JPH0739757A - Oxidation catalyst - Google Patents
Oxidation catalystInfo
- Publication number
- JPH0739757A JPH0739757A JP5191159A JP19115993A JPH0739757A JP H0739757 A JPH0739757 A JP H0739757A JP 5191159 A JP5191159 A JP 5191159A JP 19115993 A JP19115993 A JP 19115993A JP H0739757 A JPH0739757 A JP H0739757A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- complex oxide
- oxidation catalyst
- oxygen
- molar ratio
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 13
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940063746 oxygen 20 % Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229940038504 oxygen 100 % Drugs 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、一酸化炭素や炭化水素
などの可燃性ガスを燃焼させるための新規酸化触媒に関
する。FIELD OF THE INVENTION The present invention relates to a novel oxidation catalyst for burning a combustible gas such as carbon monoxide or hydrocarbon.
【０００２】[0002]
【従来技術】一般に、一酸化炭素や炭化水素などの可燃
性ガスを酸化触媒の存在下で燃焼させる接触燃焼法は、
主として自動車排気ガスの浄化を目的に研究され、多く
の酸化触媒が開発されている。また環境浄化のために、
石油脱硫触媒や室内空気浄化用触媒が開発されている。2. Description of the Related Art Generally, a catalytic combustion method of burning a combustible gas such as carbon monoxide or hydrocarbon in the presence of an oxidation catalyst is
Many oxidation catalysts have been developed mainly for the purpose of purifying automobile exhaust gas. In addition, for environmental purification,
Petroleum desulfurization catalysts and indoor air purification catalysts have been developed.
【０００３】従来から用いられている酸化触媒として
は、貴金属からなるものが最も有効なもので、三元触媒
（Ｐｔ−Ｐｄ−Ｒｈ）として、自動車の排ガス処理用と
して搭載されている。Of the oxidation catalysts that have been conventionally used, those made of a noble metal are the most effective, and they are mounted as a three-way catalyst (Pt-Pd-Rh) for treating exhaust gas of automobiles.
【０００４】[0004]
【発明が解決しようとする問題点】触媒材料に対して
は、低温活性と高温での耐久性を向上、ウインドゲイト
の拡大が要求され、これに対しては貴金属の担持量を増
加させることにより解決することができるが、貴金属を
節減するという点では相反するものであり、これらを同
時に満たすことはできないのが現状である。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention For catalyst materials, improvement in low temperature activity and durability at high temperatures, and expansion of wind gates are required. To this end, by increasing the loading amount of noble metal. Although they can be solved, they are contradictory in terms of saving precious metals, and the current situation is that they cannot be satisfied at the same time.
【０００５】前記三元触媒のうち、Ｒｈは資源的に希少
であり且つ効果であるために資源確保の面から担持量を
低減することが望まれるが、耐久性の面からその担持量
を低減するにも限界がある。また、Ｐｔに対してＰｄを
部分的に置換することも行われている。Of the above three-way catalysts, Rh is a resource scarce and effective, so it is desirable to reduce the amount of Rh supported from the viewpoint of securing resources, but from the viewpoint of durability, the amount of Rh is reduced. There are limits to what you can do. Also, Pd is partially replaced with Pd.
【０００６】従って、本発明は、従来の貴金属系の三元
触媒に代わる新規な酸化触媒を提供することを目的とす
るものである。Therefore, an object of the present invention is to provide a novel oxidation catalyst which replaces the conventional noble metal type three-way catalyst.
【０００７】[0007]
【問題点を解決するための手段】本発明者は、新規酸化
触媒材料について、複合酸化物の観点から探索したとこ
ろ、金属元素として、Ｂｉ、Ｐｂ、Ｓｒ、ＣａおよびＣ
ｕを含み、正方晶結晶構造を呈する複合酸化物が、酸化
触媒性能を有することを見出し、本発明に至ったのであ
る。The inventors of the present invention searched for a novel oxidation catalyst material from the viewpoint of a complex oxide, and found that Bi, Pb, Sr, Ca and C were used as metal elements.
The present inventors have found that a composite oxide containing u and having a tetragonal crystal structure has an oxidation catalyst performance, and has arrived at the present invention.
【０００８】本発明におけるＢｉ、Ｐｂ、Ｓｒ、Ｃａお
よびＣｕを含み、正方晶結晶構造を呈する複合酸化物の
具体的な組成としては、Ｓｒを２とした時、Ｂｉが１．
８〜２．２、Ｃａが２．０〜３．５、Ｃｕが３．０〜
４．５、Ｐｂを０．１〜０．５のモル比で含むもので、
場合によりＫ、Ｌｉ、ＮａをＳｒが２に対して、０．０
５〜０．６の割合で含有して焼結性を高めることができ
る。かかる組成からなる複合酸化物は、一部において酸
化物超電導体としても知られている。The specific composition of the complex oxide containing Bi, Pb, Sr, Ca and Cu according to the present invention and having a tetragonal crystal structure is as follows.
8-2.2, Ca 2.0-3.5, Cu 3.0-
4.5, containing Pb in a molar ratio of 0.1 to 0.5,
Depending on the case, K, Li, and Na are added to 0.0 with respect to Sr of 2.
It can be contained at a ratio of 5 to 0.6 to enhance the sinterability. The composite oxide having such a composition is also known in part as an oxide superconductor.
【０００９】また、この複合酸化物は、各金属の酸化物
を上記組成範囲に秤量混合した後、、所望により成形し
た後に８００〜９００℃の酸化性雰囲気中で１〜１００
時間焼成することにより合成することができる。In this composite oxide, the oxides of the respective metals are weighed and mixed within the above composition range and, if desired, molded and then 1 to 100 in an oxidizing atmosphere at 800 to 900 ° C.
It can be synthesized by firing for a time.
【００１０】[0010]
【作用】本発明によれば、上記複合酸化物を酸化触媒と
して用いることができる。かかる複合酸化物は、酸素濃
度が２０％以上の過剰酸素雰囲気中であっても酸化触媒
能を有するものである。According to the present invention, the above composite oxide can be used as an oxidation catalyst. Such a complex oxide has an oxidation catalytic ability even in an excess oxygen atmosphere having an oxygen concentration of 20% or more.
【００１１】上記複合酸化物単体は、酸素濃度１００〜
０％まで温度８７５℃まで全く不活性であり、炭化水素
化合物単体は図１の熱重量−示差熱分析曲線から明らか
なように、２８０〜４６０℃にかけて吸熱反応を示し分
解する化合物であるが、この炭化水素に対して上記複合
酸化物が酸素濃度が空気（約２０％）以上の雰囲気中に
共存した場合に、図２に示すように約１００℃付近から
炭化水素の分解蒸発が生じ、２５０℃付近から発熱を伴
う酸化反応により分解することがわかる。The complex oxide simple substance has an oxygen concentration of 100 to 100.
Although it is completely inactive up to 0% at a temperature of 875 ° C., the hydrocarbon compound itself is a compound that decomposes by showing an endothermic reaction from 280 to 460 ° C., as is clear from the thermogravimetric-differential thermal analysis curve of FIG. When the above complex oxide coexists with this hydrocarbon in an atmosphere having an oxygen concentration of air (about 20%) or more, the hydrocarbon is decomposed and evaporated from about 100 ° C. as shown in FIG. It can be seen that decomposition occurs from around 0 ° C. by an oxidative reaction accompanied by heat generation.
【００１２】[0012]
【実施例】原料粉末としてＢｉ2 Ｏ3 、ＰｂＯ、ＳｒＣ
Ｏ3 、ＣａＣＯ3 、ＣｕＯの各粉末を各金属のモル比が
Ｂｉ：Ｐｂ：Ｓｒ：Ｃａ：Ｃｕ＝１．９３：０．３６：
２：３．１７：４．２５となるように秤量後、最終的に
８４０℃の大気中で１５０時間仮焼して、鱗片状の結晶
粉末（ＢＳＣＣＯ粉末）を得た。この粉末を用いて、温
度−雰囲気における反応性を示差熱重量分析器を用いて
調べた。温度は、室温から１０００℃まで、雰囲気は酸
素濃度の変化をさせるために、Ｎ2 （酸素０％）、空気
（酸素２０％）、酸素１００％の３種のガスを用いた。
表１に、上記複合酸化物と炭化水素化合物（ポリメタク
リル酸）との各雰囲気中での分析結果を示した。Example As raw material powders, Bi 2 O 3 , PbO, SrC
The powder of O 3 , CaCO 3 , and CuO has a molar ratio of each metal of Bi: Pb: Sr: Ca: Cu = 1.93: 0.36:
After weighing so as to be 2: 3.17: 4.25, it was finally calcined in the air at 840 ° C. for 150 hours to obtain scale-like crystal powder (BSCCO powder). Using this powder, the reactivity in the temperature-atmosphere was examined using a differential thermogravimetric analyzer. The temperature was from room temperature to 1000 ° C., and in the atmosphere, three kinds of gas of N 2 (oxygen 0%), air (oxygen 20%), and oxygen 100% were used in order to change the oxygen concentration.
Table 1 shows the analysis results of the composite oxide and the hydrocarbon compound (polymethacrylic acid) in each atmosphere.
【００１３】[0013]
【表１】 [Table 1]
【００１４】表１から明らかなように、ＢＳＣＣＯ粉末
単体の反応温度は、酸素濃度によって多少異なるが、最
も反応し易いＮ2 ガス中でも８７４℃まで反応すること
なく安定である。一方、参考例としてポリメタクリル酸
の反応性がＮ2 中で１４６℃〜４７９℃の温度範囲で緩
やかな分解蒸発が生じる、空気中では吸熱反応、酸素中
ではわずかな発熱反応が見られる。これに対して、ＢＳ
ＣＣＯ粉末とポリメタクリル酸を９：１で混合したコン
パウンドにおいては、Ｎ2 中では炭化水素化合物単体と
の反応性の違いは見られないが、空気中（酸素２０％）
では炭化水素単体での吸熱反応（−8.6 μＶ）が発熱反
応（＋８．７μＶ）に変わり、さらに酸素中では発熱量
（示差熱分析装置の温度差の電圧値）が単体の場合の＋
６．８μＶから＋３１．５μＶに変化している。また、
酸素濃度の増加に伴い、コンパウンドの分解蒸発する温
度範囲が狭くなり、より低温で分解できるようになっ
た。As is clear from Table 1, the reaction temperature of the BSCCO powder simple substance is slightly different depending on the oxygen concentration, but is stable without reacting up to 874 ° C. even in the most reactive N 2 gas. On the other hand, as a reference example, the reactivity of polymethacrylic acid is gradually decomposed and evaporated in the temperature range of 146 ° C. to 479 ° C. in N 2 , an endothermic reaction in air and a slight exothermic reaction in oxygen are observed. In contrast, BS
In the compound in which CCO powder and polymethacrylic acid were mixed at 9: 1, there was no difference in reactivity with the hydrocarbon compound alone in N 2 , but in air (oxygen 20%)
Then, the endothermic reaction (-8.6 μV) of the hydrocarbon alone changes to the exothermic reaction (+8.7 μV), and the calorific value (voltage value of the temperature difference of the differential thermal analyzer) in oxygen is +
It has changed from 6.8 μV to +31.5 μV. Also,
As the oxygen concentration increased, the temperature range in which the compound decomposes and evaporates became narrower, and it became possible to decompose at lower temperatures.
【００１５】このように、ＢＳＣＣＯ粉末と酸素の存在
により炭化水素化合物の酸化反応を促進することができ
ることがわかった。As described above, it was found that the oxidation reaction of the hydrocarbon compound can be promoted by the presence of BSCCO powder and oxygen.
【００１６】[0016]
【発明の効果】以上詳述した通り、本発明によれば、安
価な金属からなる特定の複合酸化物を酸化触媒として用
いることができ、炭化水素などを低温で分解することが
可能となる。これによりこれまでの貴金属からなる三元
触媒に代わる安価な触媒として有用性に優れるものであ
る。As described above in detail, according to the present invention, it is possible to use a specific composite oxide made of an inexpensive metal as an oxidation catalyst, and to decompose hydrocarbons at a low temperature. As a result, it has excellent utility as an inexpensive catalyst that replaces the conventional three-way catalyst made of a noble metal.
【図１】炭化水素化合物単体の熱重量−示差熱分析曲線
を示す図である。FIG. 1 is a diagram showing a thermogravimetric-differential thermal analysis curve of a hydrocarbon compound alone.
【図２】炭化水素化合物と本発明の複合酸化物触媒との
コンパウンドの熱重量−示差熱分析曲線を示す図であ
る。FIG. 2 is a view showing a thermogravimetric-differential thermal analysis curve of a compound of a hydrocarbon compound and the complex oxide catalyst of the present invention.
Claims (1)
およびＣｕを含み、正方晶結晶構造を呈する複合酸化物
からなる酸化触媒。1. A metal element comprising Bi, Pb, Sr, and Ca.
And an oxidation catalyst comprising a complex oxide containing Cu and having a tetragonal crystal structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5191159A JPH0739757A (en) | 1993-08-02 | 1993-08-02 | Oxidation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5191159A JPH0739757A (en) | 1993-08-02 | 1993-08-02 | Oxidation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0739757A true JPH0739757A (en) | 1995-02-10 |
Family
ID=16269888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5191159A Pending JPH0739757A (en) | 1993-08-02 | 1993-08-02 | Oxidation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0739757A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014002482A1 (en) | 2012-06-25 | 2014-01-03 | パナソニック株式会社 | Carbon dioxide adsorbent |
| CN105358970A (en) * | 2013-07-02 | 2016-02-24 | 国立大学法人长崎大学 | Co sensor and method for manufacturing co sensor |
| CN107456985A (en) * | 2017-07-25 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of selective oxidation CO catalyst, its preparation method and application |
-
1993
- 1993-08-02 JP JP5191159A patent/JPH0739757A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014002482A1 (en) | 2012-06-25 | 2014-01-03 | パナソニック株式会社 | Carbon dioxide adsorbent |
| CN105358970A (en) * | 2013-07-02 | 2016-02-24 | 国立大学法人长崎大学 | Co sensor and method for manufacturing co sensor |
| CN105358970B (en) * | 2013-07-02 | 2018-01-16 | 国立大学法人长崎大学 | The manufacture method of CO sensors and CO sensors |
| CN107456985A (en) * | 2017-07-25 | 2017-12-12 | 中国科学院福建物质结构研究所 | A kind of selective oxidation CO catalyst, its preparation method and application |
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