JP4071684B2 - Method for synthesizing reactive oxygen species inclusion materials - Google Patents
Method for synthesizing reactive oxygen species inclusion materials Download PDFInfo
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- JP4071684B2 JP4071684B2 JP2003280661A JP2003280661A JP4071684B2 JP 4071684 B2 JP4071684 B2 JP 4071684B2 JP 2003280661 A JP2003280661 A JP 2003280661A JP 2003280661 A JP2003280661 A JP 2003280661A JP 4071684 B2 JP4071684 B2 JP 4071684B2
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- 238000000034 method Methods 0.000 title claims description 14
- 239000000463 material Substances 0.000 title claims description 9
- 239000003642 reactive oxygen metabolite Substances 0.000 title claims description 8
- 230000002194 synthesizing effect Effects 0.000 title claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- 239000000292 calcium oxide Substances 0.000 description 13
- 235000012255 calcium oxide Nutrition 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- -1 calcium aluminate compound Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 235000012215 calcium aluminium silicate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Inert Electrodes (AREA)
Description
本発明は、活性酸素種包接物質の合成方法、特に、多量に活性酸素種を包接する物質を、より低い熱処理温度で合成する方法に関する。 The present invention relates to a method for synthesizing a reactive oxygen species inclusion substance, and more particularly to a method for synthesizing a substance that includes a large amount of reactive oxygen species at a lower heat treatment temperature.
12CaO・Al2O3と表されるカルシウムアルミネート系化合物の一種は、その結晶格子中に空隙(ケージ)を有している。
一方、活性酸素種として、O2 -イオンラジカルやO-イオンラジカルが知られている。
One type of calcium aluminate compound expressed as 12CaO · Al 2 O 3 has voids (cages) in its crystal lattice.
On the other hand, as the active oxygen species, O 2 - ion radical and O - ion radicals are known.
一般に、O2 -イオンラジカルは、固体構造中では常にカチオンで配位されており、フリーな状態になることはほとんどない。しかしながら、12CaO・7Al2O3結晶中では、O2 -イオンラジカルは、ケージ内に存在し、カチオンと結合できず、フリーな状態になっている。このような状態を「包接」といい、この状態は、固体表面に吸着した状態と類似しており、化学的に非常に活性な状態である。 In general, O 2 - ion radical is always cations in the solid structure are coordinated, it is unlikely to become a free state. However, in the 12CaO · 7Al 2 O 3 crystal, O 2 - ion radical is present in the cage can not bind to the cation, which is a free state. Such a state is referred to as “inclusion”, and this state is similar to the state of being adsorbed on the solid surface and is a chemically very active state.
そして、12CaO・Al2O3と表されるカルシウムアルミネート系化合物の一種には１×1019cm-3程度のO2 -が包接されていることを電子スピン共鳴の測定から見いだし、フリー酸素の一部がO2 -の形でケージ内に存在することが発表されている(非特許文献１参照)。 It was found from the measurement of electron spin resonance that one of the calcium aluminate compounds expressed as 12CaO · Al 2 O 3 contained O 2 − of about 1 × 10 19 cm -3. It has been announced that some oxygen is present in the cage in the form of O 2 − (see Non-Patent Document 1).
近年、活性酸素種を多量に包接する化合物が見出され、酸化触媒、イオン伝導体、及び固体電解質燃料電池用電極等への利用が期待されている(特許文献１、非特許文献２参照)。 In recent years, compounds that include a large amount of active oxygen species have been found, and are expected to be used for oxidation catalysts, ion conductors, electrodes for solid electrolyte fuel cells, and the like (see Patent Document 1 and Non-Patent Document 2). .
この方法は、12CaO・Al2O3と表されるカルシウムアルミネート系化合物の一種を、酸素分圧104Pa以上、水蒸気分圧102Pa以下の条件下で、1,200〜1,415℃で加熱処理することにより得られるもので、活性酸素種を1020cm-3以上の高濃度に包接するものであった。
しかしながら、従来の方法では、焼成温度1,200℃以上という高い温度での処理を必要とするものであり、エネルギー原単位や炭素排出量原単位の観点からは必ずしも環境負荷の小さい合成方法ではなかった。
In this method, a kind of calcium aluminate compound expressed as 12CaO · Al 2 O 3 is heated at 1,200 to 1,415 ° C. under conditions of an oxygen partial pressure of 10 4 Pa or more and a steam partial pressure of 10 2 Pa or less. The active oxygen species was included in a high concentration of 10 20 cm −3 or more.
However, the conventional method requires treatment at a high firing temperature of 1,200 ° C. or higher, and is not necessarily a synthesis method with a small environmental load from the viewpoint of energy intensity and carbon emission intensity.
今日では、より低温で合成できる環境負荷の小さい合成方法の開発が、さらに、触媒用途等にも利用可能な、しかも、より多くの活性酸素種を包接できる合成方法の開発が強く求められている。 Today, there is a strong demand for the development of synthesis methods with low environmental impact that can be synthesized at lower temperatures, and further for the synthesis methods that can be used for catalytic applications and that can include more active oxygen species. Yes.
一方、非晶質カルシウムアルミネートは、セメント混和材として広範に利用されている(例えば、特許文献２参照)。
そして、非晶質カルシウムアルミネートは工業的に大量に生産されており、入手が容易な素材である。
しかしながら、非晶質カルシウムアルミネートは活性酸素種を多量に包接できる化合物ではない。
Amorphous calcium aluminate is industrially produced in large quantities and is an easily available material.
However, amorphous calcium aluminate is not a compound that can include a large amount of active oxygen species.
本発明者は、鋭意努力を重ねた結果、特定の化合物を出発物質として、特定の条件で処理することにより、活性酸素種をこれまでにないほど多量に包接する物質を800℃程度の熱処理温度でも得ることが可能となることなどを知見し、本発明を完成するに至った。 As a result of intensive efforts, the present inventor treated a specific compound as a starting material under a specific condition to treat a substance that includes an active oxygen species in a large amount as never before, at a heat treatment temperature of about 800 ° C. However, the present inventors have found out that it can be obtained and completed the present invention.
本発明は、CaO/Al2O3モル比で1.25〜2.5の非晶質カルシウムアルミネートを、酸素分圧４×104Pa以上、水蒸気分圧102Pa以下の条件下で、800℃以上、1,100℃未満で加熱処理する12CaO・7Al 2 O 3 であるO2 -イオンラジカルやO-イオンラジカルの活性酸素種包接物質の合成方法であり、800℃以下の温度から、酸素分圧４×104Pa以上、水蒸気分圧102Pa以下に保ち、800℃以上、1,100℃未満の温度範囲まで昇温して加熱処理する該活性酸素種包接物質の合成方法である。 In the present invention, an amorphous calcium aluminate having a CaO / Al 2 O 3 molar ratio of 1.25 to 2.5 is 800 ° C. or higher under conditions of an oxygen partial pressure of 4 × 10 4 Pa or higher and a water vapor partial pressure of 10 2 Pa or lower. , O 2 is 12CaO · 7Al 2 O 3 to a heat treatment at lower than 1,100 ° C. - ion radical and O - a synthetic method of reactive oxygen species inclusion substance ion radical, 800 ° C. from the temperature, the oxygen partial pressure of 4 This is a method for synthesizing the active oxygen species clathrate, which is heated at a temperature range of 800 ° C. or higher and lower than 1,100 ° C. while maintaining a partial pressure of 10 4 Pa or higher and a water vapor partial pressure of 10 2 Pa or lower.
本発明の活性酸素種を包接する物質の合成方法によれば、工業的に多量に生産されている素材を利用して従来よりも低い熱処理温度で合成でき、活性酸素包接量も非常に多い活性酸素発現物質が得られる。 According to the method for synthesizing a substance that includes an active oxygen species according to the present invention, it is possible to synthesize at a lower heat treatment temperature than the conventional one using a large amount of industrially produced material, and the amount of active oxygen inclusion is very large. An active oxygen-expressing substance is obtained.
以下、本発明を詳細に説明する。
なお、本発明における部や％は特に規定しない限り質量基準で示す。
Hereinafter, the present invention will be described in detail.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.
本発明でいう活性酸素種包接物質とは、一般的に12CaO・7Al2O3と(以下、C12A7という)呼ばれるカルシウムアルミネート系化合物を含む物質を総称するものである。
本発明の活性酸素種包接物質は、C12A7を、例えば、50％以上含んでいれば良く、その他のカルシウムアルミネート類が混在していても何ら差し支えない。
ここで、カルシウムアルミネート類とは、CaOとAl2O3を主体とする化合物を総称するものであり、その具体例としては、例えば、CaO・Al2O3(以下、CAという)、11CaO・7Al2O3・CaF2、11CaO・7Al2O3・CaCl2、3CaO・Al2O3(以下、C3Aという)、及び3CaO・3Al2O3・CaSO4などがある。
また、上記のほかにも、4CaO・Al2O3・Fe2O3、6CaO・2Al2O3・Fe2O3、及び6CaO・Al2O3・2Fe2O3などのカルシウムアルミノフェライト類、ダイカルシウムシリケート2CaO・SiO2、ランキナイト3CaO・2SiO2、及びワラストナイトCaO・SiO2などのカルシウムシリケート類、ゲーレナイト2CaO・Al2O3・SiO2などのカルシウムアルミノシリケート類、並びに、遊離石灰等が混在する場合もある。
The active oxygen species inclusion substance referred to in the present invention is a general term for substances containing a calcium aluminate compound generally called 12CaO · 7Al 2 O 3 (hereinafter referred to as C 12 A 7 ).
The active oxygen species inclusion material of the present invention only needs to contain, for example, 50% or more of C 12 A 7 , and other calcium aluminates may be mixed.
Here, calcium aluminate is a generic term for compounds mainly composed of CaO and Al 2 O 3 , and specific examples thereof include, for example, CaO · Al 2 O 3 (hereinafter referred to as CA), 11CaO · 7Al 2 O 3 · CaF 2 , 11CaO · 7Al 2 O 3 · CaCl 2, 3CaO · Al 2 O 3 ( hereinafter, referred to as C 3 A), and the like 3CaO · 3Al 2 O 3 · CaSO 4.
In addition to the above, calcium aluminoferites such as 4CaO · Al 2 O 3 · Fe 2 O 3 , 6CaO · 2Al 2 O 3 · Fe 2 O 3 , and 6CaO · Al 2 O 3 · 2Fe 2 O 3 , Calcium silicates such as dicalcium silicate 2CaO · SiO 2 , rankinite 3CaO · 2SiO 2 , and wollastonite CaO · SiO 2 , calcium aluminosilicates such as galenite 2CaO · Al 2 O 3 · SiO 2 , and free Lime etc. may be mixed.
本発明では、非晶質カルシウムアルミネート(以下、Ａ−ＣＡという)を出発物質としてC12A7を含む活性酸素種包接物質を得る。
Ａ−ＣＡの組成は、通常、CaO/Al2O3モル比で1.25〜2.5が好ましく、1.50〜2.00がより好ましい。CaO/Al2O3モル比が1.25未満であったり、2.5を超えると、充分な活性酸素種の包接量が得られない場合がある。
In the present invention, an active oxygen species inclusion material containing C 12 A 7 is obtained using amorphous calcium aluminate (hereinafter referred to as A-CA) as a starting material.
In general, the composition of A-CA is preferably 1.25 to 2.5, more preferably 1.50 to 2.00 in terms of a CaO / Al 2 O 3 molar ratio. When the CaO / Al 2 O 3 molar ratio is less than 1.25 or exceeds 2.5, a sufficient amount of inclusion of active oxygen species may not be obtained.
Ａ−ＣＡはセメント混和材の主原料として工業的に多量に製造されている。
その製造方法は、CaO成分として生石灰等を用い、Al2O3成分としてボーキサイトなどを用い、これらを所定の割合で配合し、例えば、電気炉等で溶融後、水や高圧空気等で急冷する方法等が挙げることができる。
A-CA is industrially produced in large quantities as the main raw material for cement admixtures.
The production method uses quick lime or the like as the CaO component, bauxite or the like as the Al 2 O 3 component, and these are blended at a predetermined ratio, for example, after being melted in an electric furnace or the like, and then rapidly cooled with water or high-pressure air or the like The method etc. can be mentioned.
上記方法にてＡ−ＣＡを合成する際の溶融温度は、1,600℃以上が好ましく、1,650℃以上がより好ましい。1,600℃未満では非晶質化しにくい傾向にある。 The melting temperature at the time of synthesizing A-CA by the above method is preferably 1,600 ° C. or higher, more preferably 1,650 ° C. or higher. If it is less than 1,600 ° C, it tends not to be amorphous.
Ａ−ＣＡを工業的に得る場合、不純物が含まれることがある。その具体例としては、例えば、Li2O、Na2O、K2O、MgO、TiO2、MnO、Fe2O3、B2O3、SiO2、P2O5、S、フッ素、及び塩素等が挙げられる。 When A-CA is obtained industrially, impurities may be contained. Specific examples thereof include, for example, Li 2 O, Na 2 O, K 2 O, MgO, TiO 2 , MnO, Fe 2 O 3 , B 2 O 3 , SiO 2 , P 2 O 5 , S, fluorine, and Examples include chlorine.
本発明の活性酸素種包接物質の合成方法において、Ａ−ＣＡを熱処理する。
熱処理方法は、Ａ−ＣＡを800℃以上、1,110℃未満で加熱処理することが必要であり、900〜1,050℃で熱処理することが好ましい。800℃未満では活性酸素種の包接量が極めて少なく、1,100℃以上では従来法と変わらないエネルギーが必要となり好ましくない。また、1,100℃以上では、焼結反応が助長され、粉砕処理が必要になる場合がある。
In the method for synthesizing a reactive oxygen species inclusion material of the present invention, A-CA is heat-treated.
As the heat treatment method, it is necessary to heat-treat A-CA at 800 ° C. or more and less than 1,110 ° C., and it is preferable to perform heat treatment at 900 to 1,050 ° C. If the temperature is less than 800 ° C, the amount of the active oxygen species is extremely small. In addition, at 1,100 ° C. or higher, the sintering reaction is promoted and pulverization may be necessary.
また、熱処理の際、酸素分圧を４×104Pa以上、水蒸気分圧を102Pa以下の条件下で行う必要がある。上記の条件を満たさないと活性酸素種の包接量を多くすることができない。 In addition, it is necessary to perform the heat treatment under conditions where the oxygen partial pressure is 4 × 10 4 Pa or more and the water vapor partial pressure is 10 2 Pa or less. If the above conditions are not satisfied, the amount of inclusion of active oxygen species cannot be increased.
なお、熱処理の過程で昇温するが、本発明では、昇温の段階から、酸素分圧を高めておくことが望ましい。
即ち、C12A7が生成する800℃程度の温度よりも低い温度領域から酸素分圧を４×104Pa以上にし、水蒸気分圧を102Pa以下に保つことが好ましく、このような方法を行うことで、より多量の活性酸素種を包接することができるC12A7を生成することが可能である。
Although the temperature is raised during the heat treatment, in the present invention, it is desirable to increase the oxygen partial pressure from the stage of temperature rise.
That is, it is preferable to set the oxygen partial pressure to 4 × 10 4 Pa or higher and the water vapor partial pressure to 10 2 Pa or lower from a temperature range lower than about 800 ° C. generated by C 12 A 7. It is possible to generate C 12 A 7 that can include a larger amount of active oxygen species.
表１に示すような様々な比表面積をもつＡ−ＣＡを合成した。
合成したＡ−ＣＡを、昇温速度20℃/min.で1,000℃まで加熱し、３時間保持した。この際、加熱開始から酸素分圧を４×104Pa、水蒸気分圧を102Paに保った。得られた物質を粉末Ｘ線回折法により同定した。また、活性酸素種の包接量を測定した。結果を表１に併記する。
A-CA having various specific surface areas as shown in Table 1 was synthesized.
The synthesized A-CA was heated to 1,000 ° C. at a temperature rising rate of 20 ° C./min. And held for 3 hours. At this time, the oxygen partial pressure was maintained at 4 × 10 4 Pa and the water vapor partial pressure was maintained at 10 2 Pa from the start of heating. The resulting material was identified by powder X-ray diffraction. In addition, the amount of inclusion of active oxygen species was measured. The results are also shown in Table 1.
＜使用材料＞
各種Ａ−ＣＡは試薬１級の炭酸カルシウム(CaCO3)と試薬１級の酸化アルミニウム(Al2O3)を所定量混合粉砕して原料を調製し、さらにシリカを３％添加して電気炉で1,650℃で３時間溶融した後、急冷して合成
Ａ−ＣＡイ：CaCO31.25モルとAl2O3１モルを使用、CaO/Al2O3モル比1.25
Ａ−ＣＡロ：CaCO31.5モルとAl2O3１モルを使用、CaO/Al2O3モル比1.50
Ａ−ＣＡハ：CaCO31.71モルとAl2O3１モルを使用、CaO/Al2O3モル比1.71
Ａ−ＣＡニ：CaCO32.00モルとAl2O3１モルを使用、CaO/Al2O3モル比2.00
Ａ−ＣＡホ：CaCO32.50モルとAl2O3１モルを使用、CaO/Al2O3モル比2.50
従来法C12A7 ：従来法で得た活性酸素包接C12A7、CaCO312モルとAl2O3７モルを混合粉砕して原料を調製し、電気炉で1,350℃で３時間焼成する工程を２回繰り返して合成。得られたC12A7を振動式ボールミルにて可能なまで粉砕した。
<Materials used>
Various A-CAs are prepared by mixing and grinding a predetermined amount of reagent grade 1 calcium carbonate (CaCO 3 ) and reagent grade 1 aluminum oxide (Al 2 O 3 ), and then adding 3% silica to the electric furnace. in was melted for 3 hours at 1,650 ° C., rapidly cooled to synthetic a-CA Lee: CaCO 3 1.25 moles of Al 2 O 3 using 1 mol, CaO / Al 2 O 3 molar ratio 1.25
A-CAro: 1.5 mol of CaCO 3 and 1 mol of Al 2 O 3 , CaO / Al 2 O 3 molar ratio 1.50
A-CA C: CaCO 3 1.71 moles of Al 2 O 3 using 1 mol, CaO / Al 2 O 3 molar ratio 1.71
A-CA Two: CaCO 3 2.00 moles of Al 2 O 3 using 1 mol, CaO / Al 2 O 3 molar ratio 2.00
A-CA Ho: 2.50 mol of CaCO 3 and 1 mol of Al 2 O 3 used, CaO / Al 2 O 3 molar ratio 2.50
Conventional method C 12 A 7 : Active oxygen inclusion C 12 A 7 obtained by the conventional method, 12 mol of CaCO 3 and 7 mol of Al 2 O 3 are mixed and pulverized, and the raw material is prepared. It is synthesized by repeating the firing process twice. The obtained C 12 A 7 was pulverized to the extent possible with a vibrating ball mill.
＜測定方法＞
活性酸素種の包接量：電子スピン共鳴(ＥＳＲ)とラマンスペクトル法により定量
<Measurement method>
Inclusion amount of reactive oxygen species: quantified by electron spin resonance (ESR) and Raman spectroscopy
Ａ−ＣＡハを使用し、表２に示す温度で熱処理したこと以外は実施例１と同様に行った。結果を表２に併記する。 The same procedure as in Example 1 was performed except that A-CA c was used and heat treatment was performed at the temperature shown in Table 2. The results are also shown in Table 2.
Ａ−ＣＡハを使用し、酸素分圧を高める温度のタイミングを表３に示すように変化したこと以外は実施例１と同様に行った。結果を表３に併記する。 The same procedure as in Example 1 was carried out except that A-CA c was used and the temperature timing for increasing the oxygen partial pressure was changed as shown in Table 3. The results are also shown in Table 3.
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