CN1331730C - Method for preceding to oxidize CO in hydrogen-riched air - Google Patents
Method for preceding to oxidize CO in hydrogen-riched air Download PDFInfo
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- CN1331730C CN1331730C CNB200610013034XA CN200610013034A CN1331730C CN 1331730 C CN1331730 C CN 1331730C CN B200610013034X A CNB200610013034X A CN B200610013034XA CN 200610013034 A CN200610013034 A CN 200610013034A CN 1331730 C CN1331730 C CN 1331730C
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Abstract
The present invention discloses a method for CO preferential oxidation in hydrogen-rich gas, which belongs to the technology of CO preferential oxidation in hydrogen-rich gas. The method comprises the following processes: Co3O4-CeO2 with the average particle diameter of 0.1mm to 10mm and the Co3O4 mass content of 2 to 96% and a catalyst with the dosage of 50 to 500 mg/cm<2> are added in a reactor, and then hydrogen-rich raw gas with 0.2 to 2.5 vol. % of O2, 0.01 to 2.5 vol. % of CO, 20 to 90 vol. % of H2 and N2 as the rest, or 5 to 40 vol. % of CO2 and/or 1 to 25 vol. % of H2O (steam) which are added on the basis of original components is led into the reactor with catalysts at the air speed of 1000 to 100000 ml/h. g (cat) to carry out reaction under normal pressure and at the temperature of 50 to 275 DEG C, so the CO in the hydrogen-rich gas is converted into CO2. The method has the advantages of low material cost of the catalyst, higher CO preferential oxidation conversion rate and better selectivity.
Description
Technical field
The present invention relates to the method for CO preferential oxidation in a kind of hydrogen-rich gas, belong to CO preferential oxidation technology in the hydrogen-rich gas.
Background technology
Mainly contain 45～75vol.%H through the reformation of hydrocarbon polymer and the hydrogen-rich gas that the water-gas reacting condition makes
2, 15～25vol.%CO
2, 0.5～2vol.%CO and a small amount of water vapor, this hydrogen-rich gas can be used as the unstripped gas of fuel cell.Because a small amount of CO can make fuel cell Pt electrode poison, and the preferential oxidation of CO is a most effectual way of removing CO in the hydrogen-rich gas at present, so the preferential oxidation of CO is one of gordian technique of fuel cell unstripped gas preparation in the hydrogen-rich gas.The existing method that is used for hydrogen-rich gas CO preferential oxidation mainly contains:
1, adopts the method for loading type Au catalyzer
This method is the catalyzer of active ingredient with Au.At present, Chang Yong load type gold catalyst carrier has: TiO
2, Fe
2O
3, CeO
2, MnO
x, NiO, MgO, Al
2O
3Deng.
Adopt the method for loading type Au catalyzer can obtain CO transformation efficiency preferably mostly at a lower temperature, but be difficult to reach gratifying CO selectivity.Hoflund etc. adopt the 10%Au/MnO of coprecipitation method preparation
XIn the time of 55 ℃, can obtain CO transformation efficiency greater than 90%.Panzera etc. consist of 1vol.%CO at unstripped gas, 1.5vol.%O with the preferential oxidation that the Au/CeOx of coprecipitation method preparation is used for CO
2, 48vol.%H
2And 49.5vol.%He, air speed is 100,000h
-1Condition under, in the time of 120 ℃, obtain 98% CO transformation efficiency, but O
2Selectivity to CO approximately only is about 40%.Grisel etc. have used with MgO, MnOx and FeOx and have been auxiliary agent, loading type Au/Al
2O
3Catalyzer is 2500h in air speed
-1, λ=4 (λ=O
2/ CO), under the condition of 70 ℃ of temperature of reaction, use Au/MnOx/MgO/Al
2O
3And Au/FeOx/MgO/Al
2O
3Reach 99% and 91% CO transformation efficiency respectively, and O
2Selectivity to CO only is 25% and 23%; And as λ=2 (λ=O
2/ CO) time, use Au/MnOx/MgO/Al
2O
3Though catalyzer can obtain 95% CO transformation efficiency, O
2Selectivity to CO has only 47%.
Gold utensil has chemically inert characteristics, the Au catalyzer only just may obtain catalytic activity preferably under the situation of high degree of dispersion and little Au granularity, also exist owing to particle is grown up or sintering causes the problem of catalyst deactivation so working load type Au catalyzer is removed the method for CO.
2, use the method for noble metal catalyst
Employing is supported on Al
2O
3, CeO
2, MgO, CeO
2-ZrO
2Deng on Pt, Pd, noble metal catalysts such as Ru, Rh.The problem that the method for use noble metal catalyst mainly exists has: (1) costs an arm and a leg, cost height in generally promoting the use of.(2) catalyst activity is subjected to H
2O and CO
2Influence bigger.(3) optimum temps of catalyst reaction is higher, considers from save energy and point of view of practicability, needs research to have highly active catalyzer at a lower temperature.
The preferential oxidation of research CO adopts the Pt noble metal catalyst more at present, but the difference on effect of the Pt Catalyst for CO preferential oxidation under the different carriers load is bigger.Discovery such as Wootsch will be with CeO under same reaction conditions
2The preferential oxidation effect that is used for CO for the pt catalyzer of carrier is better than use with CeO2-ZrO
2Catalyzer for carrier.At λ=1 (λ=2O
2/ CO), flow velocity is under the condition of 100N mL/min, uses Pt/CeO
2The effect of catalyzer CO oxidation in the time of 100 ℃ is best: the CO transformation efficiency is 78%, and selectivity is 80%; And use Pt/Ce
0.5Zr
0.5O
2Then in the time of 100 ℃, reach 69% CO transformation efficiency and 70% selectivity.Robert etc. are with Fe-Pt/Al
2O
3The catalyzer that is carried on the monoblock type ceramic monolith is used for the CO preferential oxidation, is 30 in air speed, 000h
-1, unstripped gas contains 1vol.%CO, 1vol.%O
2, 42vol.%H
2, 9vol.%CO
2, 12vol.%H
2O and 35vol.%N
2Condition under, in the time of 100 ℃, obtain 80% CO transformation efficiency and 40% CO selectivity.
Using catalyzer such as Ru, Rh, Pd also is the CO preferential oxidation method of using always.It is that active constituent, gac are the CO oxidizing reaction effect of the catalyzer (Pt/C, Ru/C, Pd/C) of carrier that Snytnikov etc. have contrasted with Pt, Ru and Pd, finds to use the effect of Pt/C and Ru/C to be better than Pd/C far away.Consist of 0.6vol.%CO, 0.6vol.%O at unstripped gas
2And 98.8vol.%H
2, air speed is 12,000ml/hg
CatCondition under, the preferential oxidation of CO uses Ru/C and Pt/C catalyzer, reaches 99.99% CO transformation efficiency and 50～60% selectivity respectively when 105～120 ℃ and 135～160 ℃; And the Pd/C catalyzer only can reach 55% CO transformation efficiency when 155 ℃ of optimum tempss.Han etc. are with Rh/MgO, Ru/ γ-Al
2O
3With Pt/ γ-Al
2O
3Catalyzer is used for the reaction of CO preferential oxidation.At flow velocity is 120N ml/min, catalyst levels 100mg, and unstripped gas is formed 1vol.%CO, 1vol.%O
2, 75vol.%H
2And 23vol.%N
2Condition under, Rh/MgO obtains about 100% CO transformation efficiency and about 45% CO selectivity at 175 ℃; And Ru/ γ-Al
2O
3With Pt/ γ-Al
2O
3Under the optimum temps of 150 ℃ and 200 ℃, obtain about 80% CO transformation efficiency and 40% CO selectivity respectively.
3, the method for working load type Cu catalyzer
The carried copper catalyzer has low price, advantage that selectivity is high.More and the effect of research at present is preferably uses CuO-CeO
2The method of catalyzer.Liu etc. adopt the CuO-CeO of urea Prepared by Sol Gel Method
2Catalyzer is at air speed 240,000ml/hg
Cat, unstripped gas 1vol.%CO, 1vol.%O
2, 50vol.%H
2Under the condition of 48vol.%He, in the time of 145 ℃, obtain 96% CO transformation efficiency and 97% CO selectivity; In air speed is 10,000ml/hg
Cat, unstripped gas consists of 1vol.%CO, 1vol.%O
2, 20vol.%CO
2, 10vol.%H
2O, 50vol.%H
2Under the condition of 18vol.%He, in the time of 165 ℃, obtain 96% CO transformation efficiency and 97% CO selectivity.
Be that the catalyzer of active ingredient is used for hydrogen-rich gas CO preferential oxidation and can obtains CO transformation efficiency and selectivity preferably with Cu, but the water in the hydrogen-rich gas have very big negative impact, a subject matter that is to use the Cu catalyzer to exist to the preferential oxidation of CO.
The content invention
The object of the present invention is to provide the method for CO preferential oxidation in a kind of hydrogen-rich gas, this method has CO transformation efficiency and selectivity preferably.
The present invention is realized that by following technical proposals the method for CO preferential oxidation in a kind of hydrogen-rich gas is characterized in that comprising following process: with median size is 0.1mm～10mm, Co
3O
4Mass content is 2～96% Co
3O
4-CeO
2, consumption is 50～500mg/cm
2The catalyzer reactor of packing into; To consist of 0.2～2.5vol.%O then
2, 0.01～2.5vol.%CO, 20～90vol.%H
2, all the other are N
2, or on this composition basis, add 5～40vol.%CO
2Or/and 1～25vol.%H
2The rich hydrogen unstripped gas of O (water vapor) is 1 with air speed, 000ml/hg
Cat～100,000ml/hg
CatThe reactor of catalyzer is equipped with in feeding; Under normal pressure, 50～275 ℃ of reactions make the CO of hydrogen-rich gas be converted into CO then
2
Above-mentioned reaction is preferably carried out under 120 ℃～200 ℃.
The present invention has the following advantages: catalyzer is made up of cobalt, cerium mixed oxide, and cost of material is relatively low.Adopt the method for CO preferential oxidation in this kind hydrogen-rich gas, 1,000ml/hg
Cat～40,000ml/hg
CatIn the air speed scope, in 120 ℃～200 ℃ wide temperature range, can obtain 100% CO transformation efficiency.In 200 ℃, O
2Selectivity to the CO oxidation is reduced to 50% by 100% gradually with the rising of temperature: when the CO transformation efficiency reached 80%, selectivity can reach on 90%; When the CO transformation efficiency reached 100%, selectivity can reach 78.7%.
Embodiment
Embodiment 1
Coprecipitation method prepares Co
3O
4-CeO
2Catalyzer is (with Co
3O
4Mass content is 80% Co
3O
4-CeO
2Be example):
(1) 0.5mol/LCe (NO
3)
3The preparation of solution: the accurate weighing 75.55 gram Ce of balance
2(CO
3)
38H
2O is measured the nitric acid of 50ml 15mol/L with graduated cylinder.Nitric acid is added drop-wise to Ce slowly
2(CO
3)
38H
2Among the O, and constantly stir until dissolving.To dissolve good Ce (NO then
3)
3Solution moves in the volumetric flask of 500ml, adds distilled water, is mixed with 0.5mol/LCe (NO
3)
3Solution.(2) Co (NO
3)
2The preparation of solution: the accurate weighing 69.616g of balance Co (NO
3)
26H
2O is to wherein adding less water until dissolving fully.(3) get the Ce (NO of 56.1ml 0.5mol/L
3)
3Solution and the Co (NO that has prepared
3)
2The solution uniform mixing.Getting an amount of mass percent is that 15～20% aqueous sodium carbonate and the Co for preparing, Ce mixing solutions and stream are titrated in the water of pH value between 8.5～9.5, constantly stirs simultaneously, and stir speed (S.S.) is about 100N/min.(5) after titration finishes, continue to stir 4 hours.Then precipitation is washed suction filtration.Use distilled water wash three times during washing, with stirring.(6) will wash and suction filtration after filter cake be placed in 80 ℃ the constant temperature oven dry 24 hours.Then that drying is good sample roasting at a certain temperature 5 hours.Promptly obtain Co
3O
4-CeO
2Catalyzer.
With Co
3O
4-CeO
2Catalyzer is used for the preferential oxidation of CO:
Use atmospheric fixed bed quartz tube reactor, the quartz tube reactor specification is Ф 10 * 2.Consumption is that 200mg, granularity are 40～60 purpose Co
3O
4-CeO
2The catalyzer reactor of packing into.At N
2Be warming up to 50 ℃ under purging, feeding consists of again: 1vol.%O
2, 1vol.%CO, 50vol.%H
2And 48vol.%N
2, air speed is 40,000ml/hg
CatUnstripped gas.Since 50 ℃, establish a temperature spot to 250 ℃ for per 50 ℃.Each temperature spot reaction 1 hour.The on-line analysis of SP-2100 type gas-chromatography, 5A molecular sieve column and GDX-502 post, TCD detects.
Under these conditions, use different cobalts, cerium mixed oxide catalyst, the result of CO preferential oxidation is as follows: 80%Co
3O
4-CeO
2Catalyzer: in the time of 50 ℃, CO transformation efficiency 4.6%, selectivity 100%; In the time of 100 ℃, CO transformation efficiency 78.1%, selectivity 96.5%; In the time of 150 ℃, CO transformation efficiency 100%, selectivity 50%; In the time of 200 ℃, CO transformation efficiency 93.2%, selectivity 46.6%; In the time of 250 ℃, CO transformation efficiency 76.2%, selectivity 38.1%.
2.5%Co
3O
4-CeO
2Catalyzer: in the time of 100 ℃, CO transformation efficiency 4.8%, selectivity 100%; In the time of 150 ℃, CO transformation efficiency 21.1%, selectivity 100%; In the time of 200 ℃, CO transformation efficiency 92.2%, selectivity 73.4%; In the time of 250 ℃, CO transformation efficiency 84.4%, selectivity 42.2%.
50%Co
3O
4-CeO
2Catalyzer: in the time of 100 ℃, CO transformation efficiency 53.4%, selectivity 91.9%; In the time of 150 ℃, CO transformation efficiency 100%, selectivity 50%; In the time of 200 ℃, CO transformation efficiency 100%, selectivity 50%; In the time of 250 ℃, CO transformation efficiency 86.5%, selectivity 43.2%.
95%Co
3O
4-CeO
2Catalyzer: in the time of 100 ℃, CO transformation efficiency 64.1%, selectivity 86.2%; In the time of 150 ℃, CO transformation efficiency 100%, selectivity 44.7%.In the time of 200 ℃, CO transformation efficiency 91.0%, selectivity 45.4%.
Embodiment 2
The unstripped gas composition is become: 1vol.%O
2, 2vol.%CO, 50vol.%H
2With 47 vol.%N
2Other conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 100 ℃ is 67.2%, and selectivity is 97.1%; The CO transformation efficiency is 82.2% in the time of 150 ℃, and selectivity is 82.2%; In the time of 200 ℃, the CO transformation efficiency is 78.1%, and selectivity is 78.1%
Embodiment 3
The unstripped gas composition is become: 1vol.%O
2, 0.5vol.%CO, 50vol.%H
2And 48.5vol.%N
2Other conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 50 ℃ is 21.3%, and selectivity is 99.2%; The CO transformation efficiency is 89.2% in the time of 100 ℃, and selectivity is 86.1%; The CO transformation efficiency is 100% in the time of 150 ℃, and selectivity is 25.0%; The CO transformation efficiency is 100% in the time of 200 ℃, and selectivity is 25.0%.
Embodiment 4
The unstripped gas composition is become: 2.5vol.%O
2, 1vol.%CO, 50vol.%H
2And 46.5vol.%N
2Other conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 50 ℃ is 22.0%, and selectivity is 100%; The CO transformation efficiency is 93.2% in the time of 100 ℃, and selectivity is 84.4%; The CO transformation efficiency is 100% in the time of 150 ℃, and selectivity is 20%; The CO transformation efficiency is 100% in the time of 200 ℃, and selectivity is 20%.
Embodiment 5
The unstripped gas composition is become: 1vol.%O
2, 1vol.%CO, 50vol.%H
2, 20vol.%CO
2And 28vol.%N
2Other conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 100 ℃ is 8.1%, and selectivity is 100%; The CO transformation efficiency is 92.4% in the time of 150 ℃, and selectivity is 70.9%; The CO transformation efficiency is 88.5% in the time of 200 ℃, and selectivity is 44.2%; The CO transformation efficiency is 76.8% in the time of 250 ℃, and selectivity is 38.4%.
Embodiment 6
The unstripped gas composition becomes: 1vol.%O
2, 1vol.%CO, 50vol.%H
2, 10vol.%H
2O and 38 vol.%N
2Other conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 150 ℃ is 100%, and selectivity is 68.3%.The CO transformation efficiency is 100% in the time of 200 ℃, and selectivity is 50%; The CO transformation efficiency is 75.7% in the time of 250 ℃, and selectivity is 37.8%.
Embodiment 7
The unstripped gas composition becomes: 1vol.%O
2, 1vol.%CO, 50vol.%H
2, 20vol.%CO
2, 10vol.%H
2O and 18vol.%N
2Other conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 150 ℃ is 49.6%, and selectivity is 86.0%; The CO transformation efficiency is 88.7% in the time of 200 ℃, and selectivity is 44.4%; The CO transformation efficiency is 70.0% in the time of 250 ℃, and selectivity is 35.0%.
Embodiment 8
The unstripped gas air speed becomes 20,000ml/hg
CatOther conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 50 ℃ is 33.7%, and selectivity is 100%; The CO transformation efficiency is 93.7% in the time of 100 ℃, and selectivity is 89.5%; The CO transformation efficiency is 100% in the time of 150 ℃, and selectivity is 50%; The CO transformation efficiency is 100% in the time of 200 ℃, and selectivity is 50%.
Embodiment 9
The unstripped gas air speed becomes 100,000ml/hg
CatOther conditions are with embodiment 1.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 100 ℃ is 58.7%, and selectivity is 97.9%; The CO transformation efficiency is 99.1% in the time of 150 ℃, and selectivity is 73.3%; The CO transformation efficiency is 70.2% in the time of 200 ℃, and selectivity is 35.1%
Embodiment 10
The unstripped gas air speed becomes 10,000ml/hg
CatOther conditions are with embodiment 7.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 150 ℃ is 100%, and selectivity is 60.6%; The CO transformation efficiency is 100% in the time of 200 ℃, and selectivity is 50%.
Embodiment 11
The unstripped gas air speed becomes 20,000ml/hg
CatOther conditions are with embodiment 7.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 150 ℃ is 100%, and selectivity is 62.9%; The CO transformation efficiency is 96.0% in the time of 200 ℃, and selectivity is 48.0%; The CO transformation efficiency is 79.8% in the time of 250 ℃, and selectivity is 39.9%.
Embodiment 12
The unstripped gas air speed becomes 80,000ml/hg
CatOther conditions are with embodiment 7.Use 80%Co
3O
4-CeO
2Catalyzer, CO preferential oxidation CO transformation efficiency in the time of 150 ℃ is 17.7%, and selectivity is 100%; The CO transformation efficiency is 92.5% in the time of 200 ℃, and selectivity is 46.3%; The CO transformation efficiency is 74.1% in the time of 250 ℃, and selectivity is 37.1%.
Claims (2)
1, the method for CO preferential oxidation in a kind of hydrogen-rich gas, it is characterized in that comprising following process: with median size is 0.1mm～10mm, Co
3O
4Mass content is 2～96% Co
3O
4-CeO
2, consumption is 50～500mg/cm
2The catalyzer reactor of packing into; To consist of 0.2～2.5vol.%O then
2, 0.01～2.5vol.%CO, 20～90vol.%H
2, all the other are N
2, or on this composition basis, add 5～40vol.%CO
2Or/and the rich hydrogen unstripped gas of 1～25vol.% water vapor is 1 with air speed, 000ml/hg
Cat～100,000ml/hg
CatThe reactor of catalyzer is equipped with in feeding; Under normal pressure, 50～275 ℃ of reactions make the CO of hydrogen-rich gas be converted into CO then
2
2, by the described method of claim 1, it is characterized in that the temperature of reaction of unstripped gas is 120 ℃～200 ℃.
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|---|---|---|---|
| CNB200610013034XA CN1331730C (en) | 2006-01-12 | 2006-01-12 | Method for preceding to oxidize CO in hydrogen-riched air |
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|---|---|---|---|
| CNB200610013034XA CN1331730C (en) | 2006-01-12 | 2006-01-12 | Method for preceding to oxidize CO in hydrogen-riched air |
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|---|---|
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| CN1331730C true CN1331730C (en) | 2007-08-15 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100500293C (en) * | 2007-04-13 | 2009-06-17 | 中国科学院山西煤炭化学研究所 | Composite CeO2-CoOx oxide carrier and its preparation process |
| CN103752317A (en) * | 2013-11-25 | 2014-04-30 | 邵建军 | Preparation of Co3O4 / CeO2 composite oxide and catalytic application |
| CN106807392A (en) * | 2017-03-07 | 2017-06-09 | 北京工业大学 | A kind of MoCeCoO for low temperature CO catalysisXThe preparation and application of catalyst |
| CN108043420B (en) * | 2017-12-15 | 2021-06-04 | 北京工业大学 | WCeCoO for low-temperature CO catalysisxCatalyst and preparation method |
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| CN1271330A (en) * | 1997-09-26 | 2000-10-25 | 丰田自动车株式会社 | Apparatus and method for reducing carbon monoxide concentration and catalyst for selectivity oxidizing carbon monoxide |
| JP2001089101A (en) * | 1999-09-17 | 2001-04-03 | Nissan Motor Co Ltd | Method for selectively removing co in hydrogen gas |
| WO2002059038A1 (en) * | 2001-01-26 | 2002-08-01 | Matsushita Electric Industrial Co., Ltd. | Hydrogen purification device and fuel cell power generation system |
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2006
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271330A (en) * | 1997-09-26 | 2000-10-25 | 丰田自动车株式会社 | Apparatus and method for reducing carbon monoxide concentration and catalyst for selectivity oxidizing carbon monoxide |
| JP2001089101A (en) * | 1999-09-17 | 2001-04-03 | Nissan Motor Co Ltd | Method for selectively removing co in hydrogen gas |
| WO2002059038A1 (en) * | 2001-01-26 | 2002-08-01 | Matsushita Electric Industrial Co., Ltd. | Hydrogen purification device and fuel cell power generation system |
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