JP2000126596A - Complex oxide, its production, and method for hydrogenating carbon dioxide - Google Patents
Complex oxide, its production, and method for hydrogenating carbon dioxideInfo
- Publication number
- JP2000126596A JP2000126596A JP30748398A JP30748398A JP2000126596A JP 2000126596 A JP2000126596 A JP 2000126596A JP 30748398 A JP30748398 A JP 30748398A JP 30748398 A JP30748398 A JP 30748398A JP 2000126596 A JP2000126596 A JP 2000126596A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- carbon dioxide
- nickel
- solution
- composite oxide
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】ニッケル酸化物及びジルコニ
ウム酸化物からなる複合酸化物、その製造方法、及びそ
れを用いた二酸化炭素を水素化する方法に関する。The present invention relates to a composite oxide comprising nickel oxide and zirconium oxide, a method for producing the same, and a method for hydrogenating carbon dioxide using the same.
【０００２】[0002]
【従来の技術】ニッケル及びジルコニウムを含有する酸
化物触媒としては、例えば、Ｚａｉｒｙｏ−ｔｏ−Ｋａ
ｎｋｙｏ，４５巻，６１４頁（１９９６年）には、アモ
ルファスＮｉ−Ｚｒを前駆体として用い、酸化還元処理
を施して得た触媒が開示されている。この触媒は、微細
なＺｒＯ2 上に金属状態のニッケルが分散した状態であ
る。2. Description of the Related Art As an oxide catalyst containing nickel and zirconium, for example, Zairyo-to-Ka is known.
nkyo, Vol. 45, p. 614 (1996) discloses a catalyst obtained by subjecting amorphous Ni-Zr as a precursor to a redox treatment. This catalyst is in a state where metallic nickel is dispersed on fine ZrO 2 .
【０００３】また、Ｎｉ−Ｚｒ合金を酸化アルミニウム
あるいは酸化チタンからなる担体表面に合金をイオンス
パッタリング法に担持したものである。これらの触媒
は、表面に局在しており、触媒活性がかならずしも高く
なく、また調製方法も煩雑な問題がある。In addition, a Ni—Zr alloy is supported on a carrier surface made of aluminum oxide or titanium oxide by an ion sputtering method. These catalysts have a problem that they are localized on the surface, the catalytic activity is not always high, and the preparation method is complicated.
【０００４】[0004]
【発明が解決しようとする課題】無機担体にニッケル酸
化物及びジルコニウム酸化物が微粒子形状で均一に分散
して埋浸している複合酸化物、その簡便な製造方法、及
びそれを触媒に用いて二酸化炭素を高活性で水素化する
ことを目的とする。SUMMARY OF THE INVENTION A composite oxide in which nickel oxide and zirconium oxide are uniformly dispersed and embedded in fine particles in an inorganic carrier, a simple method for producing the same, and a method for producing a composite oxide using the same as a catalyst. It aims at hydrogenating carbon with high activity.
【０００５】[0005]
【課題を解決するための手段】本発明は、無機担体にニ
ッケル酸化物及びジルコニウム酸化物が微粒子形状で均
一に分散して埋浸していることを特徴とする複合酸化物
に関する。SUMMARY OF THE INVENTION The present invention relates to a composite oxide characterized in that nickel oxide and zirconium oxide are uniformly dispersed in fine particles and embedded in an inorganic carrier.
【０００６】また、本発明は、無機担体が二酸化ケイ素
であることを特徴とする上記の複合酸化物に関する。[0006] The present invention also relates to the above composite oxide, wherein the inorganic carrier is silicon dioxide.
【０００７】また、本発明は、ニッケル塩アルコール溶
液及びジルコニウム塩溶液の混合溶液を、オルトケイ酸
アルキルと混合することを特徴とする上記の複合酸化物
の製造方法に関する。The present invention also relates to the above-mentioned method for producing a composite oxide, comprising mixing a mixed solution of a nickel salt alcohol solution and a zirconium salt solution with an alkyl orthosilicate.
【０００８】また、本発明は、上記の複合酸化物を触媒
として用いることを特徴とする二酸化炭素を水素化する
方法に関する。[0008] The present invention also relates to a method for hydrogenating carbon dioxide, comprising using the above-mentioned composite oxide as a catalyst.
【０００９】[0009]
【発明の実施の形態】本発明における、無機担体として
は、アルミナ、チタニア、シリカ（二酸化ケイ素）、ジ
ルコニア、アルカリ土類金属酸化物、これらの混合物な
どが挙げられる。中でも、シリカ（二酸化ケイ素）が好
ましい。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, examples of the inorganic carrier include alumina, titania, silica (silicon dioxide), zirconia, alkaline earth metal oxides, and mixtures thereof. Among them, silica (silicon dioxide) is preferable.
【００１０】本発明において、ニッケル酸化物として
は、酸化ニッケル（ＮｉＯ、ＮｉＯ2、Ｎｉ2 Ｏ）など
が挙げられる。In the present invention, examples of the nickel oxide include nickel oxide (NiO, NiO 2 , Ni 2 O).
【００１１】また、本発明は、ジルコニウム酸化物とし
ては、二酸化ジルコニウム（ＺｒＯ 2 ）などが挙げられ
る。本発明においては、ニッケル酸化物及びジルコニウ
ム酸化物が無機担体に微粒子形状で均一に分散して埋浸
していることを特徴としている。このことは、ＳＥＭ、
ＥＳＣＡなどの表面分析などの結果から確認される。The present invention also relates to a zirconium oxide.
Zirconium dioxide (ZrO Two)
You. In the present invention, nickel oxide and zirconium
Oxide is uniformly dispersed and embedded in fine particles
It is characterized by doing. This means that SEM,
It is confirmed from the results of surface analysis such as ESCA.
【００１２】また、Ｘ線回析の結果から、Ｎｉ及びＺｒ
が相溶化しておらず、各金属が単独で存在していること
が確認された。From the results of X-ray diffraction, Ni and Zr
Were not compatibilized, and it was confirmed that each metal was present alone.
【００１３】本発明における、無機担体にニッケル酸化
物及びジルコニウム酸化物が微粒子形状で均一に分散し
て埋浸していることを特徴とする複合酸化物の調製方法
としては、以下のアルコキシド法が挙げられる。In the present invention, the following alkoxide method is mentioned as a method for preparing a composite oxide characterized in that nickel oxide and zirconium oxide are uniformly dispersed in fine particles and embedded in an inorganic carrier. Can be
【００１４】硝酸ニッケル（Ｎｉ（ＮＯ3 ）2 ）などの
ニッケル塩をアルコールなどに溶解して溶液を調製す
る。同様に、硝酸ジルコニウム（ＺｒＯ（ＮＯ3 ）2 ）
などのシルコニウム塩をアルコールなどに溶解して溶液
を調製する。アルコールとしては、メタノール、エタノ
ール、プロパノール、ブタノールなど低級アルコールが
挙げられる。A solution is prepared by dissolving a nickel salt such as nickel nitrate (Ni (NO 3 ) 2 ) in alcohol or the like. Similarly, zirconium nitrate (ZrO (NO 3 ) 2 )
Is dissolved in alcohol or the like to prepare a solution. Examples of the alcohol include lower alcohols such as methanol, ethanol, propanol and butanol.
【００１５】上記の溶液を混合し、オルトケイ酸エチル
にいれ、混合、加熱して、水を添加してゲル化させる。
加熱温度は、通常、７０〜８０℃が好ましい。ゲル状物
から、溶媒および硝酸化合物などを蒸発させて除去し、
乾燥させて複合酸化物が得られる。The above solutions are mixed, put into ethyl orthosilicate, mixed, heated, and water is added to cause gelation.
Usually, the heating temperature is preferably from 70 to 80 ° C. From the gel, the solvent and nitric acid compounds are removed by evaporation,
After drying, a composite oxide is obtained.
【００１６】本発明においては、上記の複合酸化物を水
素化触媒として用いる場合は、触媒反応への前処理とし
て、水素雰囲気下、加熱処理して、水素還元することが
好ましい。加熱温度は、通常、７０〜８０℃が好まし
い。加熱時間は２〜４時間が好ましい。In the present invention, when the above-mentioned composite oxide is used as a hydrogenation catalyst, it is preferable to carry out a heat treatment in a hydrogen atmosphere to reduce hydrogen as a pretreatment to the catalytic reaction. Usually, the heating temperature is preferably from 70 to 80 ° C. The heating time is preferably 2 to 4 hours.
【００１７】本発明において、複合酸化物を触媒に用い
て、二酸化炭素の水素化によってメタンに還元すること
ができる。水素化反応は、水素ガスと二酸化炭素ガスの
混合ガスを複合酸化物に高温下で接触させる。水素ガス
と二酸化ガスの割合は、４：１〜３：１でありことが好
ましい。反応温度は２００〜３５０℃が好ましい。本反
応は、バッチでも連続でも行うことができる。In the present invention, using a composite oxide as a catalyst, carbon dioxide can be reduced to methane by hydrogenation. In the hydrogenation reaction, a mixed gas of hydrogen gas and carbon dioxide gas is brought into contact with the composite oxide at a high temperature. The ratio of the hydrogen gas to the dioxide gas is preferably 4: 1 to 3: 1. The reaction temperature is preferably from 200 to 350C. This reaction can be carried out batchwise or continuously.
【実施例】（実施例１）（複合酸化物の調製） （１）Ｎｉ（ＮＯ3 ）2 ６Ｈ2 Ｏ（Ｍｗ＝２９０．７
９）１．５ｇを１００ｍＬのメスフラスコに入れ、メタ
ノールを用いて室温にて溶解した。 （２）次に、ＺｒＯ（ＮＯ3 ）２Ｈ2 Ｏ（Ｍｗ＝２６
７．２６）０．９５ｇを（１）に入れ、溶解した。 （３）５００ｍＬの４つ口フラスコに、オルトケイ酸エ
チル２１５ｍＬを入れ、８０℃に加熱、攪拌した。 （４）（３）に（２）で調製した溶液を入れ、８０℃で
２時間、激しく攪拌した。 （５）２時間後に蒸留水１００ｍＬを滴下し、再び８０
℃で３時間激しく攪拌した。 （６）温度を室温まで戻して、一晩（８時間）、激しく
攪拌した。 （７）再び８０℃まで上昇させ、蒸留水１００ｍＬを滴
下した。 （８）２時間後、溶液がゲル化した。 （９）ゲル化物を一辺が２０ｃｍの正方形耐熱硝子板
（厚さ５ｍｍ）の上に乗せた。 （１０）ドラフトの中で、ゲル化物上から赤外線ランプ
を照射し、表面温度が約２００℃になるように調整し、
ゲル中の溶媒及び硝酸化合物（主にＮＯ2 ）を飛ばし
た。 （１１）ゲルが完全乾燥し、ＮＯ生成による赤褐色ガス
の発生が終了したら、ガラス板上から取り出した。薄い
水色の２ｍｍ程度のＮｉＯ−ＺｒＯ2 −ＳｉＯ2の粒子
が得られた。 （触媒反応への前処理、及び二酸化炭素の水素化反応） （１２）乾燥ゲル５ｇをるつぼに入れ電気炉にて５００
℃で２時間加熱した。 （１３）さらに、それを１ｇ取り、反応ラインへ固定所
床触媒として詰めた。 （１４）水素を流量が２００ｍＬ／ｍｉｎ．になるよう
にして、３００℃で３時間水素還元した。Ｎｉ−Ｚｒ−
ＳｉＯ2 （Ｎｉ，Ｚｒ＝０．１ｗｔ％）が生成した。 （１５）その後、一旦室温まで戻し、二酸化炭素と水素
の流量を調整し、昇温、反応を開始した。 反応条件は、３３０℃でＨ2 ＝３３ｍＬ／ｍｉｍ．、Ｃ
Ｏ2 ＝１３ｍＬ／ｍｉｍ．にて２００時間反応させ、そ
の後、徐々に温度を下げ、室温まで冷やした後、窒素ガ
スで置換して１日放置した。再び、３３０℃に上げて同
流量条件で反応させた。触媒量は１ｇ、空間速度は１３
００ｈｒ-1 EXAMPLES (Example 1) (Preparation of composite oxide) (1) Ni (NO 3 ) 2 6H 2 O (Mw = 290.7
9) 1.5 g was placed in a 100 mL volumetric flask and dissolved at room temperature using methanol. (2) Next, ZrO (NO 3 ) 2 H 2 O (Mw = 26
7.26) 0.95 g was placed in (1) and dissolved. (3) Ethyl orthosilicate (215 mL) was placed in a 500 mL four-necked flask, and heated and stirred at 80 ° C. (4) The solution prepared in (2) was added to (3) and stirred vigorously at 80 ° C. for 2 hours. (5) After 2 hours, 100 mL of distilled water was added dropwise, and
Stirred vigorously for 3 hours. (6) The temperature was returned to room temperature, and the mixture was vigorously stirred overnight (8 hours). (7) The temperature was raised again to 80 ° C., and 100 mL of distilled water was added dropwise. (8) After 2 hours, the solution gelled. (9) The gel was placed on a square heat-resistant glass plate (5 mm thick) having a side of 20 cm. (10) In the draft, irradiate an infrared lamp from above the gelled material to adjust the surface temperature to about 200 ° C,
The solvent and nitric acid compound (mainly NO 2 ) in the gel were removed. (11) When the gel was completely dried and the generation of reddish brown gas due to NO generation was completed, the gel was taken out from the glass plate. Light blue of about 2mm of NiO-ZrO 2 -SiO 2 particles were obtained. (Pretreatment for catalytic reaction and hydrogenation reaction of carbon dioxide) (12) 5 g of dry gel is put into a crucible and placed in an electric furnace for 500
Heated at ° C for 2 hours. (13) Further, 1 g thereof was taken and packed in a reaction line as a fixed bed catalyst. (14) The flow rate of hydrogen was 200 mL / min. Then, hydrogen reduction was carried out at 300 ° C. for 3 hours. Ni-Zr-
SiO 2 (Ni, Zr = 0.1 wt%) was produced. (15) Thereafter, the temperature was once returned to room temperature, the flow rates of carbon dioxide and hydrogen were adjusted, and the temperature was raised and the reaction was started. The reaction conditions were as follows: 330 ° C., H 2 = 33 mL / mim. , C
O 2 = 13 mL / mim. For 200 hours, and then the temperature was gradually lowered, cooled to room temperature, replaced with nitrogen gas, and left for 1 day. The temperature was raised again to 330 ° C., and the reaction was carried out under the same flow rate conditions. The catalyst amount is 1 g and the space velocity is 13
00hr -1
【発明の効果】無機担体にニッケル酸化物及びジルコニ
ウム酸化物が微粒子形状で均一に分散して埋浸している
複合酸化物、その簡便な製造方法、及びそれを触媒に用
いて二酸化炭素を高活性で水素化できる。EFFECTS OF THE INVENTION A composite oxide in which nickel oxide and zirconium oxide are uniformly dispersed and buried in the form of fine particles in an inorganic carrier, a simple production method thereof, and high activity of carbon dioxide using the same as a catalyst Can be hydrogenated.
【図１】本発明及び従来技術の触媒構造の模式図であ
る。FIG. 1 is a schematic view of the catalyst structure of the present invention and the prior art.
【図２】実施例１の触媒を用いた二酸化炭素のメタンへ
の転化反応の、反応時間と転化率の関係を示す。FIG. 2 shows the relationship between the reaction time and the conversion in the conversion reaction of carbon dioxide to methane using the catalyst of Example 1.
【図３】実施例１の触媒を用いた二酸化炭素のメタンへ
の転化反応の、反応温度とメタンへの転化率の関係を示
す。FIG. 3 shows the relationship between the reaction temperature and the conversion rate to methane in the conversion reaction of carbon dioxide to methane using the catalyst of Example 1.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G042 DA02 DB12 DC03 DD04 DE06 DE07 4G069 AA01 AA03 AA08 AA15 BA02A BA02B BA21C BA27C BA32C BB04A BB04B BB06A BB06B BB12C BC51A BC51B BC51C BC68A BC68B BC68C BE01C BE06C BE32C CC22 EB19 FA02 FB04 FB08 4G072 AA25 AA38 BB05 GG02 GG03 HH29 RR12 TT01 UU15 UU17 UU19 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4G042 DA02 DB12 DC03 DD04 DE06 DE07 4G069 AA01 AA03 AA08 AA15 BA02A BA02B BA21C BA27C BA32C BB04A BB04B BB06A BB06B BB12C BC51A BC51B BC51C BC68A BE68B07 BC68 BE68B02 A AA38 BB05 GG02 GG03 HH29 RR12 TT01 UU15 UU17 UU19
Claims (4)
ウム酸化物が微粒子形状で均一に分散して埋浸している
ことを特徴とする複合酸化物。1. A composite oxide, characterized in that nickel oxide and zirconium oxide are uniformly dispersed in fine particles and embedded in an inorganic carrier.
徴とする請求項１または２に記載の複合酸化物。2. The composite oxide according to claim 1, wherein the inorganic carrier is silicon dioxide.
ウム塩溶液の混合溶液を、オルトケイ酸アルキルと混合
することを特徴とする請求項１〜２に記載の複合酸化物
の製造方法。3. The method according to claim 1, wherein a mixed solution of a nickel salt alcohol solution and a zirconium salt solution is mixed with an alkyl orthosilicate.
として用いることを特徴とする二酸化炭素を水素化する
方法。4. A method for hydrogenating carbon dioxide, comprising using the composite oxide according to claim 1 as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30748398A JP2000126596A (en) | 1998-10-28 | 1998-10-28 | Complex oxide, its production, and method for hydrogenating carbon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30748398A JP2000126596A (en) | 1998-10-28 | 1998-10-28 | Complex oxide, its production, and method for hydrogenating carbon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000126596A true JP2000126596A (en) | 2000-05-09 |
Family
ID=17969637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30748398A Pending JP2000126596A (en) | 1998-10-28 | 1998-10-28 | Complex oxide, its production, and method for hydrogenating carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000126596A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090042998A1 (en) * | 2007-08-03 | 2009-02-12 | Daiki Ataka Engineering Co., Ltd. | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| JP2009034654A (en) * | 2007-08-03 | 2009-02-19 | Daiki Ataka Engineering Co Ltd | Hydrogenation catalyst, method of manufacturing the same, and method for producing methane gas using the same |
| WO2014158095A1 (en) * | 2013-03-28 | 2014-10-02 | Agency For Science, Technology And Research | Methanation catalyst |
| US9908104B2 (en) | 2013-06-28 | 2018-03-06 | Agency For Science, Technology And Research | Methanation catalyst |
-
1998
- 1998-10-28 JP JP30748398A patent/JP2000126596A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090042998A1 (en) * | 2007-08-03 | 2009-02-12 | Daiki Ataka Engineering Co., Ltd. | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| JP2009034654A (en) * | 2007-08-03 | 2009-02-19 | Daiki Ataka Engineering Co Ltd | Hydrogenation catalyst, method of manufacturing the same, and method for producing methane gas using the same |
| US9617196B2 (en) * | 2007-08-03 | 2017-04-11 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| US9732010B2 (en) | 2007-08-03 | 2017-08-15 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| US9731278B2 (en) | 2007-08-03 | 2017-08-15 | Hitachi Zosen Corporation | Catalyst for methanation of carbon oxides, preparation method of the catalyst and process for the methanation |
| WO2014158095A1 (en) * | 2013-03-28 | 2014-10-02 | Agency For Science, Technology And Research | Methanation catalyst |
| JP2016515470A (en) * | 2013-03-28 | 2016-05-30 | エージェンシー フォー サイエンス， テクノロジー アンド リサーチ | Methanation catalyst |
| US9802872B2 (en) | 2013-03-28 | 2017-10-31 | Agency For Science, Technology And Research | Methanation catalyst |
| US9908104B2 (en) | 2013-06-28 | 2018-03-06 | Agency For Science, Technology And Research | Methanation catalyst |
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