JP2005296880A - Active oxygen occlusion substance, and its production method - Google Patents
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000001301 oxygen Substances 0.000 title claims abstract description 117
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 117
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000126 substance Substances 0.000 title abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 20
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 230000007704 transition Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011232 storage material Substances 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 12
- 150000002484 inorganic compounds Chemical class 0.000 claims description 10
- 229910010272 inorganic material Inorganic materials 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 5
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 claims description 2
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 claims 2
- 235000019169 all-trans-retinol Nutrition 0.000 claims 1
- 239000011717 all-trans-retinol Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 239000000969 carrier Substances 0.000 abstract 1
- 239000007784 solid electrolyte Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- -1 superoxide anions Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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Abstract
Description
本発明は、活性酸素吸蔵物質及びその製造方法等に関するものであり、更に詳しくは、酸素雰囲気で加熱することにより、活性酸素を吸蔵させた、活性酸素発現能力を有する無機化合物であって、Ａ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）で表記される組成式を有し、その構造中にスーパーオキサイドアニオン（Ｏ2 - ）を吸蔵させた新規活性酸素吸蔵物質、その製造方法及び用途に関するものである。本発明は、例えば、酸化触媒や、二輪車用排ガス浄化触媒、燃焼排ガス浄化触媒などの排ガス浄化触媒としての利用が高く期待されている、活性酸素を吸蔵し、活性酸素を発現する能力を有する活性酸素吸蔵物質の技術分野において、高い活性酸素発現能力を有する新しいタイプの活性酸素吸蔵物質を製造し、提供するものであり、本発明は、例えば、酸化触媒の構成成分としての利用や、更には、本発明の活性酸素吸蔵物質を成形体とすることにより、例えば、二輪車用排ガス浄化触媒、燃焼排ガス浄化触媒などへの利用を可能にする新規活性酸素吸蔵材料とその応用技術を提供するものとして有用である。 The present invention relates to an active oxygen storage material, a method for producing the same, and more specifically, and more specifically, an inorganic compound having active oxygen expression ability, which stores active oxygen by heating in an oxygen atmosphere, 2 New active oxygen occlusion having a composition formula represented by B 2 O 5 (A: alkali or alkaline earth element, B: transition element) and having superoxide anion (O 2 − ) occluded in its structure The present invention relates to a substance, its production method and use. INDUSTRIAL APPLICABILITY The present invention is expected to be used as an exhaust gas purification catalyst such as an oxidation catalyst, a motorcycle exhaust gas purification catalyst, a combustion exhaust gas purification catalyst, and the like. In the technical field of oxygen storage materials, a new type of active oxygen storage material having a high active oxygen expression ability is produced and provided. The present invention is used as, for example, a component of an oxidation catalyst, By providing the active oxygen storage substance of the present invention as a molded body, for example, a novel active oxygen storage material that can be used for an exhaust gas purification catalyst for motorcycles, a combustion exhaust gas purification catalyst, etc. and its application technology are provided. Useful.
近年、都市部を中心に大気汚染が深刻化する中で、光化学スモッグの原因とされる炭化水素、呼吸器疾患を起こす窒素酸化物の大幅な削減を目標とした新しい基準が、環境省の中央環境審議会でまとめられ、新基準として、大気汚染防止法に基づき２００４年に告示されようとしている。具体的には、２００６〜２００７年以降に販売されるオートバイなどの二輪車の排ガス規制が、大幅に強化される予定である。すなわち、新基準では、例えば、５０ｃｃ以下の原動機付自転車は、炭化水素が走行１ｋｍ当たり０．５ｇ（現行値比で削減率７５％）、窒素酸化物が０．１５ｇ（同５０％）であり、２００６年から適用される予定である。また、２５０ｃｃを超えるオートバイでは、炭化水素が０．３ｇ（同８５％）、窒素酸化物が０．１５ｇ（同５０％）であり、２００７年から適用される予定である。 In recent years, air pollution has become more serious in urban areas, and new standards aimed at drastically reducing hydrocarbons that cause photochemical smog and nitrogen oxides that cause respiratory diseases are It is compiled by the Environmental Council and is being announced in 2004 as a new standard based on the Air Pollution Control Act. Specifically, exhaust gas regulations for motorcycles and other motorcycles sold after 2006-2007 are expected to be significantly strengthened. In other words, under the new standard, for example, a motorbike with a capacity of 50 cc or less has 0.5 g of hydrocarbon per 1 km of travel (75% reduction rate compared to the current value) and 0.15 g of nitrogen oxide (50%). It will be applied from 2006. In addition, in motorcycles over 250 cc, hydrocarbons are 0.3 g (85%) and nitrogen oxides are 0.15 g (50%), which will be applied from 2007.
炭化水素は、ガソリンの不完全燃焼により排出されるが、二輪車は、乗用車の十倍以上排出し、四輪者と二輪車の全排出量の約２０％を占める。こうした状況下において、乗用車で使用されている触媒の二輪車への使用が種々検討されているが、これらの触媒の利用は、コストの安い二輪車では割高となり、当技術分野では、より安価な二輪車用排出ガス浄化触媒の開発が切望されている。 Hydrocarbons are emitted by incomplete combustion of gasoline, but motorcycles emit more than ten times as much as passenger cars, accounting for about 20% of the total emissions of automobiles and motorcycles. Under these circumstances, the use of catalysts used in passenger cars for motorcycles has been studied in various ways, but the use of these catalysts is expensive for motorcycles with lower costs, and in this technical field, for motorcycles that are less expensive. Development of an exhaust gas purification catalyst is eagerly desired.
自動車用触媒については、今日、例えば、Ｐｔ、Ｐｄ、Ｐｔ／Ｒｈ、Ｐｄ／Ｒｈ、Ｐｔ／Ｐｄ／Ｒｈなどが、コーディエライトで造られたモノリス型の担体上に担持され、三元触媒として使用されている。更に、空燃比の変動を吸収するために、酸素貯蔵物質セリアが、助触媒成分として用いられている。これらの貴金属は、触媒活性が高いが、コストが高く、しかも大量に使用する必要があるため、回収して再利用されている。 Regarding automobile catalysts, today, for example, Pt, Pd, Pt / Rh, Pd / Rh, Pt / Pd / Rh, etc. are supported on monolithic supports made of cordierite, and are used as three-way catalysts. in use. In addition, oxygen storage material ceria is used as a promoter component to absorb air-fuel ratio fluctuations. These noble metals have high catalytic activity, but are expensive and need to be used in large quantities, and thus are collected and reused.
従来、活性酸素発現物質として知られ、実用化されている物質としては、例えば、チタニア等に代表される光触媒がある。光（紫外線）が酸化チタンに吸収されると、電子と正孔が形成される。酸化チタンの場合、励起電子による還元力よりも正孔による酸化力が大きいため、触媒表面の吸着水が正孔によって酸化され、ヒドロキシラジカル（・ＯＨ）が生成する。その一方において、空気中の酸素の還元反応が進行し、活性酸素（Ｏ2 - ）が生成される。活性酸素は、酸化反応の中間体に付いて過酸化物の形成あるいは過酸化水素（Ｈ2 Ｏ2 ）を経て水になると考えられている。また、活性酸素は、炭素―炭素結合に直接作用して有機系有害物質を分解する場合もある。 Conventionally, as a substance known as an active oxygen expression substance and put into practical use, for example, there is a photocatalyst represented by titania and the like. When light (ultraviolet light) is absorbed by titanium oxide, electrons and holes are formed. In the case of titanium oxide, since the oxidizing power due to holes is greater than the reducing power due to excited electrons, the adsorbed water on the catalyst surface is oxidized by holes and hydroxy radicals (.OH) are generated. On the other hand, the reduction reaction of oxygen in the air proceeds, and active oxygen (O 2 − ) is generated. It is believed that active oxygen becomes water through the formation of peroxides or hydrogen peroxide (H 2 O 2 ) as an intermediate in the oxidation reaction. In addition, active oxygen may directly act on a carbon-carbon bond to decompose organic harmful substances.
活性酸素を発現する他の物質としては、例えば、活性酸素種を包接する１２ＣａＯ・７Ａｌ2 Ｏ3 化合物が知られている（例えば、特許文献１参照）。この１２ＣａＯ・７Ａｌ2 Ｏ3 化合物は、カルシウムとアルミニウムを原子当量比で１２：１４とした混合原料を用い、酸素分圧１０4 Ｐａ以上、好ましくは１０5 Ｐａ以上、水蒸気分圧１Ｐａ以下に厳密に制御された乾燥酸化雰囲気で、焼成温度１２００℃以上、好ましくは１３００℃の高温度の条件下で固相反応させることにより製造される。このように、これまで、活性酸素発現物質についての研究例が種々報告されているが、当技術分野では、更なる実用価値の高い新しい活性酸素発現物質の開発が強く要請されていた。 As another substance that expresses active oxygen, for example, a 12CaO · 7Al 2 O 3 compound that includes active oxygen species is known (see, for example, Patent Document 1). This 12CaO · 7Al 2 O 3 compound uses a mixed raw material of calcium and aluminum at an atomic equivalent ratio of 12:14, and has an oxygen partial pressure of 10 4 Pa or higher, preferably 10 5 Pa or higher, and a water vapor partial pressure of 1 Pa or lower. In a dry oxidizing atmosphere controlled to a solid phase under a high temperature condition of a firing temperature of 1200 ° C. or higher, preferably 1300 ° C. Thus, various research examples on active oxygen-expressing substances have been reported so far, but in this technical field, development of new active oxygen-expressing substances with higher practical value has been strongly demanded.
このような状況の中で、本発明者らは、上記従来技術に鑑みて、チタニア等の光触媒や１２ＣａＯ・７Ａｌ2 Ｏ3 化合物などのような、活性酸素を吸蔵することで活性酸素を発現する能力を有する新規活性酸素吸蔵物質を開発することを目標として鋭意研究を積み重ねた結果、Ａ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）と表記される物質が、酸素雰囲気で加熱することにより、活性酸素を吸蔵し、高い活性酸素発現能力を有すること、そして、酸化触媒等として有用であることを見出し、更に研究を重ねて、本発明を完成するに至った。 Under such circumstances, the present inventors express active oxygen by occluding active oxygen, such as a photocatalyst such as titania or a 12CaO · 7Al 2 O 3 compound, in view of the above-described conventional technology. As a result of intensive research aimed at developing new active oxygen storage materials having the ability, a substance represented as A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element) By heating in an oxygen atmosphere, it has been found that active oxygen is occluded, has a high ability to express active oxygen, and is useful as an oxidation catalyst, and the present invention has been completed through further research. .
すなわち、本発明は、強い酸化力を有する活性酸素を吸蔵させた、高い活性酸素発現作用を有する新規活性酸素吸蔵物質を提供することを目的とするものである。
更に、本発明は、活性酸素発現能力を有する新規活性酸素吸蔵物質である、Ａ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）の成形体を作製し、例えば、酸化触媒、二輪車などの排ガス浄化触媒、及び燃焼排ガス浄化触媒などを提供することを目的とするものである。
That is, an object of the present invention is to provide a novel active oxygen storage material having a high active oxygen expression action, in which active oxygen having strong oxidizing power is stored.
Furthermore, the present invention produces a molded body of A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element), which is a novel active oxygen storage material having an active oxygen expression capability, An object of the present invention is to provide an oxidation catalyst, an exhaust gas purification catalyst such as a motorcycle, and a combustion exhaust gas purification catalyst.
上記課題を解決するための、本発明は、以下の技術的手段から構成される。
（１）酸素雰囲気で加熱することにより、活性酸素であるスーパーオキサイドアニオン（Ｏ2 - ）を構造中に吸蔵させた、Ａ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）で表記される組成式を有する無機化合物から成ることを特徴とする活性酸素発現作用を有する活性酸素吸蔵物質。
（２）酸素雰囲気で加熱することにより、活性酸素であるスーパーオキサイドアニオンを構造中に吸蔵させた、Ｃａ2 Ｆｅ2 Ｏ5 で表記される組成式を有する、前記（１）に記載の活性酸素吸蔵物質。
（３）組成式がＡ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）になるように、原料粉末を混合し、次いで、酸素雰囲気で加熱することにより、活性酸素であるスーパーオキサイドアニオンを構造中に吸蔵させた、活性酸素発現作用を有する上記組成式を有する無機化合物から成る活性酸素吸蔵物質を作製することを特徴とする活性酸素吸蔵物質の製造方法。
（４）ＣａＣＯ3 とＦｅ2 Ｏ3 の混合原料を、酸素雰囲気で加熱することにより、活性酸素であるスーパーオキサイドアニオンを構造式中に吸蔵させた、Ｃａ2 Ｆｅ2 Ｏ5 で表記される組成式を有する無機化合物から成る活性酸素吸蔵物を作製する、前記（３）に記載の活性酸素吸蔵物質の製造方法。
（５）上記混合原料を、酸素雰囲気で８００〜１５００℃で加熱する、前記（３）又は（４）に記載の活性酸素吸蔵物質の製造方法。
（６）前記（１）又は（２）に記載の活性酸素発現作用を有する活性酸素吸蔵物質又はその成形体から成ることを特徴とする酸化触媒。
（７）前記（１）又は（２）に記載の活性酸素発現作用を有する活性酸素吸蔵物質の成形体から成ることを特徴とする排ガス浄化触媒。
（８）二輪車用排ガス浄化触媒又は燃焼排ガス浄化触媒である前記（７）に記載の排ガス浄化触媒。
In order to solve the above problems, the present invention comprises the following technical means.
(1) A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition) in which superoxide anion (O 2 − ) which is active oxygen is occluded in the structure by heating in an oxygen atmosphere An active oxygen storage material having an active oxygen expression function, comprising an inorganic compound having a composition formula represented by (element).
(2) The active oxygen according to (1), which has a composition formula represented by Ca 2 Fe 2 O 5 in which a superoxide anion that is active oxygen is occluded in the structure by heating in an oxygen atmosphere. Occlusion material.
(3) Active oxygen is obtained by mixing the raw material powder so that the composition formula is A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element) and then heating in an oxygen atmosphere. A method for producing an active oxygen storage material, comprising producing an active oxygen storage material comprising an inorganic compound having the above compositional formula having an active oxygen expression action, wherein the superoxide anion is occluded in the structure.
(4) A composition represented by Ca 2 Fe 2 O 5 in which a superoxide anion which is active oxygen is occluded in the structural formula by heating a mixed raw material of CaCO 3 and Fe 2 O 3 in an oxygen atmosphere. The method for producing an active oxygen storage material according to the above (3), wherein an active oxygen storage material comprising an inorganic compound having the formula is prepared.
(5) The manufacturing method of the active oxygen storage substance as described in said (3) or (4) which heats the said mixed raw material at 800-1500 degreeC by oxygen atmosphere.
(6) An oxidation catalyst comprising the active oxygen storage material having an active oxygen expression action as described in (1) or (2) above or a molded product thereof.
(7) An exhaust gas purification catalyst comprising the molded article of the active oxygen storage material having the active oxygen expression action described in (1) or (2).
(8) The exhaust gas purification catalyst according to (7), which is a motorcycle exhaust gas purification catalyst or a combustion exhaust gas purification catalyst.
次に、本発明について更に詳細に説明する。
本発明は、酸素雰囲気で加熱することにより、Ａ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）で表記される組成式を有する無機化合物に、活性酸素であるスーパーオキサイドアニオン（Ｏ2 - ）を構造中に吸蔵させ、活性酸素発現能力を付加させたことを特徴とするものである。本発明の活性酸素を吸蔵させた無機化合物は、組成式がＡ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）になるように、原料粉末を混合し、次いで、酸素雰囲気で加熱することにより、活性酸素であるスーパーオキサイドアニオンを構造中に吸蔵させることにより作製することができる。
Next, the present invention will be described in more detail.
The present invention provides a super compound which is an active oxygen to an inorganic compound having a composition represented by A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element) by heating in an oxygen atmosphere. This is characterized in that an oxide anion (O 2 − ) is occluded in the structure to add an active oxygen expression ability. The inorganic compound occluded with active oxygen of the present invention is mixed with the raw material powder so that the composition formula is A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element), By heating in an oxygen atmosphere, the superoxide anion which is active oxygen can be occluded in the structure.
次に、本発明の新規活性酸素吸蔵物質であるＡ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）の製造方法を、原料としてＡ＝Ｃａ、Ｂ＝Ｆｅを使用した場合について説明する。しかし、本発明の製造方法は、これらの原料及び製造方法に限定されるものではなく、これらを、他のアルカリ又はアルカリ土類元素、及び他の遷移元素で置換したものでも同様に使用することができる。原料は、例えば、Ｃａ源としてＣａＣＯ3 、及びＦｅ源としてＦｅ2 Ｏ3 を使用し、原料混合比（モル比）をＣａＣＯ3 ：Ｆｅ2 Ｏ3 ＝２〜４：１〜３として粉末混合する。このとき、原料の粒度を揃えることが望ましい。次に、混合した原料に対して酸素雰囲気で加熱処理を施す。この場合、酸素濃度は１００％でも、空気雰囲気の２０％でも構わないが、酸素濃度は高い方が望ましい。また、加熱温度は８００〜１５００℃、望ましくは１０００〜１３００℃であり、加熱保持時間は１時間以上、望ましくは２〜５時間である。加熱後、炉内で徐冷することが望ましいが、加熱終了後、炉外で急冷しても構わない。 Next, the production method of A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element), which is a novel active oxygen storage material of the present invention, uses A = Ca and B = Fe as raw materials. The case will be described. However, the production method of the present invention is not limited to these raw materials and production methods, and those in which these are substituted with other alkali or alkaline earth elements and other transition elements should also be used. Can do. For example, CaCO 3 is used as the Ca source, and Fe 2 O 3 is used as the Fe source, and the raw material mixing ratio (molar ratio) is CaCO 3 : Fe 2 O 3 = 2 to 4: 1 to 3 for powder mixing. . At this time, it is desirable to make the particle sizes of the raw materials uniform. Next, the mixed raw material is subjected to heat treatment in an oxygen atmosphere. In this case, the oxygen concentration may be 100% or 20% of the air atmosphere, but a higher oxygen concentration is desirable. The heating temperature is 800 to 1500 ° C., desirably 1000 to 1300 ° C., and the heating and holding time is 1 hour or longer, desirably 2 to 5 hours. Although it is desirable to cool slowly in the furnace after heating, it may be cooled outside the furnace after the heating.
また、本発明では、加熱温度を低減するために、上記ＣａＣＯ3 及びＦｅ2 Ｏ3 の混合原料に、必要に応じて、ＬｉＦを０．１〜１ｗｔ％、望ましくは０．３〜０．５ｗｔ％添加する。原料とＬｉＦの混合は、次の通りに行うことが望ましい。ＬｉＦをエタノールに分散させた懸濁液を予め調製し、それに混合原料を投入する。その後、例えば、超音波振動装置で１５分間混合し、続いて１００℃にて６時間以上乾燥する。得られた乾燥物を軽く粉砕した後、それを酸素雰囲気で加熱する。この場合、酸素濃度は、前記と同様に、なるべく高い方が望ましい。加熱温度は６００〜１２００℃、望ましくは８００〜１０００℃であり、加熱保持時間は１時間以上、望ましくは２〜５時間である。加熱後、炉内で徐冷することが望ましいが、急冷しても構わない。これらの処理工程における、処理方法及び手段については特に制限されるものではない。 In the present invention, in order to reduce the heating temperature, the mixed raw material of CaCO 3 and Fe 2 O 3 may contain LiF in an amount of 0.1 to 1 wt%, desirably 0.3 to 0.5 wt. %Added. It is desirable to mix the raw material and LiF as follows. A suspension in which LiF is dispersed in ethanol is prepared in advance, and the mixed raw materials are added thereto. Then, for example, it mixes for 15 minutes with an ultrasonic vibration apparatus, and then it dries at 100 degreeC for 6 hours or more. After the obtained dried product is lightly pulverized, it is heated in an oxygen atmosphere. In this case, it is desirable that the oxygen concentration be as high as possible, as described above. The heating temperature is 600 to 1200 ° C., desirably 800 to 1000 ° C., and the heating and holding time is 1 hour or longer, desirably 2 to 5 hours. Although it is desirable to cool slowly in the furnace after heating, it may be cooled rapidly. The processing method and means in these processing steps are not particularly limited.
上記本発明の方法及び手段により、目的の活性酸素吸蔵物質を作製することができる。本発明の活性酸素吸蔵物質であるＣａ2 Ｆｅ2 Ｏ5 が、活性酸素を吸蔵するか否かを調べる手段としては、好適には、例えば、ＥＳＲ測定法あるいはラマン分光測定法が用いられる。例えば、後記する実施例に示すように、Ｃａ2 Ｆｅ2 Ｏ5 の場合、その７７ＫにおけるＥＳＲ測定及び室温におけるラマン分光測定が行われる。まず、ＥＳＲ測定では、例えば、ｇ＝２．０１３に明確なシグナルが発現するが、このシグナルは、Ｃａ2 Ｆｅ2 Ｏ5 の構造中にスーパーオキサイドアニオン（Ｏ2 - ）が存在することを示す。また、ラマン分光測定では、ＥＳＲ測定の結果と同様に、スーパーオキサイドアニオン（Ｏ2 - ）の存在が１０７５ｃｍ-1のシグナルから確認できる。 The target active oxygen storage material can be produced by the method and means of the present invention. As a means for examining whether or not Ca 2 Fe 2 O 5 , which is the active oxygen storage substance of the present invention, stores active oxygen, for example, an ESR measurement method or a Raman spectroscopic measurement method is preferably used. For example, as shown in the examples described later, in the case of Ca 2 Fe 2 O 5 , ESR measurement at 77 K and Raman spectroscopic measurement at room temperature are performed. First, in the ESR measurement, for example, a clear signal is expressed at g = 2.014. This signal indicates that a superoxide anion (O 2 − ) is present in the structure of Ca 2 Fe 2 O 5. . In the Raman spectroscopic measurement, the presence of superoxide anion (O 2 − ) can be confirmed from the signal at 1075 cm −1 , as in the result of ESR measurement.
これらの測定結果から、本発明の活性酸素吸蔵物質であるＣａ2 Ｆｅ2 Ｏ5 は、構造中にスーパーオキサイドアニオンを吸蔵していることを確認することができる。本発明の活性酸素吸蔵物質であるＣａ2 Ｆｅ2 Ｏ5 の結晶構造は、斜方晶系であり、ａ＝５．６００Å、ｂ＝１４．７８Å、ｃ＝５．４３０Å、単位格子容積＝４４９．４Å3 である。 From these measurement results, it can be confirmed that Ca 2 Fe 2 O 5 , which is the active oxygen storage material of the present invention, has superoxide anions stored in its structure. The crystal structure of Ca 2 Fe 2 O 5 , which is the active oxygen storage material of the present invention, is orthorhombic, with a = 5.600Å, b = 14.78Å, c = 5.430Å, and unit cell volume = 449. .4Å is 3.
本発明の活性酸素吸蔵物質であるＣａ2 Ｆｅ2 Ｏ5 が吸蔵する活性酸素は、強い酸化力を有しており、例えば、揮発性有機化合物（ＶＯＣｓ）をＣＯ2 やＨ2 Ｏにまで完全酸化分解する能力を有する。また、この活性酸素は、炭化水素の酸化反応（例えば、エポキシ化、完全酸化、部分酸化、カップリング）を引き起こす機能を有する。これらのことから、本発明の活性酸素吸蔵物質は、酸化触媒の有効成分として使用することができ、例えば、環境分野で有害化学物質を酸化分解する材料としての用途が期待される。 The active oxygen stored by Ca 2 Fe 2 O 5, which is the active oxygen storage material of the present invention, has a strong oxidizing power. For example, volatile organic compounds (VOCs) are completely converted to CO 2 and H 2 O. Has the ability to undergo oxidative degradation. The active oxygen has a function of causing a hydrocarbon oxidation reaction (for example, epoxidation, complete oxidation, partial oxidation, coupling). For these reasons, the active oxygen storage substance of the present invention can be used as an active ingredient of an oxidation catalyst, and is expected to be used as a material for oxidatively decomposing harmful chemical substances in the environmental field, for example.
以上のような特長を有する本発明の活性酸素吸蔵物質は、その製造方法において得られる粉末として利用することができる。また、粉末としての利用以外に、成形体として利用することも可能であり、成形体としての利用では、多くの利便性と新たな機能の発現が期待される。成形体の形状は、使用目的に合わせて任意に決定される。また、成形方法は、セラミックス成形体の製造において使用される通常の方法を用いることができ、例えば、鋳込み成形、加圧成形、乾式ＣＩＰ成形、射出成形、シート成形などを使用することができる。成形体の形状は、例えば、顆粒、平板、柱状、円筒管、中空糸、モノリシス、ハニカムなどが例示される。また、成形時には形状と共に成形体の緻密さ、あるいは多孔質化が求められ、これらは、その使用目的等に応じて、任意に設計することができる。 The active oxygen storage material of the present invention having the above-described features can be used as a powder obtained in the production method. In addition to use as a powder, it can also be used as a molded body, and when used as a molded body, many conveniences and new functions are expected. The shape of the molded body is arbitrarily determined according to the purpose of use. Moreover, the normal method used in manufacture of a ceramic molded body can be used for a shaping | molding method, for example, casting molding, press molding, dry CIP molding, injection molding, sheet molding etc. can be used. Examples of the shape of the molded body include granules, flat plates, columns, cylindrical tubes, hollow fibers, monolysis, and honeycombs. Further, at the time of molding, it is required to make the molded body dense or porous with the shape, and these can be arbitrarily designed according to the purpose of use.
本発明により、１）高い活性酸素発現能力を有する新規活性酸素吸蔵物質及びその製造方法を提供することができる、２）本発明の活性酸素吸蔵物質は、例えば、酸化触媒、排ガス浄化触媒、特に、二輪車用排ガス浄化触媒、燃焼排ガス浄化触媒の有効成分として有用である、３）本発明により、新しいタイプの活性酸素吸蔵物質を提供することができる、という格別の効果が奏される。 According to the present invention, 1) a novel active oxygen storage material having a high active oxygen expression ability and a method for producing the same can be provided. 2) The active oxygen storage material of the present invention includes, for example, an oxidation catalyst, an exhaust gas purification catalyst, It is useful as an effective component for motorcycle exhaust gas purification catalysts and combustion exhaust gas purification catalysts. 3) According to the present invention, a special type of active oxygen storage material can be provided.
次に、実施例により本発明を具体的に説明するが、本発明は、以下の実施例により何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by the following examples.
微粉砕器で平均１０ミクロンに粒度を揃えたＣａＣＯ3 及びＦｅ2 Ｏ3 を原料とし、混合比（モル比）をＣａＣＯ3 ：Ｆｅ2 Ｏ3 ＝２：１としてこれらの粉末を混合した。次に、混合した原料を、加熱炉に入れ、空気雰囲気で１０００℃、３時間、加熱処理を施した後、炉内で室温まで徐冷し、Ｃａ2 Ｆｅ2 Ｏ5 を合成した。このＣａ2 Ｆｅ2 Ｏ5 の室温におけるＥＳＲを測定した。その結果を図１に示す。図に示されるように、ｇ＝２．０１３に明確なシグナルが発現するが、このシグナルは、Ｃａ2 Ｆｅ2 Ｏ5 の構造中に強い酸化力を有するスーパーオキサイドアニオン（Ｏ2 - ）が存在することを示すものである。 These powders were mixed using CaCO 3 and Fe 2 O 3 having a uniform particle size of 10 microns in a fine pulverizer as raw materials and a mixing ratio (molar ratio) of CaCO 3 : Fe 2 O 3 = 2: 1. Next, the mixed raw material was put into a heating furnace, subjected to heat treatment at 1000 ° C. for 3 hours in an air atmosphere, and then slowly cooled to room temperature in the furnace to synthesize Ca 2 Fe 2 O 5 . The ESR at room temperature of this Ca 2 Fe 2 O 5 was measured. The result is shown in FIG. As shown in the figure, a clear signal appears at g = 2.013, but this signal is present in the structure of Ca 2 Fe 2 O 5 with superoxide anion (O 2 − ) having strong oxidizing power. It shows what to do.
前記実施例１と同様の方法で合成したＣａ2 Ｆｅ2 Ｏ5 の室温でのラマン分光を測定した。その結果を図２に示す。図中、スーパーオキサイドアニオン（Ｏ2 - ）の存在が、１０７５ｃｍ-1のシグナルから確認される。 Raman spectroscopy at room temperature of Ca 2 Fe 2 O 5 synthesized by the same method as in Example 1 was measured. The result is shown in FIG. In the figure, the presence of superoxide anion (O 2 − ) is confirmed from the signal at 1075 cm −1 .
以上詳述したように、本発明は、酸素雰囲気で加熱することにより、活性酸素を吸蔵させた無機化合物からなる活性酸素吸蔵物質に係るものであり、本発明により、酸素雰囲気で加熱することにより、活性酸素であるスーパーオキサイドアニオン（Ｏ2 - ）を構造中に吸蔵させ、Ａ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）で表記される組成式を有する無機化合物から成る新規活性酸素吸蔵物質を提供することができる。また、本発明は、活性酸素（スーパーオキサイドアニオン：Ｏ2 - ）を吸蔵させたＡ2 Ｂ2 Ｏ5 （Ａ：アルカリ又はアルカリ土類元素、Ｂ：遷移元素）の成形体及びその応用製品を提供することができる。例えば、炭化水素の酸化反応では、本発明の活性酸素吸蔵物質の構造中に吸蔵された活性酸素により、酸化反応（例えば、エポキシ化・完全酸化・部分酸化、カップリング）を起こすことが可能であり、本発明の新規活性酸素吸蔵物質は、環境・エネルギー・化学工業（製造プロセス）等の広い分野で利用されることが期待できる。 As described above in detail, the present invention relates to an active oxygen storage material composed of an inorganic compound in which active oxygen is stored by heating in an oxygen atmosphere, and according to the present invention, by heating in an oxygen atmosphere. , A superoxide anion (O 2 − ), which is active oxygen, is occluded in the structure, and has an inorganic composition having a composition represented by A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element) A novel active oxygen storage material comprising a compound can be provided. The present invention also relates to a molded article of A 2 B 2 O 5 (A: alkali or alkaline earth element, B: transition element) in which active oxygen (superoxide anion: O 2 − ) is occluded and its application product. Can be provided. For example, in the oxidation reaction of hydrocarbons, it is possible to cause an oxidation reaction (for example, epoxidation, complete oxidation, partial oxidation, coupling) by the active oxygen stored in the structure of the active oxygen storage material of the present invention. The novel active oxygen storage material of the present invention can be expected to be used in a wide range of fields such as environment, energy, and chemical industry (manufacturing process).
Claims (8)
The exhaust gas purification catalyst according to claim 7, which is a two-wheeled vehicle exhaust gas purification catalyst or a combustion exhaust gas purification catalyst.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006255677A (en) * | 2005-03-18 | 2006-09-28 | Univ Nagoya | Oxidation catalyst and its manufacturing method |
| JP2006297324A (en) * | 2005-04-22 | 2006-11-02 | Univ Nagoya | Production method of oxidation catalyst |
| JP2013081920A (en) * | 2011-10-12 | 2013-05-09 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
| JP2013123689A (en) * | 2011-12-15 | 2013-06-24 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
| JP2014031282A (en) * | 2012-08-01 | 2014-02-20 | Univ Of Tokyo | Highly active oxygen carrier material in chemical looping method |
| CN112811476A (en) * | 2020-12-31 | 2021-05-18 | 华中科技大学 | Nickel-doped brownmillerite type oxygen carrier and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006255677A (en) * | 2005-03-18 | 2006-09-28 | Univ Nagoya | Oxidation catalyst and its manufacturing method |
| JP4635197B2 (en) * | 2005-03-18 | 2011-02-16 | 国立大学法人名古屋大学 | Oxidation catalyst for exhaust gas purification and method for producing the same |
| JP2006297324A (en) * | 2005-04-22 | 2006-11-02 | Univ Nagoya | Production method of oxidation catalyst |
| JP4625952B2 (en) * | 2005-04-22 | 2011-02-02 | 国立大学法人名古屋大学 | Method for producing oxidation catalyst |
| JP2013081920A (en) * | 2011-10-12 | 2013-05-09 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
| JP2013123689A (en) * | 2011-12-15 | 2013-06-24 | Toyota Motor Corp | Catalyst for cleaning exhaust gas |
| JP2014031282A (en) * | 2012-08-01 | 2014-02-20 | Univ Of Tokyo | Highly active oxygen carrier material in chemical looping method |
| CN112811476A (en) * | 2020-12-31 | 2021-05-18 | 华中科技大学 | Nickel-doped brownmillerite type oxygen carrier and preparation method and application thereof |
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