CN103990470A - Supported iridium catalyst applicable to oxidation reaction of carbon monoxide and preparation method of catalyst - Google Patents
Supported iridium catalyst applicable to oxidation reaction of carbon monoxide and preparation method of catalyst Download PDFInfo
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- CN103990470A CN103990470A CN201410255005.9A CN201410255005A CN103990470A CN 103990470 A CN103990470 A CN 103990470A CN 201410255005 A CN201410255005 A CN 201410255005A CN 103990470 A CN103990470 A CN 103990470A
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- catalyst
- carrier
- iridium
- oxidation reaction
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to a supported iridium catalyst applicable to catalytic oxidation reaction of CO and a preparation method of the catalyst. The catalyst takes metal iridium as an active component, takes transition metals which are selected from one or more of Fe, Co, Ni and Cu as additives and takes Al2O3 as a carrier. The catalyst is prepared by using an impregnation method, and the catalyst is high in CO oxidation activity and stability.
Description
Technical field
The present invention relates to catalyst technical field, relate to a kind of supported iridium catalyst for carbon monoxide (CO) oxidation reaction, can be used for CO
2the purification of CO in laser instrument, CO sensor, subterranean tunnel and closed environment is eliminated.
Background technology
Along with the fast development of global economy, world energy consumption is doubled and redoubled in recent years, and Which Ecological Environment Faced serious deterioration, and the sustainable development of human society is on the hazard.Atmosphere pollution becomes current outstanding environmental problem.
Carbon monoxide CO is one of atmosphere pollution that coverage is wide, and CO gas colorless and odorless is inflammable and explosive.CO can be combined with hemoglobin after entering blood of human body by respiratory system, and then stops the combination of hemoglobin and oxygen, causes body tissue anoxic, and severe patient may suffocate.Therefore, CO gas purification has numerous application in human lives and industrial production.For example evil falls in respiratory protection equipment, tobacco, trace amounts of CO elimination, CO gas sensor and CO in closed system (as aircraft, submarine, spacecraft) and fuel cell
2the aspects such as the purification for gas of laser instrument.The most effective purification style of CO is the method that adopts catalytic oxidation, and it is converted into as environmentally friendly CO
2.
CO oxidation catalyst is mainly divided into two large class, non-precious metal catalyst and noble metal catalysts.For non-precious metal catalyst, mainly contain Co
3o
4catalyst based, CuO-MnO
xcomposite oxide catalyst (Hopcalite catalyst) etc., wherein Co
3o
4and catalyst shows very high CO oxidation activity, but it is to the H in atmosphere
2o content is very responsive, even the water of trace also can cause its rapid deactivation.For noble metal catalyst, the kind of active metal, the selection of catalyst carrier and preparation method have impact very significantly to its reactivity.Since Haruta seminar finds the metal oxide (TiO preparing by the deposition-precipitation method
2, Fe
2o
3, NiO etc.) load gold catalyst, since room temperature and even subzero CO oxidation are had to very high activity (M. Haruta, N. Yamada, J. Catal., 1989,115,301), nano catalyst has caused researcher's extensive concern.But the poor stability of nano-Au catalyst, illumination or deposit after a period of time, all can cause its inactivation, the general more complicated harshness of preparation condition of nano catalyst simultaneously, catalyst poor repeatability.For Pd, Pt catalyst, because it has high absorption property to CO, generally under higher temperature, show good CO oxidation activity.Recently, by the change of kind of carrier and preparation method's optimization, as at Pt(111) the FeOx(X. H. Bao et al. that grows on face, Science, 2010,328,1141.), at Fe (OH)
xupper load P d(Y. Q. Deng, et al., J. Catal., 2010,274,1.) etc., can obtain the CO oxidation activity suitable with nano-Au catalyst.The employing deposition-precipitation methods such as Okumura have been prepared Ir/TiO
2catalyst shows good CO oxidation activity (M. Okumura, et al., J. Catal. 2002,208 (2), 485-489.) under the condition lower than room temperature.The employing coprecipitations such as Zhang Tao have been prepared Ir-CeO
2catalyst, shows high activity (T. Zhang, et al., J. Catal. 2008,255 (2), 144-152.) to the selective oxidation of CO under hydrogen condition.
Summary of the invention
The object of the invention is to prepare a kind of supported iridium catalyst, there is higher CO oxidation activity, and there is high operational stability.
Compared with the prior art, feature of the present invention is:
(1) can significantly improve the decentralization of iridium, strengthen the activity of catalyst to CO oxidation;
(2) prepared catalyst has good stability;
(3) adopt infusion process preparation, reproducible.
The technology path of catalyst of the present invention is:
Catalyst of the present invention taking metal iridium as active component, with Al
2o
3for carrier, auxiliary agent is one or more in Fe, Co, Ni and Cu.Wherein the weight content of active component iridium is 0.01 ~ 10%, and the weight content of auxiliary agent is 0.02 ~ 40%.
The technology path of catalyst of the present invention is: adopt infusion process to prepare the carrier of modification, after having flooded, drying, roasting, reduction obtain addition agent modified Al
2o
3carrier; Then flood the precursor solution of iridium, after having flooded, drying, roasting, reduction obtain the iridium catalyst of load.
In order to be illustrated more clearly in the present invention, enumerate following examples, but without any restrictions to scope of the present invention.
Embodiment 1
Take 1.14g Nickelous nitrate hexahydrate and use 2mL deionized water dissolving, then at 2g Al
2o
3in carrier, add this nickel nitrate solution and constantly stir 30 minutes, the system of then flooding is as for 30
oin C water-bath, leave standstill 24 hours, then be placed in 100
oc oven for drying is spent the night, and 800
oin C Muffle furnace, roasting 4 hours, finally obtains NiAl
2ox carrier.Take 0.016g acetic acid iridium and use the water-soluble solution of 5mL to form precursor solution.By 0.5g NiAl
2ox carrier is 800
o5 vol.% H under C
2/ N
2in gaseous mixture, reduce 30 minutes.After reduction finishes, cool to after room temperature with hydrogen again, take out the carrier being reduced and join in the iridium precursor solution in advance configuring and flood 30 minutes, then remove excess solution, 100
oc oven for drying is spent the night, in Muffle furnace 400
oc roasting 4 hours, finally at 5 vol.% H
2/ N
2in gaseous mixture 200
ounder C, reduce 0.5h, make Ir/NiAl
2ox catalyst.
The CO catalytic oxidation activity of catalyst carries out in U-type fixed bed crystal reaction tube, and reaction gas is normal pressure, and each active testing uses 20-40 object catalyst 200mg.Reactor feed gas is 1 vol.% CO and 20 vol.% O
2, Balance Air is N
2, air speed is 15,000 ml g
1h
1.Active testing reaches after stable and carries out in reaction.
Activity rating result shows, prepared Ir/NiAl
2on Ox catalyst, the full conversion temperature of CO is 113
oc.
Embodiment 2
Take 0.95g Gerhardite and use 2mL deionized water dissolving, then at 2g Al
2o
3in carrier, add this copper nitrate solution and constantly stir 30 minutes, the system of then flooding is as for 30
oin C water-bath, leave standstill 24 hours, then be placed in 100
oc oven for drying is spent the night, and 700
oin C Muffle furnace, roasting 4 hours, obtains CuAl
2ox carrier.By 0.5g modification CuAl
2ox carrier is 700
ounder C, reduce 30 minutes.All the other steps are with embodiment 1.
Activity rating result shows, prepared Ir/CuAl
2on Ox catalyst, the full conversion temperature of CO is 100
oc.
Embodiment 3
Take 1.14g cabaltous nitrate hexahydrate and use 2mL deionized water dissolving, then at 2g Al
2o
3in carrier, add this cobalt nitrate solution and constantly stir 30 minutes, the system of then flooding is as for 30
oin C water-bath, leave standstill 24 hours, then be placed in 100
oc oven for drying is spent the night, and 600
oin C Muffle furnace, roasting 4 hours, obtains CoAl
2ox carrier.By 0.5g CoAl
2ox carrier is 600
ounder C, reduce 30 minutes.All the other steps are with embodiment 1.
Activity rating result shows, prepared Ir/CoAl
2the full conversion temperature of CO of Ox catalyst is 129
oc.
Embodiment 4
Take 1.14g six nitric hydrate iron and use 2mL deionized water dissolving, then at 2g Al
2o
3in carrier, add this iron nitrate solution and constantly stir 30 minutes, the system of then flooding is as for 30
oin C water-bath, leave standstill 24 hours, then be placed in 100
oc oven for drying is spent the night, and 500
oin C Muffle furnace, roasting 4 hours, obtains FeAl
2ox carrier.By 0.5gFeAl
2ox carrier is 500
ounder C, reduce 30 minutes.All the other steps with embodiment 1 all the other steps with embodiment 1.
Activity rating result shows, prepared Ir/FeAl
2the full conversion temperature of CO of Ox catalyst is 90
oc.
Embodiment 5
Take 0.016g acetic acid iridium and use the water-soluble solution of 5mL to form precursor solution, by 0.5gAl
2o
3join in the iridium precursor solution in advance configuring and flood 30 minutes, then remove excess solution, 100
oc oven for drying is spent the night, in Muffle furnace 400
oc roasting 4 hours, makes IrO/Al
2o
3catalyst.
Activity rating result shows, prepared IrO/Al
2o
3the full conversion temperature of CO of catalyst is 250
oc.
Embodiment 6
With embodiment 5, prepared IrO/Al
2o
3at 5 vol.% H
2/ N
2in gaseous mixture 200
ounder C, reduce 0.5h, make Ir/Al
2o
3catalyst.
Activity rating result shows, prepared Ir/Al
2o
3the full conversion temperature of CO of catalyst is 165
oc.
Claims (7)
1. for a supported iridium catalyst for CO oxidation reaction, this catalyst has high CO oxidation activity and stability, it is characterized in that:
Active component is metal Ir;
Auxiliary agent is one or more in Fe, Co, Ni and Cu;
Carrier is Al
2o
3.
2. a kind of supported iridium catalyst for CO oxidation reaction according to claim 1, the weight content that it is characterized in that active component iridium is 0.01 ~ 10%, the weight content of auxiliary agent is 0.02 ~ 40%.
3. a kind of supported iridium catalyst for CO oxidation reaction according to claim 1, is characterized in that catalyst adopts infusion process preparation, and concrete preparation process comprises:
(1) aqueous solution of the soluble-salt of formulation aid proportionally, with Al
2o
3for carrier, after having flooded, drying, that roasting obtains carrier is for subsequent use;
(2) carrier is reduced under hydrogen atmosphere, obtain the carrier after reduction;
(3) with the precursor solution of the carrier impregnation iridium after reducing, after having flooded, drying, roasting, reduction obtain finished catalyst.
4. a kind of preparation method of the supported iridium catalyst for CO oxidation reaction according to claim 4, is characterized in that carrier sintering temperature is 300 ~ 900
oc, carrier reduction temperature is 300 ~ 900
oc, the reduction temperature of catalyst is 100 ~ 500
oc.
5. a kind of preparation method of the supported iridium catalyst for CO oxidation reaction according to claim 4, is characterized in that, auxiliary agent enters Al after roasting
2o
3lattice in, form Al
2o
3the spinel structure of load.
6. a kind of preparation method of the supported iridium catalyst for CO oxidation reaction according to claim 4, is characterized in that, carrier is after reduction, and auxiliary agent part exists with the form of metallic state.
7. a kind of preparation method of the supported iridium catalyst for CO oxidation reaction according to claim 4, it is characterized in that, the presoma salt of iridium is iridium chloride, the one in acetylacetone,2,4-pentanedione iridium or acetic acid iridium, and the soluble-salt of auxiliary agent is the one in nitrate, hydrochloride or acetate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940576A (en) * | 2014-01-31 | 2016-09-14 | Asml荷兰有限公司 | Catalytic conversion of an optical amplifier gas medium |
| CN109833883A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high activity bimetallic load combustion catalyst and preparation method thereof |
| CN110252336A (en) * | 2019-06-05 | 2019-09-20 | 北京氦舶科技有限责任公司 | Monatomic noble metal catalyst and its preparation method and application |
| CN114643065A (en) * | 2020-12-17 | 2022-06-21 | 北京工业大学 | Noble metal catalyst for catalytic oxidation of CO and preparation method thereof |
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| JP2003265956A (en) * | 2002-03-14 | 2003-09-24 | Nippon Oil Corp | Catalyst for selectively oxidizing carbon monoxide, method of reducing concentration of carbon monoxide, and fuel cell system |
| CN101168130A (en) * | 2005-10-21 | 2008-04-30 | 三星Sdi株式会社 | Catalyst for oxidizing carbon monoxide and method of manufacturing the same |
| CN101428227A (en) * | 2007-11-07 | 2009-05-13 | 中国科学院大连化学物理研究所 | Iridium based bi-component supported catalyst, preparation and application thereof |
| CN102059127A (en) * | 2010-11-09 | 2011-05-18 | 华东理工大学 | Catalyst for CO normal temperature catalytic oxidation and preparation method thereof |
-
2014
- 2014-06-11 CN CN201410255005.9A patent/CN103990470A/en active Pending
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| JPH02258061A (en) * | 1989-03-30 | 1990-10-18 | Osaka Gas Co Ltd | Nox decomposing catalyst and combustion apparatus utilizing the same |
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|---|
| WANSHENG ZHANG ET AL: "Design of a novel bifunctional catalyst IrFe/Al2O3 for preferential CO oxidation", 《CATALYSIS TODAY》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105940576A (en) * | 2014-01-31 | 2016-09-14 | Asml荷兰有限公司 | Catalytic conversion of an optical amplifier gas medium |
| CN109833883A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of high activity bimetallic load combustion catalyst and preparation method thereof |
| CN110252336A (en) * | 2019-06-05 | 2019-09-20 | 北京氦舶科技有限责任公司 | Monatomic noble metal catalyst and its preparation method and application |
| CN114643065A (en) * | 2020-12-17 | 2022-06-21 | 北京工业大学 | Noble metal catalyst for catalytic oxidation of CO and preparation method thereof |
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Application publication date: 20140820 |