form a tubular crystal of several to 10 μm.
【００１２】このカオリン鉱物を加熱すると、カオリン
鉱物→メタカオリン→スピネル相（γ-アルミナ）＋非
晶質シリカ→ムライト＋クリストバライトへと相変化す
る。このようにカオリン鉱物をスピネル相と非晶質シリ
カとに相分離させるには、通常、９００〜１２００℃、
好ましくは９５０〜１０００℃の温度で、１００時間以
下、好ましくは１〜２４時間程度加熱すればよい。When this kaolin mineral is heated, it undergoes a phase change of kaolin mineral → metakaolin → spinel phase (γ-alumina) + amorphous silica → mullite + cristobalite. As described above, in order to phase-separate the kaolin mineral into the spinel phase and the amorphous silica, it is usually 900 to 1200 ° C.
It is preferable to heat at a temperature of 950 to 1000 ° C. for 100 hours or less, preferably about 1 to 24 hours.
【００１３】例えば、カオリン鉱物としてジョージア産
カオリナイトあるいは中国産ハロイサイトを用いる場合
には、９５０〜１０００℃程度の温度で、１〜２４時間
程度保持し、スピネル相と非晶質シリカとに相分離され
た熱処理物を調製することが好ましい。For example, when kaolinite from Georgia or halloysite from China is used as the kaolin mineral, it is held at a temperature of about 950 to 1000 ° C. for about 1 to 24 hours to cause phase separation into a spinel phase and amorphous silica. It is preferable to prepare the heat-treated product.
【００１４】なお、中国産ハロイサイト等のカオリン鉱
物を相分離させる熱処理温度が１２００℃よりも高くな
ると、γ-アルミナと非晶質シリカが反応してムライト
が生成するため、γ-アルミナが消失する。一方、カオ
リン鉱物の熱処理温度が９００℃よりも低いと、スピネ
ル相と非晶質シリカへの相分離が生じない。When the heat treatment temperature for phase-separating kaolin minerals such as halloysite from China is higher than 1200 ° C., γ-alumina and amorphous silica react with each other to form mullite, so that γ-alumina disappears. . On the other hand, when the heat treatment temperature of the kaolin mineral is lower than 900 ° C., phase separation into spinel phase and amorphous silica does not occur.
【００１５】なお、本発明においては、上記加熱温度に
昇温させる際には、通常、５〜３０℃／分程度の速度で
昇温させ、また上記加熱温度で上記時間保持した後、降
温させる際には、５〜５０℃／分程度の速度で降温させ
ることが望ましい。 ［アルカリまたはフッ酸による処理］本発明において
は、上記のようにして得られた熱処理物をアルカリまた
はフッ酸にて処理してγ-アルミナ多孔体を製造する。In the present invention, when the temperature is raised to the above heating temperature, the temperature is usually raised at a rate of about 5 to 30 ° C./min, and the temperature is maintained for the above time and then lowered. At this time, it is desirable to lower the temperature at a rate of about 5 to 50 ° C./minute. [Treatment with alkali or hydrofluoric acid] In the present invention, the heat-treated product obtained as described above is treated with alkali or hydrofluoric acid to produce a γ-alumina porous body.
【００１６】このように熱処理物を、アルカリまたはフ
ッ酸にて処理すると、熱処理物中の非晶質シリカが選択
的にアルカリまたはフッ酸にてその表面から内部に向か
って溶解され、該熱処理物は多孔質化される。このよう
にして得られたγ-アルミナ多孔体には、少量のシリカ
が含まれている。When the heat-treated product is treated with alkali or hydrofluoric acid as described above, the amorphous silica in the heat-treated product is selectively dissolved by the alkali or hydrofluoric acid from the surface to the inside. Is made porous. The γ-alumina porous material thus obtained contains a small amount of silica.
【００１７】上記熱処理物を、アルカリまたはフッ酸に
て処理する際には、用いられるカオリナイト鉱物の種
類、アルカリの濃度、種類あるいはフッ酸の濃度等にも
よるが、例えば、熱処理物１ｇ当りアルカリとして濃度
１〜５モル/リットル程度のＫＯＨ溶液を用いる場合には、通
常２００℃以下、好ましくは２５〜２００℃、さらに好
ましくは５０〜９０℃の温度で、通常１００時間以下、
好ましくは１分〜１００時間、さらに好ましくは５分〜
１００時間、特に好ましくは３０分〜５時間程度保持す
ることが望ましい。When the heat-treated product is treated with alkali or hydrofluoric acid, it depends on the type of kaolinite mineral used, the concentration of alkali, the type, the concentration of hydrofluoric acid, etc. When a KOH solution having a concentration of about 1 to 5 mol / liter is used as an alkali, the temperature is usually 200 ° C. or lower, preferably 25 to 200 ° C., more preferably 50 to 90 ° C., usually 100 hours or less,
Preferably 1 minute to 100 hours, more preferably 5 minutes to
It is desirable to hold for 100 hours, particularly preferably for 30 minutes to 5 hours.
【００１８】例えば、カオリン鉱物としてジョージア産
カオリナイトを用いてなる熱処理物では、５０〜９０℃
の温度で、５分〜１００時間程度アルカリ処理すること
が好ましく、また、中国産ハロイサイトを用いてなる熱
処理物では、４０〜８０℃の温度で５分〜５時間程度ア
ルカリ処理することが望ましい。For example, in the case of a heat-treated product using Georgia kaolinite as the kaolin mineral, the temperature is 50 to 90 ° C.
It is preferable to carry out the alkali treatment for about 5 minutes to 100 hours at the temperature of 1., and for the heat-treated product using the Chinese halloysite, it is desirable to carry out the alkali treatment for about 5 minutes to 5 hours at the temperature of 40 to 80 ° C.
【００１９】上記のようにカオリン鉱物の熱処理物を、
アルカリまたはフッ酸にて処理すると非晶質シリカは溶
出されて細孔が形成され、より高い比表面積と大きな全
細孔容積とを有するγ-アルミナ多孔体が得られる。As described above, the heat-treated kaolin mineral is
When treated with alkali or hydrofluoric acid, the amorphous silica is eluted to form pores, and a γ-alumina porous body having a higher specific surface area and a large total pore volume is obtained.
【００２０】上記アルカリとしては、例えば、水酸化カ
リウム、水酸化ナトリウム等が挙げられる。このように
して得られたγ-アルミナ多孔体では、通常、２〜４ｎ
ｍ付近に細孔径の揃った鋭いピークを示し、１０〜数十
ｎｍ付近にもピークを示し、平均孔径は３〜６ｎｍ程度
であり、比表面積は１００〜３５０ｍ2／ｇ程度であ
り、全細孔容積は０．５〜０．９ｍｌ／ｇ程度である。Examples of the alkali include potassium hydroxide and sodium hydroxide. In the γ-alumina porous body thus obtained, usually 2 to 4n
A sharp peak with a uniform pore size is shown in the vicinity of m, a peak is also shown in the vicinity of 10 to several tens nm, the average pore size is about 3 to 6 nm, the specific surface area is about 100 to 350 m 2 / g, and the total fineness is The pore volume is about 0.5 to 0.9 ml / g.
【００２１】このように、得られたγ-アルミナ多孔体
は、細孔径分布がシャープで、高い比表面積を有してお
り、また高温下においても高い比表面積を保持すること
ができる。このようにγ-アルミナ多孔体が高温下にお
いても大きな比表面積を保持できるのは、上記カオリン
鉱物の熱処理物をＫＯＨ等により処理した際に溶出せず
にγ-アルミナ多孔体中に固溶または残存しているシリ
カ成分が作用しているためであろうと思われる。Thus, the obtained γ-alumina porous material has a sharp pore size distribution and a high specific surface area, and can maintain a high specific surface area even at high temperatures. As described above, the γ-alumina porous body can retain a large specific surface area even at high temperature because the heat treated product of the above kaolin mineral does not elute when treated with KOH or the like, and is solid-solved in the γ-alumina porous body or This is probably because the remaining silica component is acting.
【００２２】[0022]
【発明の効果】このような本発明に係るγ-アルミナ多
孔体の製造方法によれば、高い比表面積を有し、孔径分
布がシャープであり、しかも耐熱性に優れているような
γ-アルミナ多孔体が得られる。このようなγ-アルミナ
多孔体は、分子篩、触媒担体等としての用途が期待でき
る。According to the method for producing a γ-alumina porous material according to the present invention, γ-alumina having a high specific surface area, a sharp pore size distribution, and excellent heat resistance. A porous body is obtained. Such a γ-alumina porous material can be expected to be used as a molecular sieve, a catalyst carrier and the like.
【００２３】[0023]
【実施例】以下、本発明に係るγ-アルミナ多孔体の製
造方法について、実施例によりさらに具体的に説明する
が、本発明は、これらの実施例により何等制限されるも
のではない。測定方法 ［Ｘ線回折分析］試料をめのうまたはアルミナ乳鉢で充
分粉砕した後、粉末Ｘ線回折法（ＸＲＤ）により結晶相
の同定を行なった。測定には、（株）リガク製 Ｘ線回
折計［Geigerflex］を用いた。EXAMPLES Hereinafter, the method for producing a γ-alumina porous material according to the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples. Measuring Method [X-ray Diffraction Analysis] The sample was thoroughly crushed in an agate or an alumina mortar, and then the crystal phase was identified by the powder X-ray diffraction method (XRD). An X-ray diffractometer [Geigerflex] manufactured by Rigaku Corporation was used for the measurement.
【００２４】測定条件を以下に示す。 ターゲット： Ｃｕ（グラファイトで単色化されたも
の） スキャン スピード：２ｄｅｇ.／分 チューブ電圧：４０ＫＶ チューブ電流：２０ｍＡ。The measurement conditions are shown below. Target: Cu (monochromaticized with graphite) Scan speed: 2 deg./min Tube voltage: 40 KV Tube current: 20 mA.
【００２５】また、試料中のγ-アルミナの結晶子径
を、ＸＲＤ回折図形の２θ＝４５．８゜付近の４００回
折線と、２θ＝６７．０゜付近の４４０回折線からそれ
ぞれ求めた。The crystallite diameter of γ-alumina in the sample was determined from the 400 diffraction line near 2θ = 45.8 ° and the 440 diffraction line near 2θ = 67.0 ° in the XRD diffraction pattern.
【００２６】測定には、下記に示すシェラーの式を用い
た。The following Scherrer's equation was used for the measurement.
【００２７】[0027]
【数１】 [Equation 1]
【００２８】［Ｄhkl：ｈｋｌ方向の結晶子の大きさ
（オングストローム），Ｋ：比例定数（ここでは0.
9），λ：測定Ｘ線波長（ＣｕＫα1＝1.54050オングス
トローム），β：半価幅（ラジアン）］ 熱処理によってα-アルミナが生成した試料について
は、市販のα-アルミナ（AKP-30,住友化学（株）製）と
θ-アルミナ（L20N2,旭化成工業（株）製）を用いてピ
ーク強度比をα-アルミナ率に対してプロットした検量
線を作製し、各熱処理時間に対するα-アルミナへの転
移率を見積った。[D hkl : crystallite size in the hkl direction (angstrom), K: proportional constant (0.
9), λ: measured X-ray wavelength (CuKα 1 = 1.54050 angstrom), β: half-value width (radian)] For samples in which α-alumina was formed by heat treatment, commercially available α-alumina (AKP-30, Sumitomo Chemical Co., Ltd.) and θ-alumina (L20N2, manufactured by Asahi Kasei Kogyo Co., Ltd.) were used to prepare a calibration curve in which the peak intensity ratio was plotted against the α-alumina ratio. The transfer rate was estimated.
【００２９】検量線の作成には、α-アルミナでは２θ
＝４３．３゜付近の１１３回折線を用い、θ-アルミナ
では２θ＝４４．９゜付近の１１１回折線を用い、試料
中のγ-アルミナ（スピネル相）では２θ＝４５．５゜
付近の４００回折線を用いた。 ［ＢＥＴ比表面積および細孔径分布測定］各試料の比表
面積測定を窒素吸着によるＢＥＴ法で、細孔径分布の解
析を脱離側等温線を用いてＢ．Ｊ．Ｈ．法により行なっ
た。測定には、全自動ガス吸着量測定装置（AUTOSORB-
1, QUANTA CHROME社製）を用いた。測定に際しては、試
料約０．１ｇを用いた。脱気は、１２０℃で１０ー3torr
未満になるまで１〜２時間行なった。 ［ＦＥ−ＳＥＭおよびＴＥＭ観察］各試料の粒子の状
態、細孔構造等を電界放射型走査電子顕微鏡（FE-SEM,
日本電子（株）製：JSM-890S）および透過型電子顕微鏡
（TEM,（株）日立製作所製：H-9000）にて観察した。な
お、試料には、必要に応じてＡｕ、Ｐｔを蒸着させた。 ［蛍光Ｘ線分析］蛍光Ｘ線分析によって、試料の化学組
成を分析した。装置としては、全自動蛍光Ｘ線分析装置
（RIX3000,（株）リガク 製）を用いた。測定した試料
は、中国産ハロイサイトの９５０℃，２４時間熱処理物
(i)と、その熱処理物のＫＯＨ（９０℃，１時間）処理
物(ii)である。測定に際しては、各成分の金属または化
合物を標準物質とした。中国産ハロイサイトの熱処理物
(i)については、Ｓｉ、Ａｌ、Ｆｅ、Ｔｉ成分を定量分
析し、ＫＯＨ処理物(ii)については、Ｓｉ、Ａｌ、Ｆ
ｅ、ＴｉおよびＫ成分を定量分析した。For the preparation of the calibration curve, 2θ for α-alumina
= 113. 3 diffracted lines around 43.3 °, θ-alumina 2 d = 44.9 ° around 111 diffracted lines, and γ-alumina (spinel phase) in the sample around 2 θ = 45.5 ° around. 400 diffraction lines were used. [Measurement of BET Specific Surface Area and Pore Size Distribution] The specific surface area of each sample was measured by the BET method by nitrogen adsorption, and the analysis of the pore size distribution was performed by using the desorption side isotherm. J. H. Method. For the measurement, a fully automatic gas adsorption amount measuring device (AUTOSORB-
1, QUANTA CHROME) was used. At the time of measurement, about 0.1 g of the sample was used. Degassing, 10 @ 3 torr at 120 ° C.
It carried out for 1-2 hours until it became less than. [FE-SEM and TEM observation] The state of the particles, the pore structure, etc. of each sample were examined by the field emission scanning electron microscope (FE-SEM,
It was observed with JEOL Ltd .: JSM-890S) and a transmission electron microscope (TEM, Hitachi Ltd .: H-9000). Note that Au and Pt were vapor-deposited on the sample as needed. [Fluorescent X-ray analysis] The chemical composition of the sample was analyzed by fluorescent X-ray analysis. A fully automatic X-ray fluorescence analyzer (RIX3000, manufactured by Rigaku Corporation) was used as the device. The measured sample is a heat-treated product of Chinese halloysite at 950 ° C for 24 hours.
(i) and a KOH (90 ° C., 1 hour) treated product (ii) of the heat-treated product. In the measurement, the metal or compound of each component was used as a standard substance. Heat-treated Chinese halloysite
For (i), quantitative analysis of Si, Al, Fe, and Ti components, and for KOH-treated product (ii), Si, Al, F
The e, Ti and K components were quantitatively analyzed.
【００３０】［原料の組成］[Composition of raw materials]
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【実施例１】（ａ） ジョージア産カオリナイトを用いたγ-アルミ
ナ多孔体の製造 ［ジョージア産カオリナイトの熱処理］カオリン鉱物と
して、表１に示すジョージア産カオリナイト（２ＳｉＯ
2・Ａｌ2Ｏ3・２Ｈ2Ｏ）［共立窯業原料（株）］を用い
た。Example 1 (a) γ-aluminum using Georgian kaolinite
Production of Na Porous Body [Heat Treatment of Georgia Kaolinite] As a kaolin mineral, kaolinite of Georgia (2SiO
2 · Al 2 O 3 · 2H 2 O) [Kyoritsu Ceramic Raw Materials Co., Ltd.] was used.
【００３３】このジョージア産カオリナイトをアルミナ
乳鉢で解砕した後、電気炉中で、常温から昇温速度１５
℃／分で熱処理温度９５０℃まで昇温させた。次いで、
この熱処理温度（９５０℃）で２４時間保持した。次い
で、降温速度５０℃／分で常温まで降温させた。This Georgian kaolinite was crushed in an alumina mortar and then heated in an electric furnace from room temperature to a heating rate of 15
The heat treatment temperature was raised to 950 ° C. at a rate of ° C./min. Then
This heat treatment temperature (950 ° C.) was maintained for 24 hours. Then, the temperature was decreased to room temperature at a temperature decrease rate of 50 ° C./min.
【００３４】このようにジョージア産カオリナイトを電
気炉中で熱処理したのち、得られた熱処理物のＸ線回折
分析（ＸＲＤ）および細孔径分布測定を行なった。Ｘ線
回折分析（ＸＲＤ）により、熱処理された該カオリナイ
トは、スピネル相と非晶質シリカとに相分離しているこ
とが確認された。また、アナターゼのピークも明らかに
見られるようになった。この熱処理物の比表面積は、
９．９ｍ2／ｇであり、全細孔容積は、０．０８７ｍｌ
／ｇであった。細孔半径２ｎｍ付近に０．１８dv/d(log
ｒ)の鋭いピークが見られ、また１０〜２０ｎｍ付近に
ブロードなピークが見られた。 ［ＫＯＨ処理］このようにして得られたジョージア産カ
オリナイトの熱処理物を、再びアルミナ乳鉢中にて粉砕
した後、得られた粉砕物１ｇを、テフロン製ビーカ中で
常温〜９０℃に保持された濃度：４モル／リットルのＫ
ＯＨ水溶液中に入れ、マグネチックスターラで数分〜３
日間攪拌した。After heat treating the Georgian kaolinite in an electric furnace in this manner, the heat treated product was subjected to X-ray diffraction analysis (XRD) and pore size distribution measurement. X-ray diffraction analysis (XRD) confirmed that the heat-treated kaolinite was phase-separated into a spinel phase and amorphous silica. Moreover, the peak of anatase became clear. The specific surface area of this heat-treated product is
9.9 m 2 / g, total pore volume is 0.087 ml
/ G. 0.18 dv / d (log
A sharp peak of r) was observed, and a broad peak was observed around 10 to 20 nm. [KOH treatment] The heat-treated product of Georgian kaolinite thus obtained was pulverized again in an alumina mortar, and 1 g of the obtained pulverized product was kept at room temperature to 90 ° C in a Teflon beaker. Concentration: 4 mol / liter K
Put it in the OH aqueous solution and use a magnetic stirrer for several minutes to 3
It was stirred for a day.
【００３５】なお、ＫＯＨによる処理を室温にて、３日
間行う際には、カオリン鉱物の熱処理物１ｇに対してＫ
ＯＨ溶液量を、２５ｍｌ，１００ｍｌ，２５０ｍｌと変
化させた。When the treatment with KOH is carried out at room temperature for 3 days, K is added to 1 g of the heat-treated kaolin mineral.
The amount of OH solution was changed to 25 ml, 100 ml and 250 ml.
【００３６】上記のように熱処理物をＫＯＨ処理した
後、遠心分離（1500rpm,15分）により固液分離し、０．
５モル／リットルのＫＯＨ水溶液で１回（7000rpm,15
分）、蒸留水で２〜３回（8000rpm,30分）洗浄した。After the heat-treated product was subjected to KOH treatment as described above, solid-liquid separation was performed by centrifugation (1500 rpm, 15 minutes), and
Once with 5 mol / liter KOH aqueous solution (7000 rpm, 15
Min) and washed 2-3 times with distilled water (8000 rpm, 30 minutes).
【００３７】なお、上記洗浄時間経過後、洗浄器の回転
が自然に停止するまで１５〜２０分間そのまま保持し
た。このようにして得られたＫＯＨ処理物を、６０℃お
よび１１０℃の各恒温槽中で充分に乾燥してγ-アルミ
ナ多孔体を得た。After the washing time, the washing machine was kept for 15 to 20 minutes until the rotation of the washing machine naturally stopped. The KOH-treated product thus obtained was thoroughly dried in each of the constant temperature baths at 60 ° C. and 110 ° C. to obtain a γ-alumina porous body.
【００３８】得られたγ-アルミナ多孔体（ＫＯＨ処理
物）の比表面積、全細孔容積を表２に示す。また、表２
中、ジョージア産カオリナイトの熱処理物を、９０℃で
２時間ＫＯＨ溶液にて処理してなるγ-アルミナ多孔体
の細孔径分布を図１に示す。Table 2 shows the specific surface area and total pore volume of the obtained γ-alumina porous material (KOH-treated product). Also, Table 2
FIG. 1 shows the pore size distribution of a γ-alumina porous body obtained by treating a heat-treated kaolinite produced in Georgia with a KOH solution at 90 ° C. for 2 hours.
【００３９】上記実施例において、原料のジョジージア
産カオリナイトを９５０℃で２４時間熱処理して得られ
た熱処理試料について、温度６０℃でＫＯＨ処理を行っ
たところ、非晶質シリカは、８時間でほぼ全量が溶出し
た。ＫＯＨ処理物の比表面積は、処理時間が延びるにつ
れて増大し、ＫＯＨの８時間処理試料では、２２８ｍ 2
／ｇとなった。In the above embodiment, the raw material, Jozisia
Obtained by heat-treating kaolinite produced at 950 ℃ for 24 hours
The heat-treated sample was subjected to KOH treatment at a temperature of 60 ° C.
As a result, almost all the amorphous silica was eluted in 8 hours.
It was The specific surface area of the KOH-treated product increases as the treatment time increases.
And increased to 228 m in the sample treated with KOH for 8 hours. 2
/ G.
【００４０】[0040]
【表２】 [Table 2]
【００４１】（ｂ） 中国産ハロイサイトを用いたγ-
アルミナ多孔体の製造 上記（ａ）において、ジョージア産カオリナイトに代え
て、表１に示す中国産ハロイサイト（２ＳｉＯ2・Ａｌ2
Ｏ3・４Ｈ2Ｏ）［共立窯業原料（株）製］を用い、上記
（ａ）と同様にしてγ-アルミナ多孔体を製造した。 (B) γ-using Chinese halloysite
Production of Alumina Porous Body In place of the kaolinite produced in Georgia in the above (a), halloysite (2SiO 2 · Al 2 produced in China shown in Table 1 is used.
O 3 .4H 2 O) [manufactured by Kyoritsu Ceramic Materials Co., Ltd.] was used to produce a γ-alumina porous body in the same manner as in (a) above.
【００４２】得られたγ-アルミナ多孔体（ＫＯＨ処理
物）の比表面積、全細孔容積を表３に示す。また、表３
中、中国産ハロイサイトの熱処理物を、７５℃で１時間
ＫＯＨ溶液にて処理してなるγ-アルミナ多孔体の細孔
径分布を図２に示す。Table 3 shows the specific surface area and total pore volume of the obtained γ-alumina porous material (KOH-treated product). Also, Table 3
Figure 2 shows the pore size distribution of a γ-alumina porous body obtained by treating a heat-treated Chinese halloysite product with a KOH solution at 75 ° C for 1 hour.
【００４３】[0043]
【表３】 [Table 3]
【００４４】また、原料の中国産ハロイサイトを９５０
℃で２４時間熱処理して得られた熱処理試料を、９０℃
で１時間ＫＯＨ処理してなるＫＯＨ処理試料について、
蛍光Ｘ線分析による定量分析を行なった。In addition, the raw material Chinese halloysite was 950
The heat-treated sample obtained by heat-treating for 24 hours at 90 ° C.
For KOH-treated samples that have been KOH-treated for 1 hour at
Quantitative analysis was performed by fluorescent X-ray analysis.
【００４５】結果を表４に示す。The results are shown in Table 4.
【００４６】[0046]
【表４】 [Table 4]
【００４７】γ-アルミナ多孔体の耐熱性試験 上記のようにして得られたγ-アルミナ多孔体につい
て、耐熱性試験を行なった。 Heat Resistance Test of γ-Alumina Porous Body A heat resistance test was performed on the γ-alumina porous body obtained as described above.
【００４８】測定条件を以下に示す。 （１）加熱温度を変えた耐熱性試験 実施例１により得られたジョージア産カオリナイトのＫ
ＯＨ（９０℃，１時間）処理物および、中国産ハロイサ
イトのＫＯＨ（７５℃，１時間）処理物を用いて耐熱性
試験を行なった。すなわちこれらのγ-アルミナ多孔体
約０．２ｇを磁製坩堝に入れて電気炉にて常温から昇温
速度１０℃／分で１０００℃まで昇温し、この温度（10
00℃）で１時間加熱した後、降温速度１０℃／分で常温
まで降温させ、γ-アルミナ多孔体の耐熱性を測定し
た。The measurement conditions are shown below. (1) Heat resistance test with varying heating temperature K of Georgia kaolinite obtained in Example 1
A heat resistance test was conducted using an OH (90 ° C., 1 hour) treated product and a Chinese halloysite KOH (75 ° C., 1 hour) treated product. That is, about 0.2 g of these γ-alumina porous bodies was put into a porcelain crucible and heated from room temperature to 1000 ° C. at a heating rate of 10 ° C./min.
After heating at 00 ° C) for 1 hour, the temperature was lowered to room temperature at a temperature lowering rate of 10 ° C / min, and the heat resistance of the γ-alumina porous material was measured.
【００４９】また、上記γ-アルミナ多孔体の加熱温度
（1000℃）を、１１００℃、１１５０℃、１２００℃と
変化させて耐熱性を測定した。 （２） 加熱温度１１００℃での加熱時間を変えた耐熱
性試験 上記（１）において、加熱温度１１００℃で１時間熱処
理した試料をめのう乳鉢で粉砕した後、磁製坩堝に入れ
て電気炉にて常温から昇温速度１５℃／分で１１００℃
まで昇温し、この温度（1100℃）で下記所定時間加熱保
持した後、降温速度５０℃／分で常温まで降温させ、γ
-アルミナ多孔体の耐熱性を測定した。The heat resistance was measured by changing the heating temperature (1000 ° C.) of the γ-alumina porous material to 1100 ° C., 1150 ° C. and 1200 ° C. (2) Heat resistance test with heating time changed at heating temperature of 1100 ° C In the above (1), the sample heat-treated at heating temperature of 1100 ° C for 1 hour was crushed in an agate mortar, put in a porcelain crucible and placed in an electric furnace. From normal temperature to 1100 ° C at a heating rate of 15 ° C / min
After heating to this temperature (1100 ° C) and holding for the specified time below, the temperature is lowered to room temperature at a cooling rate of 50 ° C / min.
-The heat resistance of the alumina porous body was measured.
【００５０】また、処理条件を以下に示す。 試料量： （１）で得られた処理試料全量（０．２〜
０．０５ｇ） 保持時間： ２４時間、４８時間、７２時間、２４０時
間（２４時間×３回＋１６８時間×１回）耐熱性測定結果 上記実施例１で得られた、中国産ハロイサイトからなる
γ-アルミナ多孔体（950℃,24時間熱処理物を75℃,1時
間KOH処理したもの）は、１１００℃,１時間の熱処理を
行なった後でも、その比表面積は１６２ｍ2／ｇと高い
レベルを保持した。また、ジョージア産カオリナイトか
らなるγ-アルミナ多孔体（950℃,24時間熱処理物を90
℃,1時間KOH処理したもの）は、１１００℃,１時間の熱
処理を行なった後でも１５７ｍ2／ｇと高いレベルを保
持した。The processing conditions are shown below. Sample amount: Total amount of treated sample obtained in (1) (0.2 to
0.05g) Holding time: 24 hours, 48 hours, 72 hours, 240 hours (24 hours x 3 times + 168 hours x 1 time) Results of heat resistance measurement γ- consisting of Chinese halloysite obtained in Example 1 above Alumina porous material (950 ° C, 24 hours heat treated product, 75 ° C, 1 hour KOH treated) maintains its high specific surface area of 162 m 2 / g even after 1100 ° C, 1 hour heat treatment. did. In addition, a γ-alumina porous material composed of Georgian kaolinite (heat treated at 950 ° C for 24 hours
The product treated with KOH at 1 ° C. for 1 hour maintained a high level of 157 m 2 / g even after the heat treatment at 1100 ° C. for 1 hour.
【図１】図１は、原料のジョージア産カオリナイトを９
５０℃で２４時間熱処理して得られた熱処理試料につい
て、９０℃で２時間のＫＯＨ処理してなるγ-アルミナ
多孔体の細孔径分布図である。FIG. 1 is a schematic view of a raw material of kaolinite from Georgia 9
FIG. 3 is a pore diameter distribution diagram of a γ-alumina porous body obtained by subjecting a heat-treated sample obtained by heat treatment at 50 ° C. for 24 hours to KOH treatment at 90 ° C. for 2 hours.
【図２】図２は、原料の中国産ハロイサイトを９５０℃
で２４時間熱処理して得られた熱処理試料について、７
５℃で１時間のＫＯＨ処理してなるγ-アルミナ多孔体
の細孔径分布図である。[Fig. 2] Fig. 2 shows Chinese raw material halloysite at 950 ° C.
The heat-treated sample obtained by heat-treating for 24 hours at
FIG. 3 is a pore diameter distribution diagram of a γ-alumina porous body obtained by treating with KOH at 5 ° C. for 1 hour.
Claims (3)
リカ系の共沈ゲルを加熱して、スピネル相と非晶質シリ
カとに相分離された熱処理物を調製し、次いで得られた
熱処理物をアルカリまたはフッ酸にて処理して非晶質シ
リカを溶出させることを特徴とするγ-アルミナ多孔体
の製造方法。1. A kaolin mineral and / or an alumina-silica coprecipitated gel is heated to prepare a heat-treated product in which a spinel phase and amorphous silica are phase-separated, and then the obtained heat-treated product is treated with an alkali. Alternatively, the method for producing a γ-alumina porous body is characterized in that the amorphous silica is eluted by treatment with hydrofluoric acid.
-シリカ系の共沈ゲルを９００〜１２００℃の温度で、
１００時間以下加熱して、スピネル相と非晶質シリカと
に相分離させることを特徴とする請求項１に記載のγ-
アルミナ多孔体の製造方法。2. The kaolin mineral and / or alumina.
-A silica-based coprecipitated gel at a temperature of 900 to 1200 ° C,
The γ − according to claim 1, wherein the spinel phase and the amorphous silica are phase-separated by heating for 100 hours or less.
Method for producing porous alumina body.
分〜１００時間アルカリまたはフッ酸にて処理して非晶
質シリカを溶出させることを特徴とする請求項１または
２に記載のγ-アルミナ多孔体の製造方法。3. The heat-treated product at a temperature of 200.degree.
The method for producing a γ-alumina porous body according to claim 1 or 2, wherein the amorphous silica is eluted by treatment with alkali or hydrofluoric acid for a period of minutes to 100 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06134994A JP3542632B2 (en) | 1994-03-30 | 1994-03-30 | Method for producing gamma-alumina porous body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06134994A JP3542632B2 (en) | 1994-03-30 | 1994-03-30 | Method for producing gamma-alumina porous body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07267632A true JPH07267632A (en) | 1995-10-17 |
| JP3542632B2 JP3542632B2 (en) | 2004-07-14 |
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ID=13168580
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06134994A Expired - Fee Related JP3542632B2 (en) | 1994-03-30 | 1994-03-30 | Method for producing gamma-alumina porous body |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100468525B1 (en) * | 2002-03-22 | 2005-01-27 | 재단법인서울대학교산학협력재단 | production method of porous gamma-alumina powder having mesopore and macropore |
| KR100473804B1 (en) * | 2002-08-12 | 2005-03-10 | 학교법인 포항공과대학교 | Mesoporous alumina molecular sieve, and process for preparing the same |
| KR100792617B1 (en) * | 2006-04-26 | 2008-01-09 | 한국과학기술원 | Producing Method of One-Dimensional Boehmite/Ionic Liquid Complex and One-Dimensional Mesoporous ? Alumina Using Ionic Liquid |
| KR20180081658A (en) * | 2017-01-06 | 2018-07-17 | 주식회사 효성 | Method of preparing dehydrogenation catalysts |
-
1994
- 1994-03-30 JP JP06134994A patent/JP3542632B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100468525B1 (en) * | 2002-03-22 | 2005-01-27 | 재단법인서울대학교산학협력재단 | production method of porous gamma-alumina powder having mesopore and macropore |
| KR100473804B1 (en) * | 2002-08-12 | 2005-03-10 | 학교법인 포항공과대학교 | Mesoporous alumina molecular sieve, and process for preparing the same |
| KR100792617B1 (en) * | 2006-04-26 | 2008-01-09 | 한국과학기술원 | Producing Method of One-Dimensional Boehmite/Ionic Liquid Complex and One-Dimensional Mesoporous ? Alumina Using Ionic Liquid |
| KR20180081658A (en) * | 2017-01-06 | 2018-07-17 | 주식회사 효성 | Method of preparing dehydrogenation catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3542632B2 (en) | 2004-07-14 |
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