JPH03252312A - Production of porous alumina gel - Google Patents
Production of porous alumina gelInfo
- Publication number
- JPH03252312A JPH03252312A JP2049609A JP4960990A JPH03252312A JP H03252312 A JPH03252312 A JP H03252312A JP 2049609 A JP2049609 A JP 2049609A JP 4960990 A JP4960990 A JP 4960990A JP H03252312 A JPH03252312 A JP H03252312A
- Authority
- JP
- Japan
- Prior art keywords
- gel
- alumina
- mixture
- organic solvent
- aluminum alkoxide
- 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 aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000007704 transition Effects 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 14
- 239000000919 ceramic Substances 0.000 abstract description 12
- 230000000979 retarding effect Effects 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 6
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000000352 supercritical drying Methods 0.000 description 9
- 150000004703 alkoxides Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011240 wet gel Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229960005235 piperonyl butoxide Drugs 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 241000894007 species Species 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 241001424309 Arita Species 0.000 description 1
- QQMXPYIHKPAZFM-UHFFFAOYSA-N CCO.CCO.CCO.OP(O)(O)=O Chemical compound CCO.CCO.CCO.OP(O)(O)=O QQMXPYIHKPAZFM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 101150046432 Tril gene Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QTBSBXVTEAMEQO-JVVVGQRLSA-N acetic acid Chemical class [11C](C)(=O)O QTBSBXVTEAMEQO-JVVVGQRLSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000004718 beta keto acids Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000012700 ceramic precursor Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Colloid Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、高温触媒担体に好適な高温下でも高い比表面
積を維持しうるアルミナ系多孔質ゲルの製造方法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an alumina-based porous gel that can maintain a high specific surface area even at high temperatures and is suitable for use as a high-temperature catalyst carrier.
従来、化学プロセスに使用されてきた触媒は、通常、６
００℃以下の温度に耐性であるなら通常の化学プロセス
に支障を生じることは特になかったためセラミックス触
媒が一般的に使用されても特にその耐熱性は問題になら
なかったが、近年、高温熱化学プロセスを伴う装置、特
に、触媒燃焼器は、ガスタービン、ボイラー、ジェット
エンジンなどの応用が期待され、ＮＯＸ発生の低減化、
燃焼効率の向上等の要請から、１０００℃以上の高温環
境に耐性のセラッミクスが使用されるようになってきて
いる。Catalysts traditionally used in chemical processes are typically 6
Ceramic catalysts did not pose any problems in ordinary chemical processes if they could withstand temperatures below 00°C, so even when ceramic catalysts were commonly used, their heat resistance was not a problem.However, in recent years, high-temperature thermochemical Devices that involve processes, especially catalytic combustors, are expected to be applied to gas turbines, boilers, jet engines, etc., and are expected to reduce NOx generation,
Due to the demand for improved combustion efficiency, ceramics that are resistant to high-temperature environments of 1000° C. or higher are being used.
このようなセラッミクスは、例えば、所望の組成、形状
を得るために、種々の金属酸化物等の粉末を適宜配合混
合、成形、そして焼成して製造される。しかし、この方
法では出発原料粉末自体の比表面積が低いため高温焼成
により一層比表面積が低下し、効率の高い触媒とは言え
なかった。Such ceramics are manufactured, for example, by suitably mixing powders of various metal oxides, molding, and firing in order to obtain a desired composition and shape. However, in this method, since the starting raw material powder itself has a low specific surface area, the specific surface area is further reduced by high-temperature calcination, and the catalyst cannot be said to be highly efficient.
そこで、より比表面積の高いセラッミクスを製造するた
めに、出発原料を粉末に代えて金属アルコキシド、例え
ば、アルミニウムアルコキシドやバリウムアルコキシド
を混合加水分解して形成したゲルを焼成するゾル・ゲル
法が、ＩＮＴＥＲＮＡＴＩＯＮＡＬＳＹＭＰ［］ＳＩＵ
Ｍ ＯＮ ＦＩＮＥ Ｃ錘ＡＭ［”Ｓ ＡＲＩＴＡ ’
８７に「高温触媒燃焼におりる耐熱性触媒材料の開発」
と題した荒井弘通の文献に記載されている。Therefore, in order to produce ceramics with a higher specific surface area, the sol-gel method, in which a gel formed by mixing and hydrolyzing a metal alkoxide, such as aluminum alkoxide or barium alkoxide, instead of powder as the starting material, is fired is used. []SIU
M ON FINE C weight AM ["S ARITA '
87 “Development of heat-resistant catalytic materials for high-temperature catalytic combustion”
It is described in Hiromichi Arai's literature entitled ``.
しかしながら、上記ゾル・ゲル法では、粉末として生成
するため一体化させるためには再形成が必要あること、
また、燃焼触媒として最も一般的な使用温度である１２
００℃付近での比表面積が、せいぜい５０〜６０ｍ’／
（Ｂと小さく、尚比表面積が十分に大きいとはいえなか
った。また、単純なアルミナ系では、αアルミナへの相
転移の際、粒成長が起こり急激に比表面積が低下してし
まうという問題があった。However, in the above-mentioned sol-gel method, since it is produced as a powder, reformation is required to integrate it.
In addition, 12
The specific surface area at around 00℃ is at most 50 to 60 m'/
(B was small, and the specific surface area could not be said to be sufficiently large.In addition, in simple alumina systems, grain growth occurs during the phase transition to α-alumina, resulting in a rapid decrease in the specific surface area. was there.
本発明は、以上の問題点を解決し、ゾル・ゲル法により
高温下で高い比表面積を有し、かつ一体化したパルキイ
なアルミナ系多孔質セラッミクスの前駆体ゲノベ即ち、
アルミナ系多孔質ゲルの製造方法を提供することを解決
課題とするものである。The present invention solves the above problems, and produces a precursor genome for alumina-based porous ceramics that has a high specific surface area at high temperatures and is integrated using the sol-gel method.
The object of the present invention is to provide a method for producing an alumina-based porous gel.
本発明は、アルミニウムアルコキシドに対し、アルカノ
ールアミン、βケト酸エステル、βジケトン化合物の１
種または２種以上を０．１〜５倍モルと、アルミナのα
相転移温度を遅延しうる元Ｓをアルミニウムアルコキシ
ドに対し、Ｏ，０１ｍｏｌ％〜３Ｑｍｏｌ％混合してア
ルミナ系前駆体混合物を形成する工程、必要に応じて塩
基触媒の存在下、該混合物中に存在する加水分解しろる
反応基の数に対し０． ５〜２倍モルの水で該前駆体混
合物を加水分解、ゲル化せしめる工程、および該ゲル中
の液分の大半を占める有機溶媒または少なくとも当該有
機溶媒を含む混合系の超臨界状態を経てゲルの乾燥を行
う工程からなることを特徴とするアルミナ系多孔質ゲル
の製造方法、およびアルミナのα相転移温度を遅延しろ
る元素が、シリコンおよび／またはリンであることを特
徴とする上記記載のアルミナ系多孔質ゲルの製造方法で
あり、これにより上記課題を解決することができる。The present invention provides aluminum alkoxide with alkanolamine, β-keto acid ester, and β-diketone compound.
The α of alumina is 0.1 to 5 times the mole of the species or two or more species.
A process of forming an alumina-based precursor mixture by mixing O,01 mol% to 3Q mol% of element S capable of retarding the phase transition temperature with respect to aluminum alkoxide, optionally in the presence of a base catalyst, present in the mixture 0.0 for the number of reactive groups that can be hydrolyzed. A process of hydrolyzing and gelling the precursor mixture with 5 to 2 times the mole of water, and a supercritical state of an organic solvent that accounts for most of the liquid in the gel, or a mixture system containing at least the organic solvent, produces a gel. A method for producing an alumina-based porous gel characterized by comprising a step of drying alumina, and the above-mentioned method characterized in that the element that retards the α-phase transition temperature of alumina is silicon and/or phosphorus. This is a method for producing an alumina-based porous gel, which can solve the above problems.
本発明において、アルミニウムアルコキシドとアルカノ
ールアミン、βケト酸エステル、βジケトン化合物（以
下、改質剤と言う場合がある）とアルミナのα相転移温
度を遅延しろる元素（以下、遅延化元素と略す。）の混
合によるアルミナ系前駆体混合物の形成は反応を伴うも
のであり、両者を常温ないし加温下に混合することがで
き、混和性、反応の均一性の面から有機溶媒存在下で行
うのが好ましい。もっとも、有機溶媒が存在しなくても
混合は可能である。ここで用いる有機溶媒としてはアル
ミニウムアルコキシドおよび該遅延化剤を溶解するもの
が好ましく、具体的にはメタノール、エタノール、ｎ−
プロパツール、ｉｓ。In the present invention, aluminum alkoxides, alkanolamines, β-keto acid esters, β-diketone compounds (hereinafter sometimes referred to as modifiers) and elements that retard the α-phase transition temperature of alumina (hereinafter abbreviated as retarder elements) are used. Formation of an alumina-based precursor mixture by mixing .) involves a reaction, and both can be mixed at room temperature or under heating, and from the standpoint of miscibility and uniformity of reaction, it is carried out in the presence of an organic solvent. is preferable. However, mixing is possible even without the presence of an organic solvent. The organic solvent used here is preferably one that dissolves the aluminum alkoxide and the retardant, specifically methanol, ethanol, n-
Proper Tools, is.
プロパノーノベ５ｅｃ−ブタノール等に代表されるアル
コール類、トルエン、ベンゼン、キシレン等に代表され
る芳香族系炭化水素、テトラヒドロフラン、ジメチルホ
ルムアミド、四塩化炭素等が例示されるが、溶解度の観
点からアルコール類が好ましい。Examples include alcohols such as propanobe 5ec-butanol, aromatic hydrocarbons such as toluene, benzene, and xylene, tetrahydrofuran, dimethylformamide, and carbon tetrachloride; however, from the viewpoint of solubility, alcohols are preferable.
本発明において、アルミナ系前駆体混合物の加水分解反
応により該遅延化元素はアルミニウムアルコキシドと水
を介して反応し、該遅延化元素が結合されたゲルが形成
されると共に、アルミニウムアルコキシド等由来のアル
コール等の有機溶媒が生成するので、ゲル形成後のゲル
中（ゲル中以外も包含されることは明らかである。）に
は、生成した有機溶媒、上記添加有機溶媒、該改質剤等
からなる有機溶媒が存在することになる。In the present invention, the retardation element reacts with aluminum alkoxide through water by the hydrolysis reaction of the alumina-based precursor mixture, and a gel in which the retardation element is bonded is formed, and alcohol derived from aluminum alkoxide, etc. Since organic solvents such as the above are generated, the gel after gel formation (obviously, it includes areas other than the gel) consists of the generated organic solvent, the above-mentioned added organic solvent, the modifier, etc. An organic solvent will be present.
該有機溶媒は、超臨界状態を経てなされるゲルの乾燥と
共に除去されるが（以下、超臨界乾燥と略す）、所望に
より当該有機溶媒とそれ以外の化学物質との混合系、例
えば、当該有機溶媒と二酸化炭素との混合系にてなされ
るゲルの乾燥を実施してもよい。この場合の超臨界状態
とは、当該有機溶媒の１種又は混合物または当該有機溶
媒とそれ以外の化学物質との混合物に固有の臨界温度（
Ｔ、）及び臨界圧力（Ｐｃ）を越えた状態を指し、それ
ら有機溶媒または該混合物が液体と気体の中間の性質を
示す超臨界流体の状態を意味する。The organic solvent is removed when the gel is dried through a supercritical state (hereinafter referred to as supercritical drying), but if desired, a mixed system of the organic solvent and other chemical substances, for example, the organic The gel may be dried in a mixed system of a solvent and carbon dioxide. In this case, the supercritical state refers to the critical temperature (
It refers to a state in which the organic solvent or the mixture exceeds the critical pressure (Pc) and the supercritical fluid state in which the organic solvent or the mixture exhibits properties intermediate between a liquid and a gas.
又、物質によって臨界点が違うので、それを合わせるこ
とは、超臨界流体の状態の制御が確実になるので好まし
く、従って、湿潤ゲル中の溶媒が超臨界乾燥に用いる所
望の溶媒と違う場合は、湿潤ゲル中の溶媒と超臨界乾燥
に用いる所望の溶媒とを交換する。具体的には、多量の
超臨界乾燥に用いる溶媒中に湿潤ゲルを浸漬して数時間
放置し、溶媒の拡散を利用して溶媒を交換する。Also, since the critical point differs depending on the substance, it is preferable to match the critical point because it ensures control of the state of the supercritical fluid. Therefore, if the solvent in the wet gel is different from the desired solvent used for supercritical drying, , exchange the solvent in the wet gel with the desired solvent used for supercritical drying. Specifically, a wet gel is immersed in a large amount of the solvent used for supercritical drying, left for several hours, and the solvent is exchanged using diffusion of the solvent.
従って、超臨界乾燥における該ゲル中の液分の大半を占
める有機溶媒とは、溶媒置換を実施した場合は、置換に
用いた有機溶媒を、溶媒置換を実施しない場合は、ゲル
生成系に存在する該生成した有機溶媒、上記添加有機溶
媒、該改質剤等からなる有機溶媒を意味する。Therefore, the organic solvent that occupies most of the liquid content in the gel in supercritical drying refers to the organic solvent used for replacement when solvent replacement is performed, and the organic solvent that is present in the gel production system when solvent replacement is not performed. It means an organic solvent consisting of the organic solvent produced, the organic solvent added above, the modifier, etc.
上述のようにゲル溶媒をその超臨界状態下で除くことに
より収縮のない、嵩高いゲル（エアロゲル）が生成する
。このエアロゲルは細かい気孔を多量に含む５多孔体で
あると共に該α相転移温度を遅延しうる元素を有してい
るた於、高温加熱後も高い比表面積を維持することがで
きる。As mentioned above, by removing the gel solvent under its supercritical state, a bulky gel (aerogel) without shrinkage is produced. Since this airgel is a five-porous body containing a large amount of fine pores and contains an element that can retard the α-phase transition temperature, it can maintain a high specific surface area even after high-temperature heating.
もし、高密度で気孔量の少ないゲル（キセロゲル）が生
成したならば、乾燥時に応力が発生し、数片または粉々
に割れることが多いが、超臨界乾燥の性格上応力が発生
しないため、そのようなことはなく一体性に優れる該エ
アロゲルが生成される。従って、本発明により一体化し
たエアロゲルから目的の形状を有する多孔質セラッミク
スを直接合成することが可能である。If a gel (xerogel) with high density and low porosity is formed, stress will occur during drying and it will often break into several pieces or pieces, but due to the nature of supercritical drying, no stress is generated, so This does not occur and the airgel with excellent integrity is produced. Therefore, it is possible to directly synthesize porous ceramics having a desired shape from the airgel integrated according to the present invention.
一方、該遅延化元素を使用して、または使用しないで形
成した生成ゲルを超臨界乾燥ではなく通常の大気圧下で
溶媒を徐々に蒸発させて乾燥する常圧乾燥の場合、乾燥
時に収縮が生じるため上記高密度で気孔量の少ないゲル
（キセロゲル）が生成され、加熱と共に容易に緻密化し
、高い比表面積が維持できない。On the other hand, in the case of normal pressure drying, in which the gel formed with or without the retarding element is dried by gradual evaporation of the solvent under normal atmospheric pressure rather than supercritical drying, shrinkage occurs during drying. As a result, the gel (xerogel) with high density and small amount of pores is produced, which easily becomes dense with heating and cannot maintain a high specific surface area.
尚、本発明において該超臨界乾燥処理されたゲルの高温
における焼成は、該出発原料のアルミニウムアルコキシ
ドに対し０． ０１ｍｏｌ％〜３０ｍｏｌ％の遅延化元
素を使用しているのでアルミナのα相転移温度を遅延化
元素を用いない場合に比べ遅延、即ち、より高温部にす
ることができるためより高温下においても高比表面積を
維持できる結晶構造を有するアルミナ系多孔質ゲルが得
られる。In addition, in the present invention, the supercritically dried gel is calcined at a high temperature by 0.0% with respect to the aluminum alkoxide as the starting material. Since 01 mol% to 30 mol% of the retarding element is used, the α phase transition temperature of alumina is delayed compared to when no retarding element is used. An alumina-based porous gel having a crystal structure capable of maintaining a specific surface area is obtained.
この場合、遅延化元素の添加量が、Ｑ、Ｑｌ、ｍｏｌ％
以下だと添加物の効果が十分に発揮されずにアルミナの
みと同じ結果になってしまうため好ましくなく 、３０
ｍｏｌ％以上だと添加物自体が融点が低い場合などは焼
結してしまうため、また、ある組成の化合物が結晶化し
てしまうため好ましくない。In this case, the amount of the retarding element added is Q, Ql, mol%
If it is less than 30, the effect of the additive will not be fully demonstrated and the result will be the same as that of alumina alone, which is not desirable.
If it is more than mol %, it is not preferable because it will sinter if the additive itself has a low melting point, or a compound of a certain composition will crystallize.
該遅延化元素としては、上記機能を有するものであれば
特に限定されないが、例示すれば、Ｓ】、Ｐ 、 Ｍｇ
、 Ｚｒ等が挙げられ、これら元素は単体でも使用でき
るが、これらを含有する化合物として用いることが好ま
しく、例示すれば、Ｓｉ （ＯＲ）、、Ｐ［ｌ （ＯＲ
） ３（Ｒは、アルキル基を表す。）またはそれらの部
分加水分解反応化合物、ハロゲン化物（例えば、Ｓｉ
Ｉ４、ＳｉＢｒ４．５ｉ２０１６）、その他（例えば、
Ｓｉ （ＣＨ３ＣＯＯ） ４など）、リン酸物（例えば
、Ｉｔ３ＰＤ４、Ｈ，ＰＨＯ，、ＨＰ８２０２など）等
が挙げられる。The retarding element is not particularly limited as long as it has the above function, but examples include S], P, Mg
, Zr, etc. These elements can be used alone, but it is preferable to use them as compounds containing them. Examples include Si (OR), , P[l (OR
) 3 (R represents an alkyl group) or their partial hydrolysis reaction compounds, halides (for example, Si
I4, SiBr4.5i2016), others (e.g.
Si (CH3COO) 4, etc.), phosphates (eg, It3PD4, H, PHO, HP8202, etc.), and the like.
本発明のアルミナ系前駆体混合物、ひいてはその加水分
解生成ゲルを形成するための出発原料とシテハ、アルミ
ニウムアルコキシドおよび遅延化元素あるいはそれを含
む化合物の他、他の金属アルコキシド（例えば、ＮａＤ
Ｒ，Ｋ口Ｒ、Ｃａ（ＯＲ）ｚ、Ｔｌ（ＯＲ）４．５ｒ（
ＤＲｈ 、Ｙ（ＯＲ＞３、Ｂａ （ＯＲ） ２ など、
Ｒはメチル、エチル等のアルキル基）、他の金属塩等の
無機化合物（例えば、Ｎａ［ｌ：１、ＭｇＢｒ２、Ｔｉ
Ｃｌ２等のハロゲン化物、ＮａＮＯ２，３２３口４ 、
口ａ （ＮＯ３） ２等の硝酸塩、硫酸塩、硫酸塩等）
、アルコキシド以外の有機金属化合物（例えば、Ｃ１１
ｓＣＯＯＮａ、（ＣＨ３ＣＯＯ）２Ｃａ等の酢酸塩、（
ＣＯＯＮａ） ２、（ＣＤＯＫ）２等のシニウ酸塩、Ｅ
ＤＴＡ、 ＮＴＡ等のキレート化合物との錯体等）、場
合によっては反応性のよい金属並びに酸化物微粉末（例
えば、ＣａＯ１Ｔ１０２．５１０２、Ｐ２Ｏ６、ＺｒＯ
２等）等を併用することができる。In addition to the starting materials and materials for forming the alumina-based precursor mixture of the present invention, and thus its hydrolyzed gel, aluminum alkoxides and retardation elements or compounds containing them, as well as other metal alkoxides (e.g., NaD
R, K mouth R, Ca(OR)z, Tl(OR)4.5r(
DRh, Y(OR>3, Ba(OR)2, etc.)
R is an alkyl group such as methyl or ethyl), inorganic compounds such as other metal salts (e.g. Na[l:1, MgBr2, Ti
Halides such as Cl2, NaNO2, 323 mouths 4,
(NO3) Nitrate, sulfate, sulfate, etc.)
, organometallic compounds other than alkoxides (e.g. C11
Acetate salts such as sCOONa, (CH3COO)2Ca, (
COONa) 2, (CDOK)2 and other cininates, E
complexes with chelate compounds such as DTA and NTA), and in some cases highly reactive metals and oxide fine powders (e.g. CaO1T102.5102, P2O6, ZrO
2) etc. can be used in combination.
本発明で用いられるアルミニウムアルコキシドは、一般
式（Ｒ［］＞３１ （Ｒコアルキル基）で表わされるも
のであり、具体的にはＲはメチル、エチノｖ、１１−フ
ロビル、１ｓｏ−７’ロピル、ｎ−ブチル、１ｓｏ−ブ
チノベ５ｅｃ−ブチル、ｔｅｒｔ−ブチル等がある。The aluminum alkoxide used in the present invention is represented by the general formula (R[]>31 (R corealkyl group), and specifically R is methyl, ethino-v, 11-furovyl, 1so-7'lopyl, Examples include n-butyl, 1so-butinobe5ec-butyl, and tert-butyl.
本発明で用いられるアルミニウムアルコキシド等と混合
、反応されるアルカノールアミンとしては、モノエタノ
ールアミン、モノｎ−プロパツールアミン、モノｌ５Ｏ
−プロパツールアミン、ジェタノールアミン、ジ１ｓｏ
−プロパツールアミン、トリエタノールアミン、トリｌ
５Ｏ−プロパツールアミンなどが挙げられ、同じくβケ
ト酸エステルとしては、アセト酢酸エチル、アセト酢酸
メチノベマロン酸エチル、マロン酸ジエチルなどが挙げ
られ、βジケトン化合物としては、アセチルアセトン等
が挙げられる。The alkanolamines to be mixed and reacted with aluminum alkoxide etc. used in the present invention include monoethanolamine, mono-n-propanolamine, monol5O
-propertoolamine, jetanolamine, di-1so
-Propertoolamine, triethanolamine, tril
Examples of the β-keto acid ester include ethyl acetoacetate, ethyl acetoacetate methinobemalonate, diethyl malonate, and the like. Examples of the β diketone compound include acetylacetone.
上記アルカノールアミン、βケト酸エステル、βジケト
ン化合物は、その１種または２種以上の総和カアルミニ
ウムアルコキシドに対し０． １倍モル〜５倍モルとな
るように該アルミニウムアルコキシドと混合・反応させ
られ、アルミナ系前駆体混合物が形成される。この場合
、０．１倍モル以下であると次工程の加水分解速度制御
の効果が小さく均質なゲルが得られない。又、５倍モル
以上だと安定化され過ぎてゲル化が困難であるので好ま
しくない。The above-mentioned alkanolamine, β-keto acid ester, and β-diketone compound have 0.0% relative to the total potassium aluminum alkoxide of one or more of them. It is mixed and reacted with the aluminum alkoxide in an amount of 1 to 5 times the mole to form an alumina-based precursor mixture. In this case, if the amount is 0.1 times the mole or less, the effect of controlling the hydrolysis rate in the next step is small and a homogeneous gel cannot be obtained. Moreover, if it is 5 times the mole or more, it is not preferable because it is too stabilized and gelation becomes difficult.
該アルミナ系前駆体混合物は、必要に応じて、塩基触媒
、例えば、アンモニア、ピリジン、ピペリジン、ピペラ
ジンの存在下、該混合物中に存在する加水分解しうる反
応基の数（例えば、該（Ｒ口） ３Ａ矛の未反応の旺基
、および上記アルカノールアミン、βケト酸エステノベ
βジケトン化合物と該ＲＯ基との反応生成基の数、即ち
、出発原料のアルミニウムアルコキシド、あるいは遅延
化元素を有する化合物の肛基の数、更に、アルミニウム
アルコキシド以外の添加金属アルコキシド或いは金属単
体から生成した金属アルコキシドのアルコキシド基の数
等が挙げられる。）に対して０゜５〜２倍モルの水で加
水分解される。この場合、水の量が、０．５倍モル以下
だとゲル化が困難であり、２倍モル以上だと粒子が生成
する傾向にあり、目的とする均質なゲルが作製できない
。The alumina-based precursor mixture is optionally prepared in the presence of a basic catalyst, such as ammonia, pyridine, piperidine, piperazine, to reduce the number of hydrolyzable reactive groups present in the mixture (for example, the ) The number of unreacted radicals of the 3A spear and the groups formed by the reaction between the alkanolamine, β-keto acid estenobe β-diketone compound and the RO group, that is, the starting material aluminum alkoxide or the compound having a retarding element. The number of anal groups, and the number of alkoxide groups of added metal alkoxides other than aluminum alkoxides or metal alkoxides produced from simple metals, etc.) can be hydrolyzed with 0.5 to 2 times the mole of water. . In this case, if the amount of water is less than 0.5 times the molar amount, gelation will be difficult, and if the amount of water is more than 2 times the molar amount, particles will tend to be generated, making it impossible to produce the desired homogeneous gel.
本発明の超臨界乾燥後に得られたアルミナ系多孔質ゲル
を焼成して得られるセラッミクスとしては、Ａｌ２Ｏ。The ceramics obtained by firing the alumina-based porous gel obtained after supercritical drying of the present invention include Al2O.
−８１０２系、Ａｌ２（］３−５Ｉ［１２Ｍｇ［］系（
コープイエライ））、Ａｌ□Ｄ３−２ｒＤ２系等が挙げ
られる。-8102 series, Al2(]3-5I[12Mg[] series (
Examples include Coop Yerai)), Al□D3-2rD2 system, and the like.
本発明の特徴は、ゾル・ゲル法によりアルミナ系多孔質
ゲルを合成するにあたり、アルミニウムアルコキシドを
アルカノールアミン、βケト酸エステル、βジケトン化
合物の改質剤と該遅延化元素の存在下に、適量の水で加
水分解することにより粉末ではなく一体化した均質なア
ルミナ系ゲルを形成し、これを超臨界乾燥により収縮、
割れのない一体化した均質なアルミナ系多孔質ゲルを形
成する点である。遅延化元素の添加によりα化が遅れ、
粒成長がおさえられる。これにより得られたゲル（エア
ロゲル）は高温下にさらされても高い比表面積を維持す
ることができ、高温触媒担体の前駆体として好適である
。The feature of the present invention is that when synthesizing an alumina-based porous gel by the sol-gel method, an appropriate amount of aluminum alkoxide is mixed in the presence of a modifier such as an alkanolamine, a β-keto acid ester, or a β-diketone compound and the retarding element. By hydrolyzing with water, an integrated homogeneous alumina gel is formed instead of a powder, which is then shrunk by supercritical drying.
The point is that it forms an integrated, homogeneous alumina-based porous gel without cracks. Addition of retarding elements delays α-ization,
Grain growth is suppressed. The gel (aerogel) obtained thereby can maintain a high specific surface area even when exposed to high temperatures, and is suitable as a precursor for a high-temperature catalyst carrier.
高温触媒担体は、該前駆体を８００℃〜１２００℃の範
囲で焼成することにより製造される。また高温触媒は、
触媒金属を含む溶液に高温触媒担体を浸せきさせて触媒
金属をコートする。そして、これを熱処理して高温触媒
とする。The high-temperature catalyst carrier is manufactured by firing the precursor at a temperature in the range of 800°C to 1200°C. In addition, high-temperature catalysts
A high-temperature catalyst carrier is immersed in a solution containing the catalytic metal to coat it with the catalytic metal. This is then heat-treated to form a high-temperature catalyst.
以下、本発明の具体的実施例を説胡するが、本発明はこ
れに限定されるものではない。Hereinafter, specific examples of the present invention will be explained, but the present invention is not limited thereto.
（実施例１）
アルミニウムトリｓｅ叶ブトキシド〔（ｓｅｃ−Ｂｕｌ
ｌ） ３Ａｌ〕９ｇとアセト酢酸エチル４．７５ｇを混
合し、１０ｍ１の２−ブタノールを添加した。また、シ
リコンテトラエトキシド０．３６ｇと２−ブタノール０
．２ｇを混ぜたものに、水０．０３３ｇと２−ブタノー
ル０．２ｇを混合したものを加えた。このシリコンアル
コキシドの部分加水分解物とアルミニウムト１Ｊｓｅｃ
−ブトキシドの混合物を混ぜた。これに水２．０７ｇと
２−ブタノール２０ｍ１ の混合液を徐々に添加し、そ
の後、６０℃に７２時間保ちゲル化させた。この湿潤ゲ
ルをオートクレーブ装置で２３０ ｋｇ／ｃｒｌ、 ２
７０℃のエタノールの超臨界状態でエタノールを除き、
乾燥ゲルを得た。この乾燥ゲルの比表面積は５３０ｍ２
／ｇであった。これを１２００℃、５時間で焼成して、
比表面積１２０ｍ２／ｇの多孔質セラッミクスを得た。(Example 1) Aluminum trise butoxide [(sec-Bul
l) 9 g of 3Al] and 4.75 g of ethyl acetoacetate were mixed, and 10 ml of 2-butanol was added. Also, 0.36 g of silicone tetraethoxide and 0.2 g of 2-butanol.
．． A mixture of 0.033 g of water and 0.2 g of 2-butanol was added to the 2 g mixture. This partial hydrolyzate of silicon alkoxide and aluminium 1Jsec
- A mixture of butoxides was mixed. A mixed solution of 2.07 g of water and 20 ml of 2-butanol was gradually added to this, and then kept at 60°C for 72 hours to form a gel. This wet gel was heated to 230 kg/crl in an autoclave device, 2
Remove ethanol in the supercritical state of ethanol at 70°C,
A dry gel was obtained. The specific surface area of this dry gel is 530m2
/g. This was baked at 1200℃ for 5 hours,
Porous ceramics with a specific surface area of 120 m2/g were obtained.
（実施例２）
アルミニウムトリｓｅ叶ブトキシド［：（ｓｅｃ−Ｂｕ
ｎ）３＾１］９ｇとアセト酢酸エチル４．７５ｇを混合
し、１０ｍ１の２−ブタノールを添加した。また、リン
酸トリエトキシドＣＰ［］ （ｏｃ２ｈｓ） ３ ）
０．６１ｇと２−ブタノール０．２ｇを混ぜたものに
、水０．０７３ｇと２−ブタノール０．２ｇを混合した
ものを加えた。このリン酸アルコキシドの部分加水分解
物とアルミニウム）ｌＪｓｅＣ−ブトキシドの混合物を
混ぜた。これに水２．０４ｇと２〜ブタノ一ル２０ｍ１
の混合液を徐々に添加し、その後、６０℃に７２時間
保ちゲル化させた。この湿潤ゲルをオートクレーブ装置
で２３０ ｋｇ／ｃイ、２７０℃のエタノールの超臨界
状態でエタノールを除き、乾燥ゲルを得た。この乾燥ゲ
ルの比表面積は４９Ｑｒｎ’／ｇであった。これを１２
００℃、５時間で焼成して、比表面積１００ｍ２／ｇの
多孔質セラッミクスを得た。(Example 2) Aluminum trise butoxide [:(sec-Bu
n) 3^1] and 4.75 g of ethyl acetoacetate were mixed and 10 ml of 2-butanol was added. Also, phosphoric acid triethoxide CP[] (oc2hs) 3)
A mixture of 0.073 g of water and 0.2 g of 2-butanol was added to a mixture of 0.61 g and 0.2 g of 2-butanol. A mixture of this partial hydrolyzate of phosphoric acid alkoxide and aluminum) lJseC-butoxide was mixed. Add to this 2.04g of water and 20ml of 2-butanol.
A mixed solution was gradually added thereto, and then kept at 60° C. for 72 hours to form a gel. Ethanol was removed from this wet gel using an autoclave device at 230 kg/c and 270° C. in a supercritical ethanol state to obtain a dry gel. The specific surface area of this dry gel was 49Qrn'/g. This is 12
It was fired at 00°C for 5 hours to obtain porous ceramics with a specific surface area of 100 m2/g.
（比較例１）
アルミニウムトリ５ｅｃ−ブトキシドからのみ作成した
湿潤ゲルを常圧で徐々に溶媒を蒸発させて得た乾燥ゲル
は５５０ｍ２／ｇであったが、これを１２００℃×５時
間で焼成を行うと比表面積は３ｍ２／ｇ迄低下した。(Comparative Example 1) A dry gel obtained by gradually evaporating the solvent from a wet gel made only from aluminum tri-5ec-butoxide at normal pressure had a weight of 550 m2/g. When this was done, the specific surface area decreased to 3 m2/g.
（実施例３、比較例２）
実施例１でできたエアロゲル（Ａ１２０．−５ｉｎ２）
ヲ１２００℃Ｘ１０Ｄｈで焼成した時、Ｘ線回折測定
の結果、Ａｌ２Ｏ３はγアルミナでα化していないため
９２ｍ’／ｇと高い比表面積を維持したが、実施例１て
遅延化元素を含むシリコンアルコキシドを使用しない他
は実施例１と同様に形成したアルミナのみのエアロゲル
は１２００℃Ｘ１００ｈでαアルミナ化したため１３ｍ
＋／ ｇに低下した（第１図参照）。(Example 3, Comparative Example 2) Airgel made in Example 1 (A120.-5in2)
When fired at 1,200°C and 10Dh, X-ray diffraction measurements showed that Al2O3 was γ-alumina and had not been pregelatinized, so it maintained a high specific surface area of 92 m'/g. The alumina-only airgel formed in the same manner as in Example 1 except that no
+/g (see Figure 1).
本発明は、セラッミクス前駆体ゲル中に存在する有機溶
媒を超臨界状態で徐々に除去し、さらにＳｉなどの微量
成分でα相転移を遅らせるとともに粒成長をおさえるの
で、高温度状況下においても非常に高い比表面積を維持
できるセラッミクス触媒担体もしくは触媒を焼成により
製造できる成形性、一体性に優れた前駆体を製造できる
ので、高温化学プロセスの高効率化、高温装置の効率改
善等に寄与する所は極めて広範である。The present invention gradually removes the organic solvent present in the ceramic precursor gel in a supercritical state, and uses trace components such as Si to delay α phase transition and suppress grain growth, so it can be used even under high temperature conditions. Ceramic catalyst carriers or catalysts that can maintain a high specific surface area can be produced by firing, and precursors with excellent formability and integrity can be produced, contributing to higher efficiency in high-temperature chemical processes and improved efficiency in high-temperature equipment. is extremely broad.
第１図は、実施例３及び比較例２の結果を示すグラフで
ある。
○は、実施例３、△は比較例２である。
第 １
図
０ ： Ａｆｔ Ｏｉ −Ｓ ’Ｏｙ
エアＱ ’ｆｌｙFIG. 1 is a graph showing the results of Example 3 and Comparative Example 2. ◯ indicates Example 3, and △ indicates Comparative Example 2. 1st Figure 0: Aft Oi -S'Oy Air Q'fly
Claims (2)
アミン、βケト酸エステル、βジケトン化合物の１種ま
たは２種以上を０．１〜５倍モルと、アルミナのα相転
移温度を遅延しうる元素をアルミニウムアルコキシドに
対し、０．０１ｍｏｌ％〜３０ｍｏｌ％混合してアルミ
ナ系前駆体混合物を形成する工程、必要に応じて塩基触
媒の存在下、該混合物中に存在する加水分解しうる反応
基の数に対し０．５〜２倍モルの水で該前駆体混合物を
加水分解、ゲル化せしめる工程、および該ゲル中の液分
の大半を占める有機溶媒または少なくとも当該有機溶媒
を含む混合系の超臨界状態を経てゲルの乾燥を行う工程
からなることを特徴とするアルミナ系多孔質ゲルの製造
方法。(1) 0.1 to 5 times the mole of one or more of alkanolamines, β-keto acid esters, and β-diketone compounds to the aluminum alkoxide, and an element that can retard the α-phase transition temperature of alumina to the aluminum alkoxide. 0.01 mol% to 30 mol% of the mixture to form an alumina-based precursor mixture, optionally in the presence of a base catalyst, 0.01 mol% to 30 mol% based on the number of hydrolyzable reactive groups present in the mixture. A process of hydrolyzing and gelling the precursor mixture with .5 to 2 times the mole of water, and a supercritical state of an organic solvent that accounts for most of the liquid in the gel, or a mixed system containing at least the organic solvent. A method for producing an alumina-based porous gel, comprising a step of drying the gel.
リコンおよび／またはリンであることを特徴とする請求
項１記載のアルミナ系多孔質ゲルの製造方法。(2) The method for producing an alumina-based porous gel according to claim 1, wherein the element capable of delaying the α-phase transition temperature of alumina is silicon and/or phosphorus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2049609A JPH0818825B2 (en) | 1990-03-02 | 1990-03-02 | Method for producing alumina-based porous ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2049609A JPH0818825B2 (en) | 1990-03-02 | 1990-03-02 | Method for producing alumina-based porous ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03252312A true JPH03252312A (en) | 1991-11-11 |
| JPH0818825B2 JPH0818825B2 (en) | 1996-02-28 |
Family
ID=12835977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2049609A Expired - Lifetime JPH0818825B2 (en) | 1990-03-02 | 1990-03-02 | Method for producing alumina-based porous ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0818825B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0752389A1 (en) * | 1995-07-07 | 1997-01-08 | Universite Claude Bernard - Lyon 1 | Process for the preparation of monolithic silica aerogels and silica aerogels so obtained |
| CN102503508A (en) * | 2011-10-27 | 2012-06-20 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing alumina nanometer porous thermal insulation materials |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL125855A (en) * | 1998-04-06 | 2007-06-03 | Technion R & D Foundation Ltd | Method of producing ceramic foams |
-
1990
- 1990-03-02 JP JP2049609A patent/JPH0818825B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0752389A1 (en) * | 1995-07-07 | 1997-01-08 | Universite Claude Bernard - Lyon 1 | Process for the preparation of monolithic silica aerogels and silica aerogels so obtained |
| FR2736342A1 (en) * | 1995-07-07 | 1997-01-10 | Univ Claude Bernard Lyon | PROCESS FOR THE MANUFACTURE OF MONOLITHIC SILICA AEROGELS AND SILICA AEROGELS THUS OBTAINED |
| CN102503508A (en) * | 2011-10-27 | 2012-06-20 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing alumina nanometer porous thermal insulation materials |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0818825B2 (en) | 1996-02-28 |
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