JP3162583B2 - Method and catalyst element for enhancing activity of solid catalyst - Google Patents
Method and catalyst element for enhancing activity of solid catalystInfo
- Publication number
- JP3162583B2 JP3162583B2 JP23790994A JP23790994A JP3162583B2 JP 3162583 B2 JP3162583 B2 JP 3162583B2 JP 23790994 A JP23790994 A JP 23790994A JP 23790994 A JP23790994 A JP 23790994A JP 3162583 B2 JP3162583 B2 JP 3162583B2
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- Japan
- Prior art keywords
- catalyst
- piezoelectric body
- voltage
- activity
- applying
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、著しく高い触媒活性を
実現することができる固体触媒の活性を高める方法およ
びその方法の実施に用いられる触媒素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for enhancing the activity of a solid catalyst capable of realizing a remarkably high catalytic activity, and a catalyst element used for carrying out the method.
【０００２】[0002]
【従来の技術】従来の固体触媒の活性化方法には酸化処
理、還元処理、真空排気処理等があり、これらの方法は
触媒反応前に行われるものであるが、触媒反応中にすば
やく触媒活性を変えることはできなかった。2. Description of the Related Art Conventional methods for activating a solid catalyst include an oxidation treatment, a reduction treatment, and a vacuum evacuation treatment. These methods are performed before a catalytic reaction. Could not be changed.
【０００３】本発明者は、これらの方法と全く異なる方
法、すなわち、圧電体に触媒を担持し外部から交流電圧
を与えて共振状態を発生させる方法により触媒の活性が
有意に高められることを提案した。具体的には、図４に
示すように、ストロンチウムを５モル％含むチタン酸ジ
ルコン酸鉛からなる圧電体ペレット２と、このペレット
２上に設けられ端部にリード線３が接続された電極５
と、この電極上に５０ｎｍ厚のＣｕ触媒が蒸着されてな
る触媒層４と、その片面にシリコンペーストで固着され
た温度測定用の熱電対６とから構成される触媒素子１を
用い、圧電体２に交流電圧を印加してエタノール酸化反
応を行った結果、共振周波数８５ｋＨｚ（ピーク値）に
おいてアセトアルデヒド生成の触媒活性が６倍程度増加
することを報告している（平成４年１０月３日〜５日、
日本化学会触媒学会第７０回触媒討論会（Ａ）講演要旨
（４Ｆ５２４）ｐ．６１０−６１１）。The present inventor has proposed that the activity of the catalyst can be significantly enhanced by a method completely different from these methods, that is, a method in which a catalyst is supported on a piezoelectric body and an AC voltage is externally applied to generate a resonance state. did. Specifically, as shown in FIG. 4, a piezoelectric pellet 2 made of lead zirconate titanate containing 5 mol% of strontium, and an electrode 5 provided on the pellet 2 and having a lead wire 3 connected to an end portion thereof.
And a catalyst layer 4 having a 50 nm-thick Cu catalyst deposited on the electrode and a thermocouple 6 for temperature measurement fixed on one surface thereof with a silicon paste. No. 2 reported that the catalytic activity for acetaldehyde generation increased about 6 times at a resonance frequency of 85 kHz (peak value) as a result of performing an ethanol oxidation reaction by applying an AC voltage (October 3, 1992- 5th,
Abstracts of the 70th Symposium on Catalysis of the Chemical Society of Japan (A), p. 610-611).
【０００４】このように数倍にも触媒活性が増加する理
由は、圧電体に発生した音波がその進行方向にある電子
を表面に集積させるフォノンドラッグ効果が働き、この
電子集積が吸着酸素の負電荷状態を増して吸着エタノー
ルからの水素引き抜きを促進して結果的に活性が増加す
るためであると考えられた。[0004] The reason why the catalytic activity is increased several times as described above is that a sound wave generated in the piezoelectric body has a phonon drag effect of accumulating electrons in the traveling direction on the surface, and this electron accumulation is a negative effect of adsorbed oxygen. It was considered that the charge state was increased to promote hydrogen abstraction from the adsorbed ethanol, resulting in an increase in activity.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来の
圧電体担持触媒の活性化方法によれば、触媒の作用が高
められるものの、活性化の程度は充分満足できるもので
はなかった。よって、本発明の目的は圧電体担持触媒の
活性を著しく高めることにある。However, according to the conventional method of activating a piezoelectric-supported catalyst, the effect of the catalyst is enhanced, but the degree of activation is not sufficiently satisfactory. Therefore, an object of the present invention is to remarkably increase the activity of a catalyst carrying a piezoelectric substance.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記目的を達
成するため、表面に触媒層が形成された圧電体にその固
有の共振周波数を発生させる交流電圧を印加して固体触
媒の活性を高める方法であって、前記圧電体の格子変位
の運動を妨げることなく前記交流電圧を印加することを
特徴とする固体触媒の活性を高める方法を提供するもの
である。According to the present invention, in order to achieve the above object, the activity of a solid catalyst is increased by applying an AC voltage to a piezoelectric body having a catalyst layer formed on its surface to generate its own resonance frequency. An object of the present invention is to provide a method for increasing the activity of a solid catalyst, wherein the alternating voltage is applied without hindering the movement of the lattice displacement of the piezoelectric body.
【０００７】また、本発明は、表面に触媒層が形成され
た圧電体にその固有の共振周波数を発生させる交流電圧
を印加して固体触媒の活性を高める方法であって、触媒
層表面に局所的な異常変位が発現する程度の共振エネル
ギーを圧電体に与えることを特徴とする固体触媒の活性
を高める方法を提供するものである。Another object of the present invention is a method for increasing the activity of a solid catalyst by applying an AC voltage for generating a resonance frequency unique to a piezoelectric body having a catalyst layer formed on the surface thereof. It is intended to provide a method for enhancing the activity of a solid catalyst, which is characterized by giving resonance energy to the piezoelectric element to such an extent that an abnormal displacement occurs.
【０００８】さらに、本発明は、固有の共振周波数を発
生させる交流電圧を印加するためのリード線が接合され
た圧電体の表面に触媒層が形成された触媒素子であっ
て、前記触媒層または前記圧電体に接続され圧電体の格
子変位の運動を妨げる要素が除かれていることを特徴と
する触媒素子を提供するものである。Further, the present invention is a catalyst element having a catalyst layer formed on the surface of a piezoelectric body to which a lead wire for applying an AC voltage for generating a unique resonance frequency is joined, wherein the catalyst layer or the catalyst layer is formed. An object of the present invention is to provide a catalyst element, wherein an element connected to the piezoelectric body and hindering a movement of a lattice displacement of the piezoelectric body is removed.
【０００９】[0009]
【作用】本発明では、実際に圧電体の格子変位の運動を
妨げないようにして交流電圧を印加することにより、異
常に高い触媒活性（約２００〜２０００倍）が得られて
いる。このことは、前述のフォノンドラッグ効果（従来
の電子集積効果）によっては到底説明ができない。つま
り、本発明では、圧電体の格子変位の運動を妨げないこ
とによって共振エネルギーが高まり、このエネルギーが
所定の閾値を超えたときに、触媒表面に存在する格子欠
陥や転位などの特異な場所（原子が疎の部分）に変位効
果が異常に集中して局所的に異常変位が発現することに
より、新たな反応活性点が形成されるものである。この
ため、通常考えられない程の触媒活性が得られている。According to the present invention, an abnormally high catalytic activity (about 200 to 2000 times) is obtained by applying an AC voltage so as not to actually hinder the movement of the lattice displacement of the piezoelectric body. This cannot be explained at all by the phonon drag effect (conventional electron integration effect) described above. That is, in the present invention, the resonance energy is increased by not hindering the movement of the lattice displacement of the piezoelectric body, and when this energy exceeds a predetermined threshold value, a specific location such as a lattice defect or dislocation existing on the catalyst surface ( When the displacement effect concentrates abnormally on the part where the atoms are sparse) and abnormal displacement locally appears, a new reaction active site is formed. For this reason, a catalyst activity which is not usually considered is obtained.
【００１０】共振状態における圧電体の格子変位の運動
を妨げない方法の一つは、触媒表面温度測定用の熱電対
が備え付けられていないことにより、前記圧電体の格子
変位の運動を妨げることなく交流電圧を印加することで
ある。使用する触媒の種類、反応条件に依存するが、熱
電対が備え付けられていない場合、きわめて予想外なこ
とに、触媒活性は約２００〜２０００倍に高められる。One of the methods of not hindering the movement of the lattice displacement of the piezoelectric body in the resonance state is that the thermocouple for measuring the catalyst surface temperature is not provided, so that the movement of the lattice displacement of the piezoelectric body is not hindered. That is, an AC voltage is applied. Depending on the type of catalyst used and the reaction conditions, without a thermocouple the catalyst activity is unexpectedly increased about 200 to 2000 times.
【００１１】本発明は、遷移金属、遷移金属酸化物、典
型金属酸化物、金属硫化物、金属塩等のあらゆる固体触
媒に適用可能であり、例えば、Ｆｅ、Ｃｏ、Ｎｉ、Ｐ
ｄ、Ｃｕ、Ａｇ、Ｐｔ、ＭｏＯ3 、Ｆｅ2 Ｏ3 、ＮｉＯ
等、或いはこれらの混合物にも適用できる。The present invention is applicable to all solid catalysts such as transition metals, transition metal oxides, typical metal oxides, metal sulfides, and metal salts. For example, Fe, Co, Ni, P
d, Cu, Ag, Pt, MoO 3 , Fe 2 O 3 , NiO
Etc., or a mixture thereof.
【００１２】[0012]
【実施例】以下、本発明の実施例を説明する。ただし、
本発明はこれらの実施例により限定的に解釈されるべき
ものではない。Embodiments of the present invention will be described below. However,
The present invention should not be construed as being limited by these examples.
【００１３】＜実施例１＞まず、銀電極５をもつストロ
ンチウム（５モル％）含有チタン酸ジルコン酸鉛（燒結
体）の圧電体ペレット２の端部に銀ペーストで交流電力
印加用のリード線（銀）３を固着した後、ペレット両面
にパラジウム金属を真空蒸着して５０ｎｍ厚の触媒層４
を形成した触媒素子１を作製した。<First Embodiment> First, a lead wire for applying AC power with silver paste was applied to the end of a piezoelectric pellet 2 of strontium (5 mol%) containing lead zirconate titanate (sintered body) having a silver electrode 5. After fixing (silver) 3, palladium metal is vacuum-deposited on both surfaces of the pellet to form a 50 nm thick catalyst layer 4.
Was formed to produce a catalyst element 1.
【００１４】この触媒素子１を５０Ｔｏｒｒ（約６．７
ｋＰａ）の水素雰囲気下、２００℃において１時間還元
処理した後、図３に示すような反応装置１０内に配置
し、リード線を発振器１１および増幅器１２から成る交
流電源に接続した。The catalyst element 1 is set at 50 Torr (about 6.7).
After a reduction treatment at 200 ° C. for 1 hour in a hydrogen atmosphere of kPa), it was placed in a reaction apparatus 10 as shown in FIG. 3, and the lead wires were connected to an AC power supply composed of an oscillator 11 and an amplifier 12.
【００１５】反応は、加熱ヒーター１３により加熱した
反応装置１０に反応原料であるエタノール−酸素混合ガ
スを（気体循環ポンプ１４および真空排気することによ
り）導入し、触媒素子１に交流電圧を印加することによ
り行い、反応により生成したアセトアルデヒドの生成速
度（時間当たり）をガスクロマトグラフ１５により検出
した。In the reaction, an ethanol-oxygen mixed gas as a reaction raw material is introduced into the reactor 10 heated by the heater 13 (by evacuating the gas circulation pump 14 and evacuating), and an AC voltage is applied to the catalyst element 1. The production rate (per hour) of acetaldehyde produced by the reaction was detected by gas chromatography 15.
【００１６】反応条件は反応装置１０内温度８０℃、エ
タノール分圧３０Ｔｏｒｒ（約４ｋＰａ）、酸素分圧３
０Ｔｏｒｒ（約４ｋＰａ）である。当初交流電圧の印加
は行わず、反応途中（約１．５時間後）であらかじめ実
測しておいた共振周波数８２．０ｋＨｚのサイン波を１
０Ｖで印加した。The reaction conditions are as follows: the temperature inside the reactor 10 is 80 ° C., the partial pressure of ethanol is 30 Torr (about 4 kPa), the partial pressure of oxygen is 3
0 Torr (about 4 kPa). Initially, no AC voltage was applied, and a sine wave with a resonance frequency of 82.0 kHz, which was measured in advance during the reaction (after about 1.5 hours), was set to 1
A voltage of 0 V was applied.
【００１７】この反応の経過は図２のグラフに示され
る。The course of this reaction is shown in the graph of FIG.
【００１８】交流電圧を印加しない期間（０〜１．５時
間）では生成したアセトアルデヒドの平均生成速度（Ｖ
1 ）は約０．１８μｍｏｌ／ｈであり、１．５時間後交
流電圧を印加し触媒素子を共振させたときのアセトアル
デヒドの平均生成速度（Ｖ2）は約４６μｍｏｌ／ｈで
あった。この結果、共振による活性増加割合はＶ2 ／Ｖ
1 ＝２５６倍と算出された。During the period in which no AC voltage is applied (0 to 1.5 hours), the average rate of formation of acetaldehyde (V
1 ) was about 0.18 μmol / h, and the average acetaldehyde generation rate (V 2 ) when an AC voltage was applied and the catalyst element was resonated after 1.5 hours was about 46 μmol / h. As a result, the rate of increase in activity due to resonance is V 2 / V
1 = 256 times was calculated.
【００１９】＜実施例２＞パラジウムを銀に代えた以外
は実施例１と同様な方法、装置により、エタノールの酸
化反応を行った。膜厚は５０ｎｍ、反応温度は１５０
℃、印加電圧は１５Ｖであった。Example 2 An ethanol oxidation reaction was carried out by the same method and apparatus as in Example 1 except that silver was used instead of palladium. The film thickness is 50 nm and the reaction temperature is 150
° C and the applied voltage was 15V.
【００２０】交流電圧を印加しない期間（０〜１．５時
間）では生成したアセトアルデヒドの平均生成速度（Ｖ
1 ）は約Ｏ．Ｏ５μｍｏｌ／ｈであり、１．５時間後交
流電圧を印加し触媒素子を共振させたときのアセトアル
デヒドの平均生成速度（Ｖ2）は約９８．１μｍｏｌ／
ｈであった。この結果、共振による活性増加割合はＶ2
／Ｖ1 ＝１９６２倍と算出された。During the period in which no AC voltage is applied (0 to 1.5 hours), the average rate of formation of acetaldehyde (V
1 ) is about O.D. O was 5 μmol / h, and the average generation rate (V 2 ) of acetaldehyde when an AC voltage was applied after 1.5 hours to resonate the catalyst element was about 98.1 μmol / h.
h. As a result, the rate of increase in activity due to resonance is V 2
/ V 1 = 1962 times.
【００２１】実施例１および２の反応条件・活性増加割
合を表１に示す。 ＜表１＞ ----------------------------------------------------------------------- 触媒 膜厚／ｎｍ 反応温度／℃ 印加電圧／Ｖ 活性増加割合 ----------------------------------------------------------------------- Ｐｄ ５０ ８０ １０ ２５６ Ａｇ ５０ １５０ １５ １９６２ ----------------------------------------------------------------------- Table 1 shows the reaction conditions and the rate of activity increase in Examples 1 and 2. <Table 1> ---------------------------------------------- ------------------------- Catalyst thickness / nm Reaction temperature / ℃ Applied voltage / V Activity increase rate --------- -------------------------------------------------- ------------ Pd 50 80 10 256 Ag 50 150 15 1962 ---------------------------- -------------------------------------------
【００２２】[0022]
【発明の効果】以上詳述した通り、本発明の固体触媒の
活性を高める方法によれば、表面に触媒層が形成された
圧電体にその固有の共振周波数を発生させる交流電圧を
印加して固体触媒の活性を高める方法にあって、前記圧
電体の格子変位の運動を妨げることなく前記交流電圧を
印加するようにしたため、圧電体担持触媒の活性を著し
く高めることができる。As described above in detail, according to the method for enhancing the activity of a solid catalyst of the present invention, an AC voltage for generating a resonance frequency unique to a piezoelectric body having a catalyst layer formed on its surface is applied. In the method of enhancing the activity of the solid catalyst, the AC voltage is applied without hindering the movement of the lattice displacement of the piezoelectric body, so that the activity of the catalyst carrying the piezoelectric body can be significantly increased.
【図１】本発明の方法に用いられる圧電体固体触媒素子
を示す説明図である。FIG. 1 is an explanatory view showing a piezoelectric solid catalyst element used in the method of the present invention.
【図２】本発明の方法をエタノールの酸化反応に適用し
た例を示すグラフである。FIG. 2 is a graph showing an example in which the method of the present invention is applied to an oxidation reaction of ethanol.
【図３】本発明の方法を実施するための反応系の構成例
を示す説明図である。FIG. 3 is an explanatory diagram showing a configuration example of a reaction system for performing the method of the present invention.
【図４】従来の圧電体固体触媒素子を示す説明図であ
る。FIG. 4 is an explanatory view showing a conventional piezoelectric solid catalyst element.
１ 触媒素子 ２ 圧電体ペレット ３ リード線 ４ 触媒層 ５ 電極 ６ 熱電対 １０ 反応装置 １１ 発振器 １２ 増幅器 １３ 加熱ヒーター １４ 気体循環ポンプ １５ ガスクロマトグラフ DESCRIPTION OF SYMBOLS 1 Catalyst element 2 Piezoelectric pellet 3 Lead wire 4 Catalyst layer 5 Electrode 6 Thermocouple 10 Reactor 11 Oscillator 12 Amplifier 13 Heater 14 Gas circulation pump 15 Gas chromatograph
Claims (5)
有の共振周波数を発生させる交流電圧を印加して固体触
媒の活性を高める方法であって、 前記圧電体の格子変位の運動を妨げることなく前記交流
電圧を印加することを特徴とする、固体触媒の活性を高
める方法。1. A method for increasing the activity of a solid catalyst by applying an AC voltage for generating a unique resonance frequency to a piezoelectric body having a catalyst layer formed on a surface thereof, wherein the movement of lattice displacement of the piezoelectric body is controlled. A method for enhancing the activity of a solid catalyst, characterized by applying the AC voltage without hindrance.
有の共振周波数を発生させる交流電圧を印加して固体触
媒の活性を高める方法であって、 前記触媒層または圧電体の表面に接合された熱電対が備
え付けられていないことにより、前記圧電体の格子変位
の運動を妨げることなく前記交流電圧を印加することを
特徴とする、請求項１に記載の固体触媒の活性を高める
方法。2. A method for increasing the activity of a solid catalyst by applying an alternating voltage for generating a resonance frequency unique to a piezoelectric body having a catalyst layer formed on a surface thereof, the method comprising: The method according to claim 1, wherein the AC voltage is applied without disturbing the lattice displacement movement of the piezoelectric body by not providing a bonded thermocouple. .
有の共振周波数を発生させる交流電圧を印加して固体触
媒の活性を高める方法であって、 触媒層表面に局所的な異常変位が発現する程度の共振エ
ネルギーを圧電体に与えることを特徴とする、固体触媒
の活性を高める方法。3. A method for increasing the activity of a solid catalyst by applying an AC voltage for generating a resonance frequency unique to a piezoelectric body having a catalyst layer formed on a surface thereof, the method comprising: A method for increasing the activity of a solid catalyst, characterized by giving a resonance energy to the piezoelectric body to an extent that the pressure is expressed.
印加するためのリード線が接合された圧電体の表面に触
媒層が形成された触媒素子であって、 前記触媒層または前記圧電体に接続され圧電体の格子変
位の運動を妨げる要素が除かれていることを特徴とす
る、触媒素子。4. A catalyst element having a catalyst layer formed on a surface of a piezoelectric body to which a lead wire for applying an AC voltage for generating a unique resonance frequency is joined, wherein the catalyst layer or the piezoelectric body is A catalyst element, wherein an element that is connected and hinders the movement of the lattice displacement of the piezoelectric body is removed.
電体の格子変位の運動を妨げる要素が熱電対であること
を特徴とする、請求項４に記載の触媒素子。5. The catalyst element according to claim 4, wherein the element connected to the catalyst layer or the piezoelectric body and hindering the movement of lattice displacement of the piezoelectric body is a thermocouple.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23790994A JP3162583B2 (en) | 1994-09-30 | 1994-09-30 | Method and catalyst element for enhancing activity of solid catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23790994A JP3162583B2 (en) | 1994-09-30 | 1994-09-30 | Method and catalyst element for enhancing activity of solid catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08103669A JPH08103669A (en) | 1996-04-23 |
| JP3162583B2 true JP3162583B2 (en) | 2001-05-08 |
Family
ID=17022239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23790994A Expired - Fee Related JP3162583B2 (en) | 1994-09-30 | 1994-09-30 | Method and catalyst element for enhancing activity of solid catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3162583B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7879731B2 (en) | 2007-01-30 | 2011-02-01 | Applied Materials, Inc. | Improving plasma process uniformity across a wafer by apportioning power among plural VHF sources |
| US7884025B2 (en) | 2007-01-30 | 2011-02-08 | Applied Materials, Inc. | Plasma process uniformity across a wafer by apportioning ground return path impedances among plural VHF sources |
| US7968469B2 (en) | 2007-01-30 | 2011-06-28 | Applied Materials, Inc. | Method of processing a workpiece in a plasma reactor with variable height ground return path to control plasma ion density uniformity |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025132A1 (en) * | 1996-12-04 | 1998-06-11 | Oxy L'eau Inc. | Catalytic resonance simulator |
| US7950221B2 (en) | 2003-04-25 | 2011-05-31 | Catelectric Corp. | Methods and apparatus for controlling catalytic processes, including catalyst regeneration and soot elimination |
| JP5091148B2 (en) * | 2005-10-28 | 2012-12-05 | カテレクトリック・コーポレイション | Method for controlling a catalytic process comprising catalyst regeneration and soot removal |
| US7964084B2 (en) * | 2007-09-20 | 2011-06-21 | Catelectric Corp. | Methods and apparatus for the synthesis of useful compounds |
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1994
- 1994-09-30 JP JP23790994A patent/JP3162583B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7879731B2 (en) | 2007-01-30 | 2011-02-01 | Applied Materials, Inc. | Improving plasma process uniformity across a wafer by apportioning power among plural VHF sources |
| US7884025B2 (en) | 2007-01-30 | 2011-02-08 | Applied Materials, Inc. | Plasma process uniformity across a wafer by apportioning ground return path impedances among plural VHF sources |
| US7968469B2 (en) | 2007-01-30 | 2011-06-28 | Applied Materials, Inc. | Method of processing a workpiece in a plasma reactor with variable height ground return path to control plasma ion density uniformity |
| US8076247B2 (en) | 2007-01-30 | 2011-12-13 | Applied Materials, Inc. | Plasma process uniformity across a wafer by controlling RF phase between opposing electrodes |
| US8080479B2 (en) | 2007-01-30 | 2011-12-20 | Applied Materials, Inc. | Plasma process uniformity across a wafer by controlling a variable frequency coupled to a harmonic resonator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08103669A (en) | 1996-04-23 |
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