JPH02175627A - Alumina silica compound, its production and oxygen-concentration meter, oxygen-purification apparatus and fuel cell utilizing the compound - Google Patents
Alumina silica compound, its production and oxygen-concentration meter, oxygen-purification apparatus and fuel cell utilizing the compoundInfo
- Publication number
- JPH02175627A JPH02175627A JP32931888A JP32931888A JPH02175627A JP H02175627 A JPH02175627 A JP H02175627A JP 32931888 A JP32931888 A JP 32931888A JP 32931888 A JP32931888 A JP 32931888A JP H02175627 A JPH02175627 A JP H02175627A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- silica
- alumina
- sol
- amorphous
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 44
- 239000000446 fuel Substances 0.000 title claims abstract description 15
- 238000000746 purification Methods 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 silica compound Chemical class 0.000 title claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 150000004703 alkoxides Chemical class 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 101100313164 Caenorhabditis elegans sea-1 gene Proteins 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 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 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
この発明は、基板用材料や吸着剤、或いは触媒担体等に
利用できる、非晶質または結晶質のアルミナシリカ系と
、該アルミナシリカ系の操作金部かつ経済的な製造法、
並びにこれを利用した酸素濃度計と酸素精製装置、及び
燃料電池に関する。Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to an amorphous or crystalline alumina-silica system that can be used as a substrate material, an adsorbent, a catalyst carrier, etc. Operating metal part and economical manufacturing method,
The present invention also relates to an oxygen concentration meter, an oxygen purification device, and a fuel cell using the same.
［従来の技術］
高温材料や高温触媒或いは基板材料等とじて有望視され
ているアルミナシリカ系は、アルミナ、シワ力共に溶融
温度が極めて高く、現在迄非晶質のアルミナシリカ系は
得られていない。[Prior art] Alumina-silica systems, which are considered promising as high-temperature materials, high-temperature catalysts, and substrate materials, have extremely high melting temperatures for both alumina and wrinkle resistance, and to date, amorphous alumina-silica systems have not been obtained. do not have.
例えば酸水素等を用いてアルミナとシリカの２成分系の
ものを、２０００Ｃ程度の非常に高い温度で溶融しても
、冷却時に分相と結晶化が起り、非晶質のものを作るこ
とができない。For example, even if a two-component system of alumina and silica is melted at a very high temperature of about 2000C using oxyhydrogen, phase separation and crystallization will occur during cooling, making it impossible to create an amorphous product. Can not.
一方、アルミナとシワ力の粉末を用いたムライト等の作
製が検討されているが、焼結性が悪く多くの問題点が残
されている。On the other hand, the production of mullite using alumina and wrinkle-resistant powder has been considered, but many problems remain due to poor sinterability.
［発明が解決しようとする課題］
この発明は、今迄得られなかった上記非晶質または結晶
質のアルミナシリカ系と、該アルミナシリカ系を、安価
な原料を用い比較的低温かつ苗筒な操作により、経済的
に作ることができる製造法、並びに上記アルミナシリカ
系を利用した酸素濃度計と酸素精製装置、及び燃料電池
を提供することを目的としている。[Problems to be Solved by the Invention] The present invention is directed to the above-mentioned amorphous or crystalline alumina-silica system, which has not been available until now, and the alumina-silica system, which can be produced using inexpensive raw materials at relatively low temperatures and in seedling tubes. The object of the present invention is to provide a manufacturing method that can be manufactured economically through various operations, as well as an oxygen concentration meter, an oxygen purification device, and a fuel cell using the alumina-silica system.
［課題を解決するための手段］
上記目的を達成するため、この発明の非晶質または結晶
質のアルミナシリカ系は、組成が下記の化学式で表され
ることを特徴とする。[Means for Solving the Problems] In order to achieve the above object, the amorphous or crystalline alumina-silica system of the present invention is characterized in that its composition is represented by the following chemical formula.
ＸＡＪ１２ｉ３・（１００Ｘ） ５ｈｏ２＊×−〇〜１
００
尚、上記組成の膜状、塊状、粉末状等の、非晶質または
結晶質のアルミナシリカ系は、アルミニューム塩とシリ
コンアルコキシドに、水、溶媒、或いは更に酸を加えて
ゾルを作り、該ゾルを乾燥してゲル化した後、熱処理す
ることにより製造することができる。XAJ12i3・(100X) 5ho2＊×−〇〜1
00 Incidentally, amorphous or crystalline alumina-silica in the form of a film, lump, powder, etc. having the above composition can be obtained by adding water, a solvent, or an acid to aluminum salt and silicon alkoxide to make a sol. It can be produced by drying the sol to form a gel and then heat-treating it.
また、上記アルミナシリカ系を利用した酸素濃度計は、
結晶質のアルミナシリカ系を、酸素分圧の異なる２系間
に介在させ、上記２系に生じた起電力の値を使用して、
酸素の濃度を測定するように構成したことを特徴とする
。In addition, the oxygen concentration meter using the alumina-silica system mentioned above is
A crystalline alumina-silica system is interposed between two systems with different oxygen partial pressures, and using the value of the electromotive force generated in the two systems,
The device is characterized in that it is configured to measure the concentration of oxygen.
また、酸素精製装置は、結晶質のアルミナシリカ系の両
端に外部から電位差を印加して、強制的に酸素だりを一
方側に移動させるように構成したことを特徴とする。Further, the oxygen purification device is characterized in that a potential difference is applied from the outside to both ends of the crystalline alumina-silica system to forcibly move oxygen to one side.
また、燃料電池は、結晶質のアルミナシリカ系の両側に
電極を設け、燃料と酸化剤を連続的に供給するようにし
たことを特徴とする。Further, the fuel cell is characterized in that electrodes are provided on both sides of the crystalline alumina-silica system, and fuel and oxidizing agent are continuously supplied.
［作用］
この発明のアルミナシリカ系は、アルミナとシリカの粉
末を熱処理するものでなく、アルミラム塩とシリコンア
ルコキシドを加水分解してゲルをつくり、このアルミナ
シリカ系の配位化合物を熱分解してつくるという、全く
新規な方法で作られ、低温では非晶質の、高温では結晶
質のアルミナシリカ系を作ることができる。[Function] The alumina-silica system of the present invention does not heat-treat alumina and silica powders, but hydrolyzes aluminum rum salt and silicon alkoxide to form a gel, and thermally decomposes this alumina-silica coordination compound. The alumina-silica system is made using a completely new method called "manufacturing", which is amorphous at low temperatures and crystalline at high temperatures.
そしてゾル状の配位化合物はどのような形状にでも形成
することができ、粉末状、塊状、膜状等のアルミナシリ
カ系を得ることができる。The sol-like coordination compound can be formed into any shape, and an alumina-silica system in the form of powder, lump, film, etc. can be obtained.
一般に、シリコンチップ、シリコンウェハ等の基板とし
ては、アルミナ等が用いられているが、シリコンチップ
或いはウェハとの熱膨張係数の差が大きい（アルミナ７
Ｘ１０ Ｋ 、シリコン３．５Ｘ１０ Ｋ ＞ので
、チップ搭載時にシリコンとの熱膨張の不整合が起こる
とされている。Generally, alumina and the like are used as substrates for silicon chips, silicon wafers, etc., but there is a large difference in thermal expansion coefficient from that of silicon chips or wafers (alumina 7
X10K, silicon 3.5X10K>, so it is said that thermal expansion mismatch with silicon occurs when the chip is mounted.
しかるに、×ＡＵ−０３・（１００−χ＞ Ｓ、Ｏ２で
表されるこの発明のアルミナシリカ系は、χ−５〜９０
…ＯＩ％ＡｉｚＯよ組成を変えることにより、熱膨張係
数を０．８８〜７．０Ｘ１０ Ｋ迄自由に制御するこ
とが可能でおる。そこで、ＡムＯ，−Ｓζ０２系の組成
で、
区が３．５Ｘ１ｏ Ｋ となる組成は、３０Ａ〕２
０３・７０５ｉｎ２から
５０Ａツユ０３・５０ ＳｔＯ□組成であり、これらの
組成を選ぶことにより、この発明のアルミナシリカ系は
基板材料としての利用が可能である。However, the alumina-silica system of the present invention represented by ×AU-03・(100-χ>S, O2
...By changing the composition such as OI%AizO, it is possible to freely control the thermal expansion coefficient from 0.88 to 7.0×10 K. Therefore, in the composition of the AmuO,-Sζ02 system, the composition where the ward is 3.5X1o K is 30A]2
The compositions are 03.705in2 to 50A, 03.50StO□, and by selecting these compositions, the alumina-silica system of the present invention can be used as a substrate material.
表１は、この発明のアルミナシリカ系の各処理温度にお
ける比表面積（ｍ７Ｑ＞を示す。Table 1 shows the specific surface area (m7Q>) of the alumina-silica system of the present invention at each treatment temperature.
表１
表１より、８００Ｃで熱処理したものの中でχ−１０Ａ
ｊ！、０．が最も比表面積か大きく、Ａ ｆ、、０．の
導入量の増加と共に減少してゆく傾向を示している。Table 1 From Table 1, among those heat-treated at 800C, χ-10A
j! ,0. has the largest specific surface area, A f,,0. It shows a tendency to decrease as the amount of introduction increases.
一般に、高温での触媒担体にはアルミナが用いられてい
るが、１０００’Ｃ以上になると比表面積が減少し始め
、１２００’Ｃでは１ｍ２／Ω程度になることか知られ
ている。Generally, alumina is used as a catalyst carrier at high temperatures, but it is known that the specific surface area begins to decrease at temperatures above 1000'C, and is approximately 1 m2/Ω at 1200'C.
しかし、この発明のアルミナシリカ系でアルミナ導入量
の多いχ−〇〜９０Ａλユ０６組成では８００’Ｃでの
比表面積はそれ程人きくないが、温度を上昇させても比
表面積の減少率は低く、１０００″Ｃでは略２０〜５６
ｍ２／ｇ、１３００’Ｃでも略１０〜２５ｍ２／Ｑの値
を持っている。また、アルミナ導入量の多い組成は耐熱
性及び耐熱衝撃性に優れていることから、自動車用排気
ガス或いは高温ボイラー用排気ガス等の、清浄化用触媒
担体としての利用が可能である。However, in the alumina-silica system of this invention with the χ-0~90Aλ Yu06 composition in which a large amount of alumina is introduced, the specific surface area at 800'C is not so good, but the rate of decrease in the specific surface area is low even when the temperature is increased. , approximately 20 to 56 at 1000″C
m2/g, it has a value of approximately 10 to 25 m2/Q even at 1300'C. In addition, since a composition containing a large amount of alumina has excellent heat resistance and thermal shock resistance, it can be used as a catalyst carrier for cleaning automobile exhaust gas, high-temperature boiler exhaust gas, etc.
また、χ−４０〜８０Ａ几Ｏ６系組成のものを酸素分圧
の異なる系１と系２間に介在させる。Further, a χ-40 to 80A O6 composition is interposed between systems 1 and 2 having different oxygen partial pressures.
ここで系１を排気ガス系、系２を大気圧系とする。この
ような系は酸素の化学ポテンシャルに関する一種の濃淡
電池を形成する。酸素分圧の高い系２とＡム０「Ｓ；０
２系の界面では、酸素分子が解離して酸素イオンの形で
ＡＪ・Ｏｊ−ＳｉＯ□系を通り、系１に向かって移動し
ようとする駆動力が働き、酸素イオンの移動に伴い高分
圧側に正、低分斤側に負の電位差が生じる。Here, system 1 is assumed to be an exhaust gas system, and system 2 is assumed to be an atmospheric pressure system. Such a system forms a kind of concentration cell for the chemical potential of oxygen. System 2 with high oxygen partial pressure and Am0 "S;0
At the interface of system 2, a driving force acts that causes oxygen molecules to dissociate and move in the form of oxygen ions through the AJ・Oj-SiO A positive potential difference is generated on the lower side, and a negative potential difference is generated on the lower side.
ＡλユＯ，−Ｓ、Ｏ，系は８００’Ｃ以上の高温で、イ
オン輸率がｔｉ＝ｌとなるので、自動車用排気ガスの酸
素濃度センサとして用いる場合、高分圧側の大気圧中の
酸素分圧は既知なので、生じた起電力の値を使って低圧
側の排気ガス中の酸素分圧を求めることができる。Since the AλyuO,-S,O, system has an ion transfer number of ti=l at a high temperature of 800'C or higher, when used as an oxygen concentration sensor for automobile exhaust gas, the Since the oxygen partial pressure is known, the oxygen partial pressure in the exhaust gas on the low pressure side can be determined using the value of the generated electromotive force.
この様に酸素濃度計（センサ）では、固体電解質の両端
の酸素濃度の差を起電力として検出することができる。In this way, the oxygen concentration meter (sensor) can detect the difference in oxygen concentration between both ends of the solid electrolyte as an electromotive force.
尚、Ａ Ｉ’、Ｏ，−３，０，系の両端に外部から電位
差を印加して強制的に酸素だけを一方の側に移動させる
酸素ポンプとしての利用が可能である。１例として、混
合ガスから純粋な酸素を精製することもできる。In addition, it is possible to use it as an oxygen pump in which a potential difference is applied from the outside to both ends of the A I', O, -3,0, system to forcibly move only oxygen to one side. As an example, pure oxygen can also be purified from a gas mixture.
また、Ｘ ＝ ５０ Ａｌｘｏｔ以上のＡ九０３ＳｒＯ
Ｊ。In addition, A903SrO with X = 50 Alxot or higher
J.
組成は、高温迄非常に安定で、高温での熱的耐久性も強
く、燃料電池としても非常に有望である。The composition is very stable up to high temperatures and has strong thermal durability at high temperatures, making it very promising as a fuel cell.
［実施例］
実施例１
硝酸アルミニウム、酢酸アルミニウム、及び塩化アルミ
ニウムを、化学式に従い所定量計りとり、水を加えて溶
解させ、この溶液に触媒としての酸を加えて攪はんした
後、溶媒としてアルコールを加え、攪はんしながらエチ
ルシリケ１〜を加え、加水分解してゾルを作製し、該ゾ
ル中に基板をデイツプするか、基板にゾルをスプレー法
で塗布し、７０〜８０’Ｃで水とアルコルを蒸発させ、
更に空気或いは酸素雰囲気下で２００〜１０００’Ｃの
間で熱処理することにより、アルミナシリカ系の非晶質
膜を得ることかできた。[Example] Example 1 Weigh out predetermined amounts of aluminum nitrate, aluminum acetate, and aluminum chloride according to the chemical formula, add water to dissolve them, add acid as a catalyst to this solution, stir it, and then use it as a solvent. Add alcohol and add ethyl silica 1~ with stirring, hydrolyze to prepare a sol, dip the substrate in the sol, or apply the sol to the substrate by spraying, and heat at 70-80'C. Evaporate water and alcohol
Furthermore, an alumina-silica amorphous film could be obtained by heat treatment at 200 to 1000'C in an air or oxygen atmosphere.
実施例２
実施例１で作ったゾルを３５°Ｃで放置してゲル化させ
、このゲルを乾燥させて水及びアルコールを蒸発させ、
更に空気或いは酸素雰囲気下で２００〜１００００Ｃで
熱処理し、塊状または粉末状のアルミナシリカ系を得た
。Example 2 The sol prepared in Example 1 was allowed to stand at 35°C to gel, and this gel was dried to evaporate water and alcohol.
Further, heat treatment was performed at 200 to 10,000 C in an air or oxygen atmosphere to obtain alumina-silica in the form of lumps or powder.
実施例３
硝酸アルミニウム、塩化アルミニウム、或いは流酸アル
ミニウムを化学式（こ従い所定量計りとり、純水をＨ−
０／ Ａ Ｊ−０３８ｒＯｚ＝ １０〜３０ｈａえ、そ
の後触媒として１規定の酸をモル比で酸／ Ａ １−Ｏ
ｈ Ｓｈｏよ−０，０３加え、攪はんしながら溶解さ
せる。この溶液に溶媒を、溶媒／Ａ 、ｔ’：ＬＯ，−
Ｓ、Ｏよ−１〜１０加え、高分子のシートで覆い均一に
なる迄連続的に潰はんする。この溶液にエチルシリケー
トを加え、磁気スターシー等の上で連続的に加熱腺はん
（３０〜６０’Ｃで１〜３時間）して加水分解を行い、
この溶液を３５°Ｃの恒温槽に静置して重量減少が殆ど
なくなったら１００’Ｃ迄昇温して乾燥ゲルを作りこの
乾燥ゲルを２００〜８００’Ｃて熱処理して非晶質の塊
状或いは粉末状アルミナシリカ系を得ｌご 。Example 3 Weigh out a specified amount of aluminum nitrate, aluminum chloride, or aluminum sulfuric acid according to the chemical formula (according to the chemical formula), and add pure water to H-
0/A J-038rOz= 10~30ha, then add 1N acid as a catalyst at a molar ratio of acid/A 1-O
h Add Shoyo-0.03 and dissolve while stirring. Add a solvent to this solution, solvent/A, t': LO, -
Add 1 to 10% of S and O, cover with a polymer sheet, and mash continuously until uniform. Ethyl silicate is added to this solution and hydrolyzed by continuous heating (at 30-60'C for 1-3 hours) on a magnetic starch etc.
This solution is left in a constant temperature bath at 35°C, and when there is almost no weight loss, the temperature is raised to 100'C to form a dry gel. This dried gel is heat-treated at 200 to 800'C to form an amorphous mass. Alternatively, obtain a powdered alumina-silica type.
実施例４
硝酸アルミニウムを化学式に従い所定量計りとり、水を
モル比で、ｌ−１，０／ Ａ Ｒ，Ｏ，−Ｓｉ ０゜１
０〜２０加え、更に触媒としてモル比で、１規定Ｈσ／
Ａｆ□○、−３ｒＯ２＝ ２〜８加え、高分子のシー１
〜で覆い、均一になる迄攪はんする。Example 4 Weigh out a predetermined amount of aluminum nitrate according to the chemical formula, and add water at a molar ratio of 1-1,0/A R,O,-Si 0゜1
0 to 20, and further as a catalyst in molar ratio, 1N Hσ/
Af □○, -3rO2 = 2 to 8 plus polymer sea 1
Cover with ~ and stir until uniform.
この溶液にシリコンエキシトＳ ； （ＯＣ２ｔ−１ｒ
＞＋を化学式に従い計りとり、６０〜７０’Ｃで加熱し
ながら２時間攬はんして加水分解し、約３５’Ｃの恒温
槽でゲルを作製する。このゲルを実施例３に準じて熱処
理し、大きな塊状の非晶質アルミナシリカ系を得た。Add silicon excito S to this solution; (OC2t-1r
＞+ is weighed out according to the chemical formula, stirred for 2 hours while heating at 60-70'C to be hydrolyzed, and a gel is prepared in a constant temperature bath at about 35'C. This gel was heat-treated according to Example 3 to obtain a large block of amorphous alumina-silica.
以上実＃ｆＡ４例について説明したが、アルミラム塩に
は、硝酸アルミニウムＡＪ２ （Ｎ （Ｊ）ｔ））Ｊ
・９目２０、塩化アルミニウムＡｊ、ＣＪ２３・６Ｈ，
○、流酸アルミニウムＡ叉２（ＳＯψ３・１８ Ｈ，Ｏ
、アルミニウムホルモアセテート
ＡＪｌ！ （ＯＨ）（ＯＯＣＨ）（ＯＯＣＣＨ３）等
を使用することができ、溶媒としてのアルコールにはメ
チルアルコール、エチルアルコール、１−プロパツール
、１−ブタノール、エチレングリコール等を使用するこ
とができる。また、加水分解を促進するために使用され
る触媒には塩酸、硝酸、酢酸等の酸を使用できるが、触
媒の使用は必ずしも必要ではない。Above, we have explained the actual #fA4 examples, but aluminum nitrate AJ2 (N (J)t))J
・9 eyes 20, aluminum chloride Aj, CJ23・6H,
○, aluminum sulfuric acid A-2 (SOψ3・18 H, O
, aluminum formacetate AJl! (OH)(OOCH)(OOCCH3), etc. can be used, and as the alcohol as a solvent, methyl alcohol, ethyl alcohol, 1-propanol, 1-butanol, ethylene glycol, etc. can be used. Furthermore, acids such as hydrochloric acid, nitric acid, and acetic acid can be used as catalysts to promote hydrolysis, but the use of catalysts is not always necessary.
次に、この発明のアルミナシリカ系を利用した、酸素濃
度計と酸素精製装置及び燃料電池につき説明する。Next, an oxygen concentration meter, an oxygen purification device, and a fuel cell using the alumina-silica system of the present invention will be explained.
第１図は酸素濃度計の原理図を示し、１はアルミナシリ
カ系、２はその系１側に、３は系２側に設けられた電極
であり、前記したように両端の酸素濃度の差を起電力と
して検出し、酸素濃度を計測する。尚、両端に外部から
電位差を印加して強制的に酸素だけを一方側に移動させ
るように構成すると、酸素精製装置として使用すること
ができる。Figure 1 shows the principle diagram of an oxygen concentration meter, in which 1 is an alumina-silica system, 2 is an electrode provided on the system 1 side, and 3 is an electrode provided on the system 2 side, and as mentioned above, the difference in oxygen concentration between the two ends. is detected as an electromotive force and the oxygen concentration is measured. In addition, if a potential difference is applied from the outside to both ends to forcefully move only oxygen to one side, it can be used as an oxygen purification device.
第２図は燃料電池の原理図を示し、４はアルミナシリ力
系、５及び６はその両側に設けられた白金製の多孔質電
極であり、還元剤としての燃料（Ｈ，＞７と酸化剤（０
２）８を連続的に供給すると、生成酸化物が間断なく除
去される。Figure 2 shows the principle diagram of a fuel cell, where 4 is an alumina silica system, 5 and 6 are platinum porous electrodes provided on both sides, and the fuel as a reducing agent (H, >7 and the oxidizing agent (0
2) When 8 is continuously supplied, the produced oxide is removed without interruption.
正 極・・・１／２０□＋２ｅ−→０２−負 極・・・
１」よ＋Ｏ”’−−＋ Ｈ２Ｏ＋２８全反応・・何
４＋１／２ ０ｚ →＋−１ｚ。Positive pole...1/20□+2e-→02-negative pole...
1''+O'''--+ H2O+28 total reaction...what 4+1/2 0z →+-1z.
［発明の効果］
この発明は前記のように構成され、非晶質のアルミナシ
リカ系は基板用ガラス膜や任意な低熱膨張係数を持つ塊
状ガラスとして、また、微小で均一な粒径を持つ非晶質
のアルミナシリカ系は、高温材料、高温触媒、吸着剤等
として利用でき、製造法も、安価な原料を使用し比較的
低温で操作金部につくることができて極めて経済的であ
り、酸素濃度計、酸素生成装置、燃料電池等として利用
できる等、多々の用途を有する。[Effects of the Invention] The present invention is constructed as described above, and the amorphous alumina-silica system can be used as a glass film for substrates, as a lump glass having an arbitrary low coefficient of thermal expansion, and as a non-crystalline glass with a fine and uniform particle size. Crystalline alumina-silica can be used as high-temperature materials, high-temperature catalysts, adsorbents, etc., and the manufacturing method is extremely economical as it can be made into operating parts at relatively low temperatures using inexpensive raw materials. It has many uses, such as being used as an oxygen concentration meter, oxygen generator, fuel cell, etc.
第１図は酸素）開度計の原理図、第２図は燃料電池の原
理図である。
１．４・・・アルミナシリカ系 ２．３・・・電極５．
６・・・多孔質電極 ７・・・燃料 ８・・・酸化剤第
１区
第２図Fig. 1 is a diagram of the principle of an oxygen (oxygen) opening gauge, and Fig. 2 is a diagram of the principle of a fuel cell. 1.4... Alumina silica type 2.3... Electrode 5.
6...Porous electrode 7...Fuel 8...Oxidizer 1st section Figure 2
Claims (5)
質のアルミナシリカ系。 ＸＡｌ＿２Ｏ＿３・（１００−Ｘ）ＳｉＯ＿２＊Ｘ＝０
〜１００(1) Amorphous or crystalline alumina-silica whose composition is represented by the chemical formula below. XAl_2O_3・(100-X)SiO_2*X=0
~100
、溶媒、或いは更に酸を加えてゾルを作り、該ゾルを乾
燥してゲル化した後、熱処理してなることを特徴とする
、請求項１記載の化学式を有する膜状、塊状、粉末状等
の、非晶質または結晶質のアルミナシリカ系の製造法。(2) A sol is prepared by adding water, a solvent, or an acid to aluminum salt and silicon alkoxide, and the sol is dried to gel, and then heat-treated. A method for producing amorphous or crystalline alumina-silica in the form of a film, lump, powder, etc. having the chemical formula:
素分圧の異なる２系間に介在させ、上記２系に生じた起
電力の値を使用して、酸素の濃度を測定するように構成
したことを特徴とする、酸素濃度計。(3) The crystalline alumina-silica system according to claim 1 is interposed between two systems having different oxygen partial pressures, and the concentration of oxygen is measured using the value of the electromotive force generated in the two systems. An oxygen concentration meter characterized by being configured as follows.
に外部から電位差を印加して、強制的に酸素だけを一方
側に移動させるように構成したことを特徴とする、酸素
精製装置。(4) An oxygen purification device characterized in that a potential difference is applied from the outside to both ends of the crystalline alumina-silica system according to claim 1, so that only oxygen is forcibly moved to one side.
に電極を設け、燃料と酸化剤とを連続的に供給するよう
に構成したことを特徴とする、燃料電池。(5) A fuel cell characterized in that electrodes are provided on both sides of the crystalline alumina-silica system according to claim 1, so that fuel and oxidizing agent are continuously supplied.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32931888A JPH02175627A (en) | 1988-12-28 | 1988-12-28 | Alumina silica compound, its production and oxygen-concentration meter, oxygen-purification apparatus and fuel cell utilizing the compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32931888A JPH02175627A (en) | 1988-12-28 | 1988-12-28 | Alumina silica compound, its production and oxygen-concentration meter, oxygen-purification apparatus and fuel cell utilizing the compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02175627A true JPH02175627A (en) | 1990-07-06 |
Family
ID=18220121
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32931888A Pending JPH02175627A (en) | 1988-12-28 | 1988-12-28 | Alumina silica compound, its production and oxygen-concentration meter, oxygen-purification apparatus and fuel cell utilizing the compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02175627A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021101478A (en) * | 2018-08-31 | 2021-07-08 | Ｍｉｒａｉ−Ｌａｂｏ株式会社 | Photovoltaic power generation panel, pavement structure, and wall surface structure |
-
1988
- 1988-12-28 JP JP32931888A patent/JPH02175627A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021101478A (en) * | 2018-08-31 | 2021-07-08 | Ｍｉｒａｉ−Ｌａｂｏ株式会社 | Photovoltaic power generation panel, pavement structure, and wall surface structure |
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