CN101062478A - Catalyst for carbon monoxide oxidation in hydrogen and preparation method thereof - Google Patents
Catalyst for carbon monoxide oxidation in hydrogen and preparation method thereof Download PDFInfo
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- CN101062478A CN101062478A CN 200610011795 CN200610011795A CN101062478A CN 101062478 A CN101062478 A CN 101062478A CN 200610011795 CN200610011795 CN 200610011795 CN 200610011795 A CN200610011795 A CN 200610011795A CN 101062478 A CN101062478 A CN 101062478A
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Abstract
The invention relates to a CO catalyst made of the carrier and the active carbon. The active carbon, carbon black, middle hole carbon, carbon nanometer tube as the carrier, metal platinum, silver and iron in single or compound form to be the active element, with metal weighing 0. 5-25%, silver or iron percentage to platinum being 16:1-16, and platinum: iron: Nickel being 10:1-5:1-5 in weight. It has excellent activity and selectivity, easy for manufacturing, low in cost, unnecessary for extra oxygen, safe in CO and O2 reaction, improved in catalyst energy utilization.
Description
Technical field
The present invention relates to the catalyst of selectivity oxidizing carbon monoxide in the hydrogen, specifically a kind of Catalysts and its preparation method that is used for low temperature selective oxidation hydrogen carbon monoxide.
Background technology
In recent years, the fuel cell (PEMFCs) that with hydrogen is fuel is in light weight because of it, volume is little, do not produce secondary pollution, have characteristics such as high energy utilization rate at low temperature and be widely studied and applied, fuel cell more and more be it is believed that it is desirable motor vehicle in future, the energy source of semiworks etc.For fear of the hydrogen that stores high pressure onboard, and be used to produce the hydrogen of the energy mainly from methyl alcohol and hydro carbons; Fuel cell need come the oxidation of hydrogen and the oxygen reduction of catalysis low temperature with the platinum electrode catalyst, but platinum electrode is easy to be poisoned by a small amount of imperfect combustion product carbon monoxide at a lower temperature, thereby make the utilization rate of fuel cell reduce [S.Gottesfeld, J.Pafford, J.Electrochem.Soc.135 (1988) 2651].Mainly address this problem at present from two aspects, the one, solve the ability of platinum electrode anti-carbon monoxide, the 2nd, reduce the content of carbon monoxide as far as possible, from the catalysis angle and handle on the complexity, second method is easier; In the method for various reduction carbon monoxide contents, it is the simplest and inexpensive method that the catalytic oxidation of carbon monoxide is eliminated; The catalyst of maximum selectivity oxidizing carbon monoxide of people's research is Al
2O
3The Pt that supports, Rh, noble metal catalysts such as Ru.The research of the Pt catalyst that oxide supports is the most extensive, but in reaction system, they adopt the carbon monoxide in the excess of oxygen deoxidation hydrogen, be easy to the heavy explosion of the system of inducing reaction, simultaneously excess of oxygen (greater than stoichiometric proportion) will with hydrogen reaction, the hydrogen in the consume fuel gas, thereby the utilization rate [M.J.Kahlich of hydrogen in the reduction fuel cell, H.A.Gasteiger, R.J.Behm, J.Catal.171 (1997) 93].The Ru-mordenite catalyst has 100% selectivity to carbon monoxide, but temperature that need be very high [H.Igarashi, H.Uchida, M.Wantanabe, Chem.Lett. (2000) 1262].The metallic catalyst that metal oxide supports is the optional catalyst of the low temperature elimination of carbon monoxide, Au/Al
2O
3Catalyst is 100 ℃ of selectivity with carbon monoxide oxidation of 50%, and the particle size of gold is greatly about 5-10nm[G.K.Bethke, and H.H.Kung, Appl.Catal.A 194 (2000) 43] its weak point is: cost of material greater catalytic agent selectivity is low.
With regard to the catalyst of selectivity oxidizing carbon monoxide in the hydrogen, require it can eliminate a spot of carbon monoxide at a lower temperature, but do not lose hydrogen, promptly require catalyst that higher selectivity is arranged.If carbon monoxide and hydrogen exist with stoichiometric ratio in reaction gas, and fully with hydrogen balance, this research will have more challenge so.Because amount of oxygen increases, though can improve the conversion ratio of carbon monoxide, hydrogen is consumed simultaneously, and selectivity is also along with decline, and this will reduce the utilization ratio of fuel; Silver successfully has been used for the reaction of ethylene epoxidizing as a kind of oxidation catalyst preferably, and also demonstrates active [G.G.Xia, Y.G.Yin, WS.Willis etal J.Catal.185 (1999) 91] preferably for the low-temperature oxidation of carbon monoxide.But up to the present, silver catalyst does not also have to perform well in the carbon monoxide in the selective oxidation hydrogen.And in metal platinum, add argent and other metal component (as iron and nickel) can obtain good catalytic activity and selectivity at a lower temperature.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that is used for low temperature selective oxidation hydrogen carbon monoxide.
Another object of the present invention provides a kind of Preparation of catalysts method that is used for low temperature selective oxidation hydrogen carbon monoxide.
To achieve these goals, catalyst provided by the invention is made up of carrier and active component, and carrier is active carbon, carbon black, mesoporous carbon or CNT; Active component is:
Metal platinum, silver or iron; Or
The bi-component metal of silver and iron one of them and platinum formation; Or
Three component metals that metal platinum and iron and nickel constitute;
Wherein active component accounts for the percentage by weight 0.5-25% of carrier; The weight ratio of silver or iron and platinum is 16 in the bi-component metal: 1-16, the weight ratio of platinum and iron, nickel is 10 in three component metals: 1-5: 1-5.
The method of the above-mentioned catalyst of preparation provided by the invention, key step is:
The aqueous solution of the one pack system soluble metallic salt of preparation active component is immersed on the carrier, and room temperature is dried in the shade, 60-120 ℃ of oven dry, and active component accounts for the percentage by weight 0.5-25% of carrier; Described one pack system slaine is the nitrate or the six hydration chloroplatinic acids of the halide salt of the nitrate of silver or acetate, iron or nitrate, nickel.
Described method, impregnation sequence wherein are change arbitrarily.
Described method, impregnation sequence wherein are first platinum-impregnated, flood silver then or/and iron.
Catalyst provided by the invention can be used on the reaction of carbon monoxide in the oxidizes hydrogen gas, and reaction pressure is a normal pressure, reaction temperature-80-300 ℃.Wherein catalyst carries out in-situ treatment through hydrogen, unstripped gas or helium before use, gas flow 20-50ml/min, and treatment temperature 100-700 ℃, the time is 1-4 hour.Wherein catalyst carries out the gas of in-situ treatment, and elder generation is with helium and then switch to hydrogen, helium behind the perhaps first hydrogen.
The present invention has following advantage:
1) catalyst provided by the invention has good active and selectivity, advantages of higher stability at low temperature; In the hydrogen in the CO selective oxidation reaction, reaction temperature can be reduced to subzero three component catalysts under cryogenic conditions, and the selectivity of low temperature can reach 100%, and the conversion ratio of CO maximum approximately is 100%, has solved the problem that platinum electrode is poisoned basically.
2) catalyst of the present invention prepares easily, and it is good to repeat performance, and price is low, greatly reduces the Preparation of catalysts cost, and good application prospects is arranged.
3) catalyst of the present invention is in application process, and reaction does not need the oxygen of unnecessary metering ratio, and carbon monoxide and oxygen exist with stoichiometric proportion in reaction gas, and security is good, improves the energy utilization rate of catalyst.
Description of drawings
Figure 1A is the oxygen conversion of the different silver-colored loadings of 2wt% for the loading of platinum of the present invention;
Figure 1B is the carbon monoxide conversion ratio of the different silver-colored loadings of 2wt% for the loading of platinum of the present invention.
Fig. 2 is iron/active carbon, iron platinum/active carbon and platinum iron nickel/activated-carbon catalyst carbon monoxide conversion ratio.
Specific implementation method
The present invention is further described below by example, but the present invention is not limited in following embodiment.
Adopt equi-volume impregnating to prepare activated carbon loaded silver catalyst, be dissolved in 3 ml deionized water in the total amount ratio of active component and carrier silver nitrate 0.189g, to wherein adding 1 gram absorbent charcoal carrier, stirring the back placed two days in room temperature, 60 ℃ of oven dry, the loading that obtains silver is 12% supported catalyst.500 ℃ of processing are after 2 hours under unstripped gas for they, and active component mainly exists with the form of argent.
Adopting infusion process is precursor with six hydration chloroplatinic acids, and carbon black is the catalyst of preparing carriers.The concentration that takes by weighing platinum is 1.909% aqueous solution 1.048g, adds 6 milliliters of ethanol and 7 milliliters of ionized waters, then to wherein adding the 1g carbon black, stir the back and placed two days in room temperature, and 120 ℃ of oven dry, the loading that obtains platinum is 2% supported catalyst.The reaction procatalyst was handled 2 hours at 500 ℃ with hydrogen.
The concentration that takes by weighing a certain amount of platinum respectively according to the weight ratio of silver, platinum is 1.909% the aqueous solution, to wherein adding the 1g carbon black, stirs the back and places two days in room temperature, and the silver nitrate aqueous solution of 0.094g, 120 ℃ of oven dry are flooded in 120 ℃ of oven dry again.The reaction procatalyst was handled 2 hours at 500 ℃ with hydrogen.The mass ratio of silver, platinum is 6: 2,1: 2, and 2: 2,2: 3.Bimetallic silver, platinum catalyst can pass through graded impregnation, and as elder generation's dipping silver back platinum-impregnated, or dipping is silver-colored after the first platinum-impregnated, also can use co-impregnation, and the catalytic activity of the catalyst that dipping silvery is equipped with after the experiment confirm elder generation platinum-impregnated is good.
Embodiment 4
The concentration that takes by weighing 1.571g platinum according to the weight ratio of platinum is 1.909% the aqueous solution, to wherein adding the 1g active carbon, stir the back and placed two days 120 ℃ of oven dry in room temperature, flood the aqueous solution of 0.030g nine nitric hydrate iron and 0.017g Nickelous nitrate hexahydrate again, 120 ℃ of oven dry.The reaction procatalyst was handled 2 hours at 500 ℃ with hydrogen.The mass ratio of platinum, iron, nickel is 8.6: 1.2: 1.Three component platinum, iron, Raney nickel can pass through graded impregnation, as flooding earlier platinum-impregnated behind iron and the nickel simultaneously, or dipping iron and nickel after the first platinum-impregnated, also can use three's co-impregnation.
When silver/activated-carbon catalyst was used for the reaction of low temperature hydrogen selectivity oxidizing carbon monoxide, different pretreatment conditions were to the influence of reaction.Taking by weighing 0.12g 40-60 purpose loading is the catalyst of 12%Ag, should consist of 1%CO by gas, 0.5%O
2, H
2Balance, reaction pressure are normal pressure, and flow velocity is 50ml/min.The reaction procatalyst earlier through 200 ℃ of helium handle 2 hours then hydrogen handled 1 hour for 200 ℃, perhaps react procatalyst and handled 2 hours through 200 ℃ of hydrogen, 300 ℃, 400 ℃, 500 ℃ earlier.Concrete outcome is as shown in table 1:
Table 1: silver/activated-carbon catalyst behind different pretreatment conditions under the low temperature to hydrogen in selectivity oxidizing carbon monoxide reactive activity and selectivity
| Pretreatment condition | The complete conversion temperature of oxygen (℃) | Carbon monoxide maximum conversion temperature (℃) | Carbon monoxide maximum conversion (%) | Cryogenic selective (%) |
| H 2/200℃ H 2/300℃ H 2/400℃ H 2/ 500 ℃ He/200 ℃ H then 2/100℃ | ＞200 107 80 80 70 | - 96 75 75 70 | - 11.7 18.6 21.0 32.5 | 50-70 |
Embodiment 6
The platinum/carbon nano-tube catalyst is used for the reaction of low temperature hydrogen selectivity oxidizing carbon monoxide.Take by weighing the catalyst that the 0.060g loading is 2%Pt, should consist of 1%CO by gas, 0.5%O
2, H
2Balance, reaction pressure are normal pressure, and flow velocity is 25ml/min.The reaction procatalyst was handled 2 hours for 500 ℃ through hydrogen earlier, and reaction result is as shown in table 2:
Show under the 2:2% platinum/carbon nano-tube catalyst low temperature selectivity oxidizing carbon monoxide reactive activity and selectivity in the hydrogen
| Catalyst | The complete conversion temperature of oxygen (℃) | Carbon monoxide maximum conversion temperature (℃) | Carbon monoxide maximum conversion (%) | Cryogenic selective (%) |
| 2% platinum/carbon nano-tube | 90 | 90 | 86 | 100 |
Embodiment 7
The loaded catalyst of silver, platinum bi-component is used for the influence to reactivity worth of low temperature hydrogen CO selective oxidation when reaction silver, platinum mass ratio.The loading of platinum is 2wt%, and the loading of silver is respectively 1wt%, 2wt%, 4wt%, 6wt%, takes by weighing the catalyst that the 0.060g loading is 2%Pt, should consist of 1%CO by gas, 0.5%O
2, H
2Balance, reaction pressure are normal pressure, and flow velocity is 25ml/min.The reaction procatalyst was handled 2 hours for 500 ℃ through hydrogen earlier, and reaction result as shown in Figure 1.
Embodiment 8
Iron, iron and platinum bi-component and platinum, iron and nickel three components load on and are used for low temperature hydrogen CO selective oxidation reaction on the active carbon.Reaction gas consists of 1%CO, 0.5%O2, and H2 balance, reaction pressure are normal pressure, and flow velocity is 25ml/min, and catalyst amount is 0.060g.The reaction procatalyst was handled 2 hours for 500 ℃ through hydrogen earlier, and reaction result as shown in Figure 2.
Claims (7)
1. a catalyst that is used for the oxidizes hydrogen gas carbon monoxide is made up of carrier and active component, and carrier is active carbon, carbon black, mesoporous carbon or CNT; Active component is:
Metal platinum, silver or iron; Or
The bi-component metal of silver and iron one of them and platinum formation; Or
Three component metals that metal platinum and iron and nickel constitute;
Wherein active component accounts for the percentage by weight 0.5-25% of carrier; The weight ratio of silver or iron and platinum is 16 in the bi-component metal: 1-16, the weight ratio of platinum and iron, nickel is 10 in three component metals: 1-5: 1-5.
2. method for preparing the described catalyst of claim 1, key step is:
The aqueous solution of the one pack system soluble metallic salt of preparation active component is immersed on the carrier, and room temperature is dried in the shade, 60-120 ℃ of oven dry, and active component accounts for the percentage by weight 0.5-25% of carrier; Described one pack system slaine is the nitrate or the six hydration chloroplatinic acids of the halide salt of the nitrate of silver or acetate, iron or nitrate, nickel.
3. method as claimed in claim 2, impregnation sequence wherein are change arbitrarily.
4, as claim 2 or 3 described methods, impregnation sequence wherein is first platinum-impregnated, floods silver then or/and iron.
5, the application of the described catalyst of claim 1 reaction of carbon monoxide in oxidizes hydrogen gas, reaction pressure is a normal pressure, reaction temperature-80-300 ℃.
6, application as claimed in claim 5, wherein catalyst carries out in-situ treatment through hydrogen, unstripped gas or helium before use, gas flow 20-50ml/min, treatment temperature 100-700 ℃, the time is 1-4 hour.
7, application as claimed in claim 6, wherein catalyst carries out the gas of in-situ treatment, and elder generation is with helium and then switch to hydrogen, helium behind the perhaps first hydrogen.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013016841A1 (en) * | 2011-08-01 | 2013-02-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Nanoparticles |
| CN102039121B (en) * | 2009-10-21 | 2013-06-05 | 中国科学院大连化学物理研究所 | Platinum/carbon nanotube catalyst and preparation method and application thereof |
| CN110534752A (en) * | 2019-08-15 | 2019-12-03 | 上海电力大学 | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof |
| CN110586155A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in CO selective oxidation purification reaction in hydrogen-rich gas |
| CN112563519A (en) * | 2020-07-23 | 2021-03-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intermetallic compound-carbon nanotube composite material and preparation method and application thereof |
-
2006
- 2006-04-26 CN CN 200610011795 patent/CN101062478A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102039121B (en) * | 2009-10-21 | 2013-06-05 | 中国科学院大连化学物理研究所 | Platinum/carbon nanotube catalyst and preparation method and application thereof |
| WO2013016841A1 (en) * | 2011-08-01 | 2013-02-07 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Nanoparticles |
| CN110534752A (en) * | 2019-08-15 | 2019-12-03 | 上海电力大学 | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof |
| CN110534752B (en) * | 2019-08-15 | 2022-11-18 | 上海电力大学 | Iron and nitrogen co-doped carbon-oxygen reduction catalyst and preparation method thereof |
| CN110586155A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in CO selective oxidation purification reaction in hydrogen-rich gas |
| CN112563519A (en) * | 2020-07-23 | 2021-03-26 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intermetallic compound-carbon nanotube composite material and preparation method and application thereof |
| CN112563519B (en) * | 2020-07-23 | 2022-04-12 | 中国科学院苏州纳米技术与纳米仿生研究所 | Intermetallic compound-carbon nanotube composite material and preparation method and application thereof |
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