JPH0741313A - Method for selectively oxidizing carbon monoxide and catalyst used for the same method - Google Patents
Method for selectively oxidizing carbon monoxide and catalyst used for the same methodInfo
- Publication number
- JPH0741313A JPH0741313A JP5258805A JP25880593A JPH0741313A JP H0741313 A JPH0741313 A JP H0741313A JP 5258805 A JP5258805 A JP 5258805A JP 25880593 A JP25880593 A JP 25880593A JP H0741313 A JPH0741313 A JP H0741313A
- Authority
- JP
- Japan
- Prior art keywords
- carbon monoxide
- catalyst
- cobalt
- oxide
- hydrogen
- 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 62
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 title abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 claims abstract description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 9
- DOTULABPLBJFQR-UHFFFAOYSA-N [O--].[O--].[Co++].[Zn++] Chemical compound [O--].[O--].[Co++].[Zn++] DOTULABPLBJFQR-UHFFFAOYSA-N 0.000 claims description 9
- 229910003321 CoFe Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 15
- LNBBNXBJWLVZLB-UHFFFAOYSA-N cobalt;oxozinc Chemical compound [Zn].[Co]=O LNBBNXBJWLVZLB-UHFFFAOYSA-N 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- 229910052596 spinel Inorganic materials 0.000 abstract description 5
- 239000011029 spinel Substances 0.000 abstract description 5
- 229910002518 CoFe2O4 Inorganic materials 0.000 abstract 2
- 229910003119 ZnCo2O4 Inorganic materials 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000012154 double-distilled water Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QNZMDVQBVILNJW-UHFFFAOYSA-N [Co]=O.[O-2].[Fe+2] Chemical compound [Co]=O.[O-2].[Fe+2] QNZMDVQBVILNJW-UHFFFAOYSA-N 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VVXZCXPNMAKNAL-UHFFFAOYSA-N [AlH3].O=[Co] Chemical compound [AlH3].O=[Co] VVXZCXPNMAKNAL-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- LTXHKPDRHPMBKA-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2] LTXHKPDRHPMBKA-UHFFFAOYSA-N 0.000 description 1
- KFCWRPFNNIEZRY-UHFFFAOYSA-H dialuminum;trisulfate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KFCWRPFNNIEZRY-UHFFFAOYSA-H 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- -1 iron oxide cobalt cobalt Chemical compound 0.000 description 1
- PCIREHBGYFWXKH-UHFFFAOYSA-N iron oxocobalt Chemical compound [Fe].[Co]=O PCIREHBGYFWXKH-UHFFFAOYSA-N 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- PTSZYEWEQITNAC-UHFFFAOYSA-N zinc dinitrate dihydrate Chemical compound O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O PTSZYEWEQITNAC-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- IFMFZGXDUBNWFJ-UHFFFAOYSA-N zinc oxocobalt oxygen(2-) Chemical compound [Co]=O.[O-2].[Zn+2] IFMFZGXDUBNWFJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、一酸化炭素の選択的酸
化方法および該方法に用いられる触媒に関する。TECHNICAL FIELD The present invention relates to a method for selectively oxidizing carbon monoxide and a catalyst used in the method.
【０００２】[0002]
【従来の技術およびその課題】特公昭５５−３３３７７
号公報には、スピネル型の結晶構造を持つＣｏイオンを
含むフェライトの存在下において、有毒成分として一酸
化炭素および酸化窒素を含むガス体を、加熱処理するこ
とにより、一酸化炭素および酸化窒素を同時に無毒化す
る方法が開示されているが、一酸化炭素および水素を含
むガス体について一酸化炭素のみを選択的に酸化させる
ことについては勿論のこと、一酸化炭素および水素を含
有するガス体についても記載されていない。2. Description of the Related Art JP-B-55-33377
In the publication, in the presence of ferrite containing Co ions having a spinel type crystal structure, a gas body containing carbon monoxide and nitric oxide as toxic components is heat-treated to remove carbon monoxide and nitric oxide. Although a method for detoxifying at the same time is disclosed, not only for a gas body containing carbon monoxide and hydrogen but also for selectively oxidizing only carbon monoxide, a gas body containing carbon monoxide and hydrogen is disclosed. Is also not listed.
【０００３】特開昭５８−９２８５０号公報には、還元
性ガスに感応して抵抗値が変化する金属酸化物半導体、
該金属酸化物半導体に装備された電極、および酸化触媒
を用いたガス選択透過性フィルターよりなる検知ガスの
選択性を有するガス検知素子が開示され、該ガス選択透
過性フィルターの素材として、ＮｉＯ、Ｃｏ２Ｏ３、Ｃ
ｏＯ、ＺｎＯ、ＳｎＯ２、Ｆｅ２Ｏ３、Ｖ２Ｏ５、Ａｇ
２Ｏ、ＣｕＯ等の各種金属酸化物触媒などが例示され、
これらの酸化触媒を用いたガス選択透過性フィルターに
よりＣＯガス、Ｈ２ガス、エタノール、イソブタンおよ
びメタンを順次選択的に透過しうる旨教示されている。
しかしながら、特開昭５８−９２８５０号公報には、一
酸化炭素と水棄との系において一酸化炭素を選択的に透
過するための酸化触媒および反応条件について具体的に
記載されておらず、しかも酸化触媒としてスピネル型コ
バルト酸化物を用いることについても記載されていな
い。Japanese Patent Laid-Open No. 58-92850 discloses a metal oxide semiconductor whose resistance value changes in response to a reducing gas,
Disclosed is a gas detection element having detection gas selectivity, which comprises an electrode equipped on the metal oxide semiconductor and a gas selection permeable filter using an oxidation catalyst, and NiO as a material of the gas selection permeable filter. Co 2 O 3 , C
oO, ZnO, SnO 2 , Fe 2 O 3 , V 2 O 5 , Ag
Examples include various metal oxide catalysts such as 2 O and CuO,
It is taught that CO gas, H 2 gas, ethanol, isobutane and methane can be sequentially selectively permeated by a gas selective permeable filter using these oxidation catalysts.
However, JP-A-58-92850 does not specifically describe an oxidation catalyst and reaction conditions for selectively permeating carbon monoxide in a system of carbon monoxide and water dump, and There is no mention of using spinel-type cobalt oxide as the oxidation catalyst.
【０００４】特開昭６３−２５２９０８号公報には、水
素、一酸化炭素またはブタンをそれぞれ１容量％含む空
気について、金超微粒子固定化コバルトフェライト（Ｃ
ｏＦｅ２Ｏ３）担持ハニカム触媒を用いたところ、水
素、一酸化炭素およびブタンの酸化開始温度がそれぞれ
５２℃、２３℃および１９０℃であった旨記載されてい
るが、酸化触媒として酸化鉄コバルトＣｏＦｅ２Ｏ４ま
たは酸化コバルト亜鉛ＺｎＣｏ２Ｏ４を使用することに
ついては記載されていない。Japanese Unexamined Patent Publication (Kokai) No. 63-252908 discloses cobalt ultrafine particles-immobilized cobalt ferrite (C) for air containing 1% by volume of hydrogen, carbon monoxide or butane.
It is described that when using an oFe 2 O 3 ) supported honeycomb catalyst, the oxidation start temperatures of hydrogen, carbon monoxide and butane were 52 ° C., 23 ° C. and 190 ° C., respectively. The use of CoFe 2 O 4 or cobalt zinc oxide ZnCo 2 O 4 is not mentioned.
【０００５】特開昭６４−８３５１３号公報には、アル
カリ土類金属化合物に金超微粒子を固定化した金超微粒
子固定化アルカリ土類金属化合物よりなり、水素および
一酸化炭素の低温酸化活性にすぐれた酸化触媒が開示さ
れているが、酸化触媒として、スピネル型コバルト酸化
物を用いることについては記載されていない。Japanese Unexamined Patent Publication (Kokai) No. 64-83513 discloses an ultrafine gold particle-immobilized alkaline earth metal compound in which ultrafine gold particles are immobilized on an alkaline earth metal compound, and has a low temperature oxidation activity of hydrogen and carbon monoxide. Although excellent oxidation catalysts are disclosed, there is no mention of using spinel type cobalt oxides as the oxidation catalyst.
【０００６】特開平１−９４９４５号公報には、金の超
微粒子を酸化鉄を主成分とする金属酸化物（ＭｅＯ）に
固定化したものを触媒担体上に担持してなり、常温にお
ける一酸化炭素の酸化活性にすぐれた金超微粒子固定化
金属酸化物担持触媒体が開示されているが、一酸化炭素
の酸化触媒としてスピネル型コバルト酸化物を用いるこ
とについては記載されていない。Japanese Patent Laid-Open No. 1-94945 discloses that ultrafine gold particles are immobilized on a metal oxide (MeO) containing iron oxide as a main component and supported on a catalyst carrier. Although a metal oxide-supported catalyst on which ultrafine gold particles are immobilized, which has excellent carbon oxidation activity, is disclosed, there is no description about using spinel-type cobalt oxide as an oxidation catalyst for carbon monoxide.
【０００７】表面、Ｖｏｌ．２８ Ｎｏ．５（１９９
０）には、水素または一酸化炭素１容量％空気混合ガス
について、Ｃｏ３Ｏ４金属酸化物触媒上での一酸化炭素
と水素の酸化反応率と温度との関係について開示されて
いるが、それぞれの酸化開始温度が比較的低く、水素に
対する一酸化炭素の選択性も満足すべき状態にない。Surface, Vol. 28 No. 5 (199
0) discloses the relationship between the oxidation reaction rate of carbon monoxide and hydrogen and the temperature on a Co 3 O 4 metal oxide catalyst for hydrogen or carbon monoxide 1% by volume air mixed gas. The respective oxidation initiation temperatures are relatively low, and the selectivity of carbon monoxide with respect to hydrogen is not satisfactory.
【０００８】従来実用化されているＳｎＯ２系半導体
（ＳｎＯ２に、例えば、ＰｔまたはＰｄを０．５重量％
添加したもの）によるＣＯセンサの反応性は、素子の作
動温度により変化し、１００℃以下の低温では、ＣＯの
感度が最も大きく、次いでエタノール、水素である。し
かし、１００℃以下では、応答速度が遅くなり、また水
蒸気吸着等による阻害もうけやすい。それでセンサに一
定周期の温度サイクルを与え、周期的にセンサを３００
〜４００℃程度に加熱し、水分や雑ガスが脱離した一定
の状態を保つことによって低温度での検知に良好な再現
性を得ることにしている。したがって、センサに一定周
期の温度サイクルを与える必要のない程度の高温におい
て、ＣＯの感度の高い素子の開発が要望されている。A SnO 2 based semiconductor that has been practically used in the past (for example, 0.5 wt% of Pt or Pd in SnO 2 is used.
The reactivity of the CO sensor with (added) changes depending on the operating temperature of the element, and at a low temperature of 100 ° C. or lower, the sensitivity of CO is greatest, followed by ethanol and hydrogen. However, if the temperature is 100 ° C. or lower, the response speed becomes slower, and water vapor adsorption or the like tends to cause inhibition. Therefore, the sensor is given a constant temperature cycle, and the sensor is periodically moved to 300
By heating to about 400 ° C. and maintaining a constant state in which moisture and miscellaneous gas are desorbed, good reproducibility is obtained for detection at low temperature. Therefore, there is a demand for the development of an element having high CO sensitivity at a high temperature at which it is not necessary to apply a constant temperature cycle to the sensor.
【０００９】本発明は、少量の一酸化炭素および水素を
含有する酸素含有ガスを、特定の酸化触媒の存在下、２
００〜４００℃の比較的高温下に熱処理することによ
り、一酸化炭素のみを選択的に酸化することのできる一
酸化炭素の選択的酸化方法、および該方法に用いられる
触媒を提供することを目的とするものである。また、本
発明は、少量の一酸化炭素および水素を含有する酸素含
有ガスについて、従来のＳｎＯ２系半導体によるＣＯセ
ンサの場合のように、センサに一定周期の温度サイクル
を与える必要がない、ＣＯセンサまたはＨ２センサ用の
ガスフィルターとして利用しうる一酸化炭素の選択的酸
化方法、および該方法に用いられる触媒を提供すること
を目的とするものである。According to the present invention, an oxygen-containing gas containing a small amount of carbon monoxide and hydrogen is added in the presence of a specific oxidation catalyst to 2
An object of the present invention is to provide a method for selectively oxidizing carbon monoxide, which is capable of selectively oxidizing only carbon monoxide by heat treatment at a relatively high temperature of 00 to 400 ° C., and a catalyst used in the method. It is what Further, according to the present invention, for an oxygen-containing gas containing a small amount of carbon monoxide and hydrogen, it is not necessary to apply a constant temperature cycle to the sensor as in the case of a conventional CO sensor using SnO 2 based semiconductor. An object of the present invention is to provide a method for selectively oxidizing carbon monoxide that can be used as a gas filter for a sensor or an H 2 sensor, and a catalyst used in the method.
【００１０】[0010]
【問題点を解決するための手段】本発明は、少量の一酸
化炭素および水素を含有する酸素含有ガスを、酸化鉄コ
バルトＣｏＦｅ２Ｏ４または酸化コバルト亜鉛ＺｎＣｏ
２Ｏ４のスピネル型コバルト酸化物よりなる触媒の存在
下、一酸化炭素が実質上完全に酸化される最低温度ない
し水素が実質上酸化されない最高温度の温度範囲で、一
酸化炭素のみを接触的に反応させ、該温度範囲が、酸化
鉄コバルト触媒を用いた場合２１５〜４０１℃範囲にあ
り、酸化コバルト亜鉛触媒を用いた場合２０９〜４０１
℃の範囲にあることを特徴とする一酸化炭素の選択的酸
化方法；および酸化鉄コバルトＣｏＦｅ２Ｏ４または酸
化コバルト亜鉛ＺｎＣｏ２Ｏ４のスピネル型コバルト酸
化物よりなり、該方法に用いられる触媒を提供するもの
である。According to the present invention, an oxygen-containing gas containing a small amount of carbon monoxide and hydrogen is added to iron oxide cobalt cobalt CoFe 2 O 4 or cobalt oxide zinc ZnCo.
In the presence of a catalyst composed of 2 O 4 spinel-type cobalt oxide, only carbon monoxide is catalytically contacted in the temperature range from the lowest temperature at which carbon monoxide is substantially completely oxidized to the highest temperature at which hydrogen is not substantially oxidized. And the temperature range is 215 to 401 ° C. when the iron oxide cobalt oxide catalyst is used, and 209 to 401 when the cobalt oxide zinc oxide catalyst is used.
A method for the selective oxidation of carbon monoxide characterized by being in the range of ° C; and a catalyst used in the method, comprising a spinel-type cobalt oxide of iron oxide cobalt CoFe 2 O 4 or cobalt zinc oxide ZnCo 2 O 4. Is provided.
【００１１】本発明において、少量の一酸化炭素および
水素を含有する酸素含有ガスとしては、例えば一酸化炭
素０．２〜１容量％、および水素０．２〜１容量％を含
有し、該一酸化炭素を二酸化炭素に酸化するのに必要な
酸素を含有するガスが包含されるが、該酸素含有ガスの
具体例として空気があげられる。また、少量の一酸化炭
素および水素を含有する酸素含有ガスの具体例として、
一酸化炭素および水素で汚染されている空気、湯沸器な
どの不完全燃焼排ガス、火災の時に発生するガス、自動
車などの排ガスなどがあげられる。In the present invention, the oxygen-containing gas containing a small amount of carbon monoxide and hydrogen contains, for example, 0.2 to 1% by volume of carbon monoxide and 0.2 to 1% by volume of hydrogen. A gas containing oxygen necessary for oxidizing carbon oxide to carbon dioxide is included, and a specific example of the oxygen-containing gas is air. Further, as a specific example of the oxygen-containing gas containing a small amount of carbon monoxide and hydrogen,
Examples include air polluted with carbon monoxide and hydrogen, incomplete combustion exhaust gas from water heaters, gas generated during a fire, and exhaust gas from automobiles.
【００１２】本発明における触媒は、スピネル型コバル
ト酸化物としての酸化鉄コバルトＣｏＦｅ２Ｏ４または
酸化コバルト亜鉛ＺｎＣｏ２Ｏ４である。The catalyst in the present invention is iron oxide cobalt CoFe 2 O 4 or cobalt oxide zinc ZnCo 2 O 4 as a spinel type cobalt oxide.
【００１３】本発明における触媒として用いられる酸化
鉄コバルトは、例えば、硝酸コバルト水溶液と硝酸鉄水
溶液とをコバルト：鉄モル比が１：２になるように混合
し、この混合水溶液にＮａ２ＣＯ３水溶液を滴下して得
られる沈澱物を、洗浄、乾燥し、通常６００℃〜８００
℃で６〜８時間、好ましくは６００℃で６時間焼成する
ことにより得られる。The iron oxide cobalt used as the catalyst in the present invention is obtained by mixing an aqueous solution of cobalt nitrate and an aqueous solution of iron nitrate so that the molar ratio of cobalt: iron is 1: 2, and adding Na 2 CO 3 to the mixed aqueous solution. The precipitate obtained by dropping the aqueous solution is washed and dried, and usually 600 ° C to 800 ° C.
It is obtained by firing at 6 ° C for 6 to 8 hours, preferably at 600 ° C for 6 hours.
【００１４】本発明における触媒として用いられる酸化
コバルト亜鉛は、例えば、硝酸コバルト水溶液と酢酸亜
鉛水溶液とをコバルト：亜鉛モル比が２：１になるよう
に混合し、この混合水溶液にＮａ２ＣＯ３水溶液を滴下
して得られる沈澱物を、洗浄、乾燥し、通常６００℃〜
８００℃で６〜８時間、好ましくは８００℃で８時間焼
成することにより得られる。The cobalt zinc oxide used as a catalyst in the present invention is prepared by mixing an aqueous solution of cobalt nitrate and an aqueous solution of zinc acetate at a cobalt: zinc molar ratio of 2: 1 and adding Na 2 CO 3 to the mixed aqueous solution. The precipitate obtained by dropping the aqueous solution is washed and dried, usually at 600 ° C or higher.
It is obtained by baking at 800 ° C. for 6 to 8 hours, preferably at 800 ° C. for 8 hours.
【００１５】本発明方法において、一酸化炭素の接触反
応は、酸素含有ガス中に含有される一酸化炭素が実質上
完全に酸化される最低温度ないし、共存する水素が実質
上酸化されない最高温度の温度範囲で行なわれる。ここ
に、一酸化炭素が実質上完全に酸化される最低温度と
は、一酸化炭素の転化率が８０％に達する温度、好まし
くは該転化率が９０％に達する温度を意味し、共存する
水素が実質上酸化されない最高温度とは、水素の転化率
が２０％に達する温度、好ましくは該転化率が１０％に
達する温度を意味する。具体的には、該温度範囲は、酸
化鉄コバルト触媒を用いた場合、２１５〜４０１℃、好
ましくは２２８〜３７７℃の範囲にあり、酸化コバルト
亜鉛触媒を用いた場合には、２０９〜４０１℃、好まし
くは２１６〜３７７℃の範囲にある。酸化鉄コバルト触
媒を用いた場合の反応温度が２１５℃未満であるか、あ
るいは酸化コバルト亜鉛触媒を用いた場合の反応温度が
２０９℃未満であると、水素は全く酸化されず、一酸化
炭素の酸化選択性は高くなるが、一酸化炭素の転化率が
低下するため好ましくなく、酸化鉄コバルト触媒を用い
た場合の反応温度が４０１℃を超えるか、あるいは酸化
コバルト亜鉛触媒を用いた場合の反応温度が４０１℃を
超えると、一酸化炭素が完全に酸化されると共に、水素
の転化率も２０％を超えて増大し、一酸化炭素の酸化選
択性が低下するため好ましくない。In the method of the present invention, the catalytic reaction of carbon monoxide has a minimum temperature at which carbon monoxide contained in the oxygen-containing gas is substantially completely oxidized or a maximum temperature at which coexisting hydrogen is not substantially oxidized. It is carried out in the temperature range. Here, the minimum temperature at which carbon monoxide is substantially completely oxidized means a temperature at which the conversion rate of carbon monoxide reaches 80%, preferably a temperature at which the conversion rate reaches 90%, and coexisting hydrogen is present. The maximum temperature at which hydrogen is not substantially oxidized means the temperature at which the conversion rate of hydrogen reaches 20%, preferably the temperature at which the conversion rate reaches 10%. Specifically, the temperature range is 215 to 401 ° C, preferably 228 to 377 ° C when the iron oxide cobalt catalyst is used, and 209 to 401 ° C when the cobalt oxide zinc catalyst is used. , Preferably in the range of 216 to 377 ° C. When the reaction temperature when the iron oxide cobalt oxide catalyst is used is less than 215 ° C. or when the reaction temperature when the cobalt oxide zinc catalyst is used is less than 209 ° C., hydrogen is not oxidized at all and carbon monoxide Although the oxidation selectivity is high, it is not preferable because the conversion rate of carbon monoxide is lowered, and the reaction temperature when using the iron oxide cobalt catalyst exceeds 401 ° C or the reaction when using the cobalt zinc oxide catalyst. When the temperature exceeds 401 ° C., carbon monoxide is completely oxidized, the conversion rate of hydrogen increases by more than 20%, and the oxidation selectivity of carbon monoxide decreases, which is not preferable.
【００１６】[0016]
【発明の効果】本発明によれば、酸素含有ガス中に含有
される一酸化炭素が実質上完全に酸化される最低温度な
いし、共存する水素が実質上酸化されない最高温度の温
度範囲が、広くかつ２００〜４００℃の高温領域にある
ため、一酸化炭素を選択的に酸化することが可能であ
り、ＣＯセンサまたはＨ２センサ用のガスフィルターと
して利用した場合、センサに一定周期の温度サイクルを
与える必要がなく利用しうる一酸化炭素の選択的酸化方
法、および該方法に用いられる触媒が提供される。According to the present invention, the temperature range of the lowest temperature at which carbon monoxide contained in an oxygen-containing gas is substantially completely oxidized or the highest temperature at which coexisting hydrogen is not substantially oxidized is wide. Moreover, since it is in a high temperature range of 200 to 400 ° C., it is possible to selectively oxidize carbon monoxide, and when used as a gas filter for a CO sensor or an H 2 sensor, the sensor is subjected to a constant cycle of temperature. Provided is a method for selectively oxidizing carbon monoxide that can be utilized without the need to provide it, and a catalyst used in the method.
【００１７】[0017]
【実施例】以下、製造例、実施例および比較例により本
発明をさらに詳しく説明する。EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples.
【００１８】製造例１ 硝酸コバルト６水和物２．５２重量％水溶液１３３ｇ
と、硝酸鉄９水和物３．４９重量％水溶液２６６ｇとを
混合してコバルト対鉄のモル比が１対２となる混合水溶
液を得た。この混合水溶液にＮａ２ＣＯ３１．０５重量
％水溶液６００ｇを滴下して沈澱物を得た。この沈澱物
を２回蒸留水を用いて洗浄し、乾燥し、６００℃で６時
間焼成して酸化鉄コバルト触媒（触媒１）を得た。Production Example 1 133 g of 2.52% by weight aqueous solution of cobalt nitrate hexahydrate
And 266 g of a 3.49 wt% aqueous solution of iron nitrate nonahydrate were mixed to obtain a mixed aqueous solution having a cobalt to iron molar ratio of 1: 2. To this mixed aqueous solution, 600 g of 1.05% by weight Na 2 CO 3 aqueous solution was added dropwise to obtain a precipitate. The precipitate was washed with double distilled water, dried, and calcined at 600 ° C. for 6 hours to obtain an iron cobalt oxide catalyst (catalyst 1).
【００１９】製造例２ 製造例１における６００℃で６時間の焼成に代えて８０
０℃で８時間焼成した以外、製造例１と同様にして酸化
鉄コバルト触媒（触媒２）を得た。Production Example 2 Instead of firing at 600 ° C. for 6 hours in Production Example 1, 80
An iron oxide cobalt catalyst (catalyst 2) was obtained in the same manner as in Production Example 1 except that the calcination was performed at 0 ° C. for 8 hours.
【００２０】製造例３ 硝酸コバルト６水和物２．６３重量％水溶液２６６ｇと
硝酸亜鉛２水和物１．９８重量％水溶液１３３ｇとを混
合して、コバルト対亜鉛のモル比が２対１となる混合水
溶液を得た。この混合水溶液にＮａ２ＣＯ３１．０５重
量％水溶液６００ｇを滴下して沈澱物を得た。得られた
沈澱物を２回蒸留水を用いて洗浄し、乾燥し、６００℃
で６時間焼成して酸化コバルト亜鉛触媒（触媒３）を得
た。Production Example 3 266 g of a 2.63 wt% aqueous solution of cobalt nitrate hexahydrate and 133 g of a 1.98 wt% aqueous solution of zinc nitrate dihydrate were mixed to give a molar ratio of cobalt to zinc of 2: 1. A mixed aqueous solution was obtained. To this mixed aqueous solution, 600 g of 1.05% by weight Na 2 CO 3 aqueous solution was added dropwise to obtain a precipitate. The precipitate obtained is washed with double distilled water, dried and dried at 600 ° C.
The mixture was calcined for 6 hours to obtain a cobalt zinc oxide catalyst (catalyst 3).
【００２１】製造例４ 製造例３における６００℃で６時間の焼成に代えて８０
０℃で８時間焼成した以外、製造例３と同様にして酸化
コバルト亜鉛触媒（触媒４）を得た。Production Example 4 Instead of firing at 600 ° C. for 6 hours in Production Example 3, 80
A cobalt zinc oxide catalyst (catalyst 4) was obtained in the same manner as in Production Example 3 except that the baking was performed at 0 ° C for 8 hours.
【００２２】比較触媒１ 四酸化三コバルト触媒（ナカライ（株）製）を比較触媒
１として用いた。Comparative Catalyst 1 A tricobalt tetraoxide catalyst (manufactured by Nakarai Co., Ltd.) was used as Comparative Catalyst 1.
【００２３】比較触媒２ 硝酸コバルト６水和物２．４１重量％水溶液１３３ｇと
硫酸アルミニウム９水和物３．１０重量％水溶液２６６
ｇとを混合して、混合水溶液を得た。この混合水溶液に
１．０５重量％Ｎａ２ＣＯ３水溶液を滴下して沈澱物を
得た。この沈澱物を２回蒸留水を用いて洗浄し、乾燥
し、６００℃で６時間焼成して酸化アルミニウムコバル
ト（ＣｏＡｌ２Ｏ４）触媒（比較触媒２）を得た。Comparative catalyst 2 133 g of a 2.41% by weight aqueous solution of cobalt nitrate hexahydrate and an aqueous solution of 3.10% by weight of aluminum sulfate nonahydrate 266
and g were mixed to obtain a mixed aqueous solution. A 1.05 wt% Na 2 CO 3 aqueous solution was added dropwise to this mixed aqueous solution to obtain a precipitate. The precipitate was washed with double distilled water, dried, and calcined at 600 ° C. for 6 hours to obtain an aluminum cobalt oxide (CoAl 2 O 4 ) catalyst (comparative catalyst 2).
【００２４】比較触媒３ 比較触媒２において、６００℃で６時間の焼成に代えて
８００℃で８時間焼成した以外、比較触媒２と同様にし
て、酸化アルミニウムコバルト触媒（比較触媒３）を得
た。Comparative Catalyst 3 An aluminum cobalt oxide catalyst (Comparative Catalyst 3) was obtained in the same manner as Comparative Catalyst 2, except that Comparative Catalyst 2 was calcined at 800 ° C. for 8 hours instead of 600 ° C. for 6 hours. .
【００２５】実施例１ 外径６ｍｍ、内径４ｍｍの連続流通式リアクターに、前
記触媒１の粉末０．２ｇに対し、希釈剤ＳｉＯ２を容量
で５対３の割合で混合したものを充填し、一酸化炭素１
容量％、水素１容量％、酸素５容量％および残り窒素よ
りなる反応ガスを用いて、反応ガス流量５０ｍｌ／ｍｉ
ｎ（ＳＶ＝１．５×１０４ｈ−１・ｍｌ／ｇ）の条件
下、反応温度を変化させて、一酸化炭素および水素の接
触的酸化反応実験を行ない、一酸化炭素および水素の酸
化反応による転化率と反応温度との関係を求めた。得ら
れた結果を表１および表２に示す。Example 1 A continuous flow reactor having an outer diameter of 6 mm and an inner diameter of 4 mm was filled with 0.2 g of the powder of the catalyst 1 mixed with a diluent SiO 2 in a volume ratio of 5: 3, Carbon monoxide 1
A reaction gas flow rate of 50 ml / mi using a reaction gas consisting of vol.%, Hydrogen 1 vol.%, Oxygen 5 vol.% And the remaining nitrogen.
Under the condition of n (SV = 1.5 × 10 4 h −1 · ml / g), the reaction temperature was changed and the catalytic oxidation reaction experiment of carbon monoxide and hydrogen was conducted to oxidize carbon monoxide and hydrogen. The relationship between the conversion rate by the reaction and the reaction temperature was determined. The obtained results are shown in Tables 1 and 2.
【００２６】実施例２〜４および比較例１〜３ 実施例１の触媒１に代えて、それぞれ表１に示される触
媒を用いた以外、実施例１と同様の実験を行なった。得
られた結果を表１および表２に示す。Examples 2 to 4 and Comparative Examples 1 to 3 The same experiment as in Example 1 was carried out except that the catalysts shown in Table 1 were used instead of the catalyst 1 of Example 1. The obtained results are shown in Tables 1 and 2.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【表２】 [Table 2]
Claims (2)
酸素含有ガスを、酸化鉄コバルトＣｏＦｅ２Ｏ４または
酸化コバルト亜鉛ＺｎＣｏ２Ｏ４のスピネル型コバルト
酸化物よりなる触媒の存在下、一酸化炭素が実質上完全
に酸化される最低温度ないし水素が実質上酸化されない
最高温度の温度範囲で、一酸化炭素のみを接触的に反応
させ、該温度範囲が、酸化鉄コバルト触媒を用いた場合
２１５〜４０１℃範囲にあり、酸化コバルト亜鉛触媒を
用いた場合２０９〜４０１℃の範囲にあることを特徴と
する一酸化炭素の選択的酸化方法。1. An oxygen-containing gas containing a small amount of carbon monoxide and hydrogen is oxidized in the presence of a catalyst composed of a spinel-type cobalt oxide of iron oxide cobalt CoFe 2 O 4 or cobalt zinc oxide ZnCo 2 O 4. In the temperature range from the lowest temperature at which carbon is substantially completely oxidized to the highest temperature at which hydrogen is not substantially oxidized, only carbon monoxide is catalytically reacted, and the temperature range is 215 when an iron oxide cobalt catalyst is used. To 401 ° C, and in the case of using a cobalt zinc oxide catalyst, it is in the range of 209 to 401 ° C.
化コバルト亜鉛ＺｎＣｏ２Ｏ４のスピネル型コバルト酸
化物よりなり、請求項１記載の方法に用いられる触媒。2. A catalyst for use in the method according to claim 1, which comprises a spinel-type cobalt oxide of iron oxide cobalt CoFe 2 O 4 or cobalt zinc oxide ZnCo 2 O 4 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5258805A JPH0741313A (en) | 1993-07-27 | 1993-07-27 | Method for selectively oxidizing carbon monoxide and catalyst used for the same method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5258805A JPH0741313A (en) | 1993-07-27 | 1993-07-27 | Method for selectively oxidizing carbon monoxide and catalyst used for the same method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0741313A true JPH0741313A (en) | 1995-02-10 |
Family
ID=17325301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5258805A Pending JPH0741313A (en) | 1993-07-27 | 1993-07-27 | Method for selectively oxidizing carbon monoxide and catalyst used for the same method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0741313A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100522042B1 (en) * | 2002-07-15 | 2005-10-18 | 김희정 | Process for Preparing Catalyst for Oxidizing Carbon Monoxide |
| EP1896178A1 (en) * | 2005-06-29 | 2008-03-12 | Samsung Engineering Co., Ltd. | Metal oxide catalyst for hydrogen generation and method of producing the same |
| KR100847443B1 (en) * | 2007-02-23 | 2008-07-22 | 고려대학교 산학협력단 | Cr-free catalysts for high temperature water gas shift reaction to remove carbon monoxide |
| JP2011078947A (en) * | 2009-10-09 | 2011-04-21 | Agc Seimi Chemical Co Ltd | Ammonia decomposition catalyst and ammonia decomposition method |
| WO2013108424A1 (en) * | 2012-01-19 | 2013-07-25 | トヨタ自動車株式会社 | Exhaust gas purifying catalyst and method for producing same |
-
1993
- 1993-07-27 JP JP5258805A patent/JPH0741313A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100522042B1 (en) * | 2002-07-15 | 2005-10-18 | 김희정 | Process for Preparing Catalyst for Oxidizing Carbon Monoxide |
| EP1896178A1 (en) * | 2005-06-29 | 2008-03-12 | Samsung Engineering Co., Ltd. | Metal oxide catalyst for hydrogen generation and method of producing the same |
| EP1896178A4 (en) * | 2005-06-29 | 2011-10-05 | Samsung Eng Co Ltd | Metal oxide catalyst for hydrogen generation and method of producing the same |
| KR100847443B1 (en) * | 2007-02-23 | 2008-07-22 | 고려대학교 산학협력단 | Cr-free catalysts for high temperature water gas shift reaction to remove carbon monoxide |
| JP2011078947A (en) * | 2009-10-09 | 2011-04-21 | Agc Seimi Chemical Co Ltd | Ammonia decomposition catalyst and ammonia decomposition method |
| WO2013108424A1 (en) * | 2012-01-19 | 2013-07-25 | トヨタ自動車株式会社 | Exhaust gas purifying catalyst and method for producing same |
| CN104053503A (en) * | 2012-01-19 | 2014-09-17 | 丰田自动车株式会社 | Exhaust gas purifying catalyst and method for producing same |
| JPWO2013108424A1 (en) * | 2012-01-19 | 2015-05-11 | トヨタ自動車株式会社 | Exhaust gas purification catalyst and method for producing the same |
| US9314775B2 (en) | 2012-01-19 | 2016-04-19 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst and method for producing same |
| CN104053503B (en) * | 2012-01-19 | 2016-11-02 | 丰田自动车株式会社 | Exhaust emission control catalyst and manufacture method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4921829A (en) | Catalyst for purifing exhaust gases | |
| US4157316A (en) | Polyfunctional catalysts | |
| Yao | The oxidation of hydrocarbons and CO over metal oxides: IV. Perovskite-type oxides | |
| US5500198A (en) | Composite catalyst for carbon monoxide and hydrocarbon oxidation | |
| US4010238A (en) | Proces for selective removal of nitrogen oxides from waste gases | |
| EP0222497B1 (en) | Method of simultaneous oxidation of carbon monoxide and unburned fuel in methanol-fueled vehicle exhaust | |
| US5384301A (en) | Catalyst for elemental sulfur recovery process | |
| KR970009558B1 (en) | Copper oxide and ceria catalyst | |
| US4552733A (en) | Polyfunctional catalysts and method of use | |
| US5283055A (en) | Process using novel catalysts for the selective reduction of nitrogen oxides | |
| EP0208434A1 (en) | Process for removing nitrogen oxides and carbon monoxide simultaneously | |
| Lindstedt et al. | High-temperature catalytic reduction of nitrogen monoxide by carbon monoxide and hydrogen over La1− xSrxMO3 perovskites (M= Fe, Co) during reducing and oxidising conditions | |
| US4018710A (en) | Reduction catalysts and processes for reduction of nitrogen oxides | |
| JPH03186346A (en) | Catalyst for purifying exhaust gas and catalyst structure | |
| US5192515A (en) | Reduction of nitrogen oxide and carbon monoxide in effluent gases | |
| JPH0741313A (en) | Method for selectively oxidizing carbon monoxide and catalyst used for the same method | |
| US4228138A (en) | Catalysis | |
| US3801697A (en) | Process for reducing the content of nitrogen oxides in the exhaust gases from internal combustion engines | |
| EP0741607B1 (en) | Method of making a catalyst | |
| JPH0220561B2 (en) | ||
| JP2001058130A (en) | Catalyst for nitrogen oxide decomposition | |
| Imamura et al. | Oxidation of acetic acid on Co Bi composite oxide catalysts | |
| JP4016193B2 (en) | Denitration catalyst | |
| JP3634795B2 (en) | Nitrogen oxide and / or sulfur oxide adsorbent | |
| US5302365A (en) | Process for the catalytic combustion of methane |