CN101549296B - Method for preparing water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst - Google Patents
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Abstract
A method for preparing water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst uses a sol-gel method for preparing a nanometer oxide carrier CeO2. Then Cu(NO3)2 is dissolved in concentrated ammonia liquor or organic amine. Then the dissolved Cu(NO3)2 is impregnated to the carrier through an impregnation method. The catalyst prepared according to the invention has the advantages of high catalyst activity and excellent water-resistant carbon-dioxide-resistant performance in the condition of lower reaction temperature, high airspeed and longer reaction time compared with the CuO/CeO2 catalyst prepared by other method.
Description
Technical field
The invention belongs to a kind of Preparation of catalysts method, relate in particular to a kind of preparation method of water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst.
Technical background
Proton Exchange Membrane Fuel Cells (PEMFC) becomes current important building stand-by power supply, electric automobile and moves one of focus of equipment field of power supplies research with the advantage of its high efficiency, high reliability and good working environment and operating characteristics.The desirable feedstock of PEMFC is a hydrogen, but because hydrogen is difficult to store, transportation, existing main steam reforming, partial oxidation or the self-heating recapitalization that adopts alcohols or hydro carbons, again through hydrogen-rich gas that water-the vapour conversion makes as PEMFC fuel, the product of this moment consists of: 40-75%H
2, 15-25%CO
2, 10-25%H
2O, 0-25%N
2And 0.5-1.0%CO (gas volume mark), and the maximum patience of fuel cell Pt electrode pair CO is no more than 100ppm, so CO concentration will be eliminated less than 100ppm in advance.
The CO selective oxidation has had the history in more than 40 year under the rich hydrogen condition, at present the catalyst of bibliographical information mainly is divided into two big classes: a class is to be the noble metal catalyst of representative with Pt, Pd, Ru, Rh, Au, though noble metal catalyst has advantages such as reaction temperature is low, but because its reserves are few, price is high, selection of catalysts is low etc. shortcoming has limited its further application; Another kind of is one-component oxide or composite oxides, particularly CuO-CeO such as base metal such as Cu, Mn, Co, Ni, Fe
2Catalyst is all showing α-Fe than Au/ aspect active and the selectivity
2O
3And Pt/Al
2O
3Catalytic performance and economy that two class catalyst are more superior.But,, therefore require CuO/CeO owing to all can contain a certain amount of water and carbon dioxide usually in the reformation gas
2Catalyst must have very strong anti-water and resistant to carbon dioxide ability, and this is that can the decision catalyst move towards practical key factor.As the CuO-CeO of (A rolled up 155 pages in 2003 224 referring to the applied catalysis chemistry) reports such as Avgouropoulos with the firing method preparation
2Catalyst is O in reaction atmosphere
2/ CO=1.25, and 15% CO is arranged
2Under the condition that exists, 140 ℃, air speed 120,000ml g
-1h
-1The time, the CO conversion ratio is for dropping to 49% from 60% in the 168h, but selectivity remains on more than 99%; Bring up to 160 ℃, air speed when reaction temperature and be reduced to 25000ml h
-1g
-1The time, the CO conversion ratio is brought up to more than 99.5%, but selectivity reduces to 72%; The H of adding 10% in reaction atmosphere
2After the O, reaction temperature need be brought up to 190 ℃, just can reach identical conversion ratio and selectivity.
The CuO/CeO that Kim etc. prepare with coprecipitation
2Catalyst (rolling up 171 pages in 2007 167) O in reaction atmosphere referring to the surface catalysis chemical research
2/ CO=1, and 10%H is arranged
2O and 15% CO
2Under the condition that exists, 170 ℃ of reaction temperatures, air speed 15000mlg
-1h
-1The time, CO conversion ratio 99%, selectivity though CO is dropped to below the 100ppm, has only been kept 2h more than 75%, and the stability of catalyst reaches application requirements far away.
The Cu load capacity of usefulness citric acid-Hydrothermal Preparation such as Avgouropoulos is 25wt%CuO/CeO
2Catalyst (B.2006 year 67 is rolled up 1 page referring to the applied catalysis chemistry) under anhydrous situation, is realized the complete oxidation under the CO rich hydrogen condition for 150 ℃, and corresponding selectivity is 72%; In the hydrogen rich gas atmosphere of carbonated 15%, the 175 ℃ of corresponding conversion ratios of complete oxidation that can realize CO are 65%; In the hydrogen rich gas atmosphere of catalyst at moisture 10%, carbonated 15%, the conversion ratio of CO is 99% in the time of 200 ℃, and corresponding conversion ratio is 55%, and has carried out stability test with this understanding.In the testing time of 150h, realized about 99% conversion ratio.But reaction temperature is too high, and the testing time is shorter, is difficult to reach practical requirement.
This shows, in the hydrogen-rich gas that contains water and carbon dioxide, with the CuO/CeO of preparations such as coprecipitation, citric acid-hydro-thermal method, coprecipitation
2Catalyst, its CO selective oxidation reaction is along with the adding reaction temperature of water and carbon dioxide increases substantially, and the stability of catalyst reduces greatly simultaneously, therefore studies the CuO/CeO of a kind of highly active anti-water, resistant to carbon dioxide
2It is significant that catalyst moves towards practical application to the PEMFC fuel cell.
Summary of the invention
The preparation method who the purpose of this invention is to provide the CO oxidation catalyst under a kind of rich hydrogen condition with water-resistant carbon-dioxide-resistant ability.
The object of the invention can realize by the following method: with Prepared by Sol Gel Method nano-oxide support C eO
2, then with Cu (NO
3)
2Be dissolved in concentrated ammonia liquor or the organic amine, it be impregnated on the carrier with infusion process.
This Preparation of catalysts method is as follows:
(1) support C eO
2Preparation: cerous nitrate is dissolved in the deionized water, the aqueous solution of precipitating reagent is dropwise added wherein to pH to 8-14, form colloidal sol, when the precipitating reagent aqueous solution dropwises after, continue stirring 1-3 hour, leave standstill aging 20-24h under the room temperature, form gel,, use absolute ethanol washing 4-6 time gel deionized water filtering and washing 4-6 time, 75-85 ℃ of dry 4-6h under air atmosphere, 110-120 ℃ of dry 10-20h, 400-600 ℃ of roasting 4-6h makes CeO
2Nano-oxide, sieves and makes 40-60 purpose carrier at compressing tablet;
(2) mol ratio of pressing copper nitrate and concentrated ammonia liquor or organic amine is 1: in the 4-20 scope, copper nitrate is dissolved in concentrated ammonia liquor or the organic amine, is heated to the copper nitrate dissolving at 60-80 ℃, make the complex solution of cupric;
(3) to satisfy the requirement of CuO load capacity 2-15wt% by the amount of copper complex solution, the cupric complex solution of step (2) preparation is impregnated into the CeO of step (1) preparation
2On the carrier, dry 12-20h under the room temperature, 110-120 ℃ of dry 10-20h is that 1-8 ℃/min is warmed up to 400-750 ℃ of roasting 4-6h then with the heating rate.
Aforesaid precipitating reagent is NaOH, ammonium carbonate, sodium carbonate or ammoniacal liquor.Compared with the prior art, the CuO/CeO of this method preparation
2Have following substantive distinguishing features:
1) catalyst of this method preparation has solved CuO/CeO
2The difficult problem of water funk and carbon dioxide, have good water-resistant carbon-dioxide-resistant ability.When reaction temperature is 140 ℃, component is CO: O
2: H
2: H
2O: N
2=1: 1: 50: 10:, realized that in 1000h CO remains on the conversion ratio more than 99.5%, corresponding C O at 38 o'clock
2Selectivity is more than 85%.When catalyst adds 15%CO
2After, catalyst can realize still that 150 ℃ of reaction temperatures CO concentration will be controlled at the requirement below the 100ppm, corresponding conversion ratio is more than 75%, and still do not have inactivation behind the operation 1600h.
2) catalyst of this method preparation is than other CuO/CeO
2Catalyst has lower reaction temperature, and good selectivity is arranged simultaneously.When the anhydrous no carbon dioxide of catalyst, 110 ℃ of conversions fully that can realize CO, corresponding selectivity is more than 95%; When catalyst had 10% water to exist, the reaction temperature that realization CO transforms fully will be brought up to 140 ℃, and corresponding conversion ratio is more than 85%; As 10% water, when 15% carbon dioxide exists simultaneously, can realize the conversion ratio of CO more than 99.8% for 150 ℃, selectivity is more than 75%.
The specific embodiment
Make the catalyst that with the following method embodiment is prepared on the microreactor on the microreactor of normal pressure continuous-flow, carry out CO catalytic oxidation performance evaluation.With the 0.200g catalyst reactor of packing into, catalyst 250-350 ℃ through air preliminary treatment 1h, estimate then.Mix CO, CO in the gas before and after adopting GC-8A gas chromatograph (FID) analytical reactions
2Concentration, wherein the chromatographic column adopting carbon molecular sieve separates, and the methanator of dress Ni catalyst in one of the series connection behind the post makes CO and CO after the separation
2Successively all be converted into methane, and then enter flame ionization ditector.Analyzing the concentration of oxygen change detector with the GC-8A gas chromatograph is thermal conductivity cell detector (TCD), and the analytical column inserts is the 13X molecular sieve.The reaction raw materials overall flow rate is 100mlmin
-1, form the three kinds of situations that are divided into:
Anhydrous no carbon dioxide: CO: O
2: H
2: N
2=1: 1: 50: 48
There is water not have carbon dioxide: CO: O
2: H
2: H
2O: N
2=1: 1: 50: 10: 38
There is water that carbon dioxide is arranged: CO: O
2: H
2: H
2O: CO
2: N
2=1: 1: 50: 10: 15: 23
Embodiment 1
1) gets Ce (NO
3)
36H
2O 65g is dissolved in the 2500ml deionized water, and it is even that the 300ml concentrated ammonia liquor is dissolved in the 4000ml deionized water for stirring.Under stirring fast, the aqueous solution that will contain concentrated ammonia liquor dropwise joins in the aqueous solution of cerous nitrate, stops to drip when the pH that forms colloidal sol is 10, continues to stir 2 hours.Left standstill under the room temperature 20 hours, with deionized water suction filtration, washing 4 times, each consumption 1000ml carries out alcohol with the absolute ethyl alcohol of 2000ml and exchanges 4 times, at every turn consumption 500ml.75 ℃ of dry 4h, 110 ℃ of dry 20h.Be that 3 ℃/min is warmed up to 500 ℃ of roasting 5h with heating rate in the air atmosphere.Make CeO
2Nano-oxide, the compressing tablet fragmentation makes carrier after being screened to the 40-60 order.
2) get 75gCu (NO
3)
23H
2O joins (mol ratio is 1: 14.5) in the 300ml concentrated ammonia solution, and 75 ℃ are heated to copper nitrate and all dissolve, and make the network and the solution that contain CuO mass fraction 7.1%.
3) get CeO
2Carrier 10g to its network that contains CuO mass fraction 7.1% and solution that adds 15.7g, makes and contains the CuO/CeO that the CuO load capacity is 10.0wt%
2Catalyst.Dry 12h under the room temperature, 110 ℃ of dry 20h.After to enter Muffle furnace be that 4 ℃/min is warmed up to 650 ℃, roasting 4h with heating rate.
The catalyst that makes just can be realized the complete oxidation under the CO rich hydrogen condition for 110 ℃ under anhydrous situation, corresponding selectivity is 95%; In the hydrogen rich gas atmosphere of catalyst moisture 10%, the 140 ℃ of corresponding conversion ratios of complete oxidation that can realize CO are 85%; In the hydrogen rich gas atmosphere of catalyst at moisture 10%, carbonated 15%, 150 ℃ of 99.8% the conversion ratios that can realize CO, corresponding conversion ratio is 75%.
Embodiment 2
1) gets Ce (NO
3)
36H
2O 65g is dissolved in the 1000ml deionized water, and it is even that the 200ml concentrated ammonia liquor is dissolved in the 4000ml deionized water for stirring.Under stirring fast, the aqueous solution that will contain concentrated ammonia liquor dropwise joins in the aqueous solution of cerous nitrate.When the pH that forms colloidal sol is 9, stop to drip, continue to stir 1.5 hours.Left standstill under the room temperature 24 hours, with deionized water suction filtration, washing 4 times, each consumption 1000ml carries out alcohol with the absolute ethyl alcohol of 2500ml and exchanges 5 times, at every turn consumption 500ml.80 ℃ of dry 6h, 120 ℃ of dry 15h.Be that 5 ℃/min is warmed up to 400 ℃ of roasting 4h with heating rate in the air atmosphere.Make CeO
2Nano-oxide, compressing tablet fragmentation are screened to carrier behind the 40-60 order.
2) get the 75g copper nitrate and join (mol ratio is 1: 7.25) in the 150ml ethylenediamine, 65 ℃ are heated to copper nitrate and all dissolve, and make the network and the solution that contain CuO mass fraction 11.8%.
3) get CeO
210g to its solution that contains CuO mass fraction 11.8% that adds 14.95g, makes and contains the CuO/CeO that the CuO load capacity is 15.0wt%
2Catalyst.Dry 20h under the room temperature, 110 ℃ of dry 12h.After to enter Muffle furnace be that 8 ℃/min is warmed up to 650 ℃, roasting 5h with heating rate.
The catalyst that makes just can be realized the complete oxidation under the CO rich hydrogen condition for 120 ℃ under anhydrous situation, corresponding selectivity is 92%; In the hydrogen rich gas atmosphere of catalyst moisture 10%, the 145 ℃ of corresponding conversion ratios of complete oxidation that can realize CO are 83%; In the hydrogen rich gas atmosphere of catalyst at moisture 10%, carbonated 15%, the 155 ℃ of complete oxidations that can realize CO, corresponding conversion ratio is 72%.
Embodiment 3
1) gets Ce (NO
3)
36H
2O 65g is dissolved in the 4000ml deionized water, and it is even that the 600ml concentrated ammonia liquor is dissolved in the 4000ml deionized water for stirring.Under stirring fast, the aqueous solution that will contain concentrated ammonia liquor dropwise joins in the aqueous solution of cerous nitrate.When the pH that forms colloidal sol is 11, stop to drip, continue to stir 3 hours.Under the room temperature, left standstill 24 hours.Filter, wash 4 times, each deionized water consumption 1000ml carries out alcohol with the absolute ethyl alcohol of 2500ml and exchanges 5 times, at every turn consumption 500ml.80 ℃ of dry 4h, 110 ℃ of dry 20h.Be that 10 ℃/min is warmed up to 450 ℃ of roasting 4h and makes CeO with heating rate in the air atmosphere
2Nano-oxide, compressing tablet fragmentation are screened to behind the 40-60 order stand-by.
2) get the 75g copper nitrate and join (mol ratio is 1: 18.6) in the 500ml diethylamine, 80 ℃ are heated to copper nitrate and all dissolve, and make the solution that contains CuO mass fraction 4.7%.
3) get CeO
210g to its solution that contains CuO mass fraction 4.7% that adds 6.6g, makes and contains the CuO/CeO that the CuO load capacity is 3.0wt%
2Catalyst.Dry 20h under the room temperature, 120 ℃ of dry 20h.Entering Muffle furnace after laggard is that 6 ℃/min is warmed up to 600 ℃, roasting 4h with heating rate.
The catalyst that makes can be realized the complete oxidation under the CO rich hydrogen condition for 125 ℃ under anhydrous situation, corresponding selectivity is 90%; In the hydrogen rich gas atmosphere of catalyst moisture 10%, the 150 ℃ of corresponding conversion ratios of complete oxidation that can realize CO are 80%; In the hydrogen rich gas atmosphere of catalyst at moisture 10%, carbonated 15%, the 160 ℃ of complete oxidations that can realize CO, corresponding conversion ratio is 70%.
Embodiment 4
1) gets Ce (NO
3)
36H
2O 65g is dissolved in the 3000ml deionized water, and it is even that 200g NaOH is dissolved in the 4000ml deionized water for stirring.Under stirring fast, the aqueous solution that will contain NaOH dropwise joins in the aqueous solution of cerous nitrate.When the pH that forms colloidal sol is 13, stop to drip, continue to stir 1 hour.Under the room temperature, left standstill 24 hours.Filter, wash 6 times, each deionized water consumption 1000ml carries out alcohol with the absolute ethyl alcohol of 2000ml and exchanges 4 times, at every turn consumption 500ml.80 ℃ of dry 4h, 110 ℃ of dry 20h.Be that 2.5 ℃/min is warmed up to 550 ℃ of roasting 4h with heating rate in the air atmosphere.Make CeO
2Nano-oxide, compressing tablet fragmentation are screened to behind the 40-60 order stand-by.
2) get the 75g copper nitrate and join (mol ratio is 1: 4.54) in the 250ml 6mol/L EDTA solution, the low-grade fever copper nitrate all dissolves, and makes the solution that contains CuO mass fraction 4.8%.
3) get CeO
210g to its solution that contains CuO mass fraction 4.8% that adds 16.9g, makes and contains the CuO/CeO that the CuO load capacity is 7.5wt%
2Catalyst.Dry 20h under the room temperature, 120 ℃ of dry 20h.After to enter Muffle furnace be that 8 ℃/min is warmed up to 500 ℃, roasting 5h with heating rate.
The catalyst that makes can be realized the complete oxidation under the CO rich hydrogen condition for 130 ℃ under anhydrous situation, corresponding selectivity is 85%; In the hydrogen rich gas atmosphere of catalyst moisture 10%, the 160 ℃ of corresponding conversion ratios of complete oxidation that can realize CO are 75%; In the hydrogen rich gas atmosphere of catalyst at moisture 10%, carbonated 15%, the 170 ℃ of complete oxidations that can realize CO, corresponding conversion ratio is 65%.
Embodiment 5
1) gets Ce (NO
3)
36H
2O 65g is dissolved in the 2000ml deionized water, and it is even that the 350ml concentrated ammonia liquor is dissolved in the 4000ml deionized water for stirring.Under stirring fast, the aqueous solution that will contain concentrated ammonia liquor dropwise joins in the aqueous solution of cerous nitrate.When the pH that forms colloidal sol is 14, stop to drip, continue to stir 1 hour.Under the room temperature, left standstill 20 hours.Wash to solution 5 times, each deionized water consumption 1000ml carries out alcohol with the absolute ethyl alcohol of 2000ml and exchanges 4 times, at every turn consumption 500ml.80 ℃ of dry 4h in the air atmosphere, 120 ℃ of dry 20h.Be that 10 ℃/min is warmed up to 400 ℃ of roasting 4h with heating rate in the air atmosphere.Make CeO
2Nano-oxide, compressing tablet fragmentation are screened to behind the 40-60 order stand-by.
2) get the 75g copper nitrate and join (mol ratio is 1: 19.4) in the 400ml concentrated ammonia solution, the low-grade fever copper nitrate all dissolves, and makes the solution that contains CuO mass fraction 5.6%.
3) get CeO
210g to its solution that contains CuO mass fraction 5.6% that adds 25.5g, makes and contains the CuO/CeO that the CuO load capacity is 12.5wt%
2Catalyst.Dry 14h under the room temperature, 120 ℃ of dry 20h.After to enter Muffle furnace be that 4 ℃/min is warmed up to 700 ℃, roasting 5h with heating rate.
The catalyst that makes can be realized the complete oxidation under the CO rich hydrogen condition for 115 ℃ under anhydrous situation, corresponding selectivity is 90%; In the hydrogen rich gas atmosphere of catalyst moisture 10%, the 145 ℃ of corresponding conversion ratios of complete oxidation that can realize CO are 80%; In the hydrogen rich gas atmosphere of catalyst at moisture 10%, carbonated 15%, the 152 ℃ of complete oxidations that can realize CO, corresponding conversion ratio is 70%.
Claims (2)
1. the preparation method of a water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst is characterized in that comprising the steps:
(1) support C eO
2Preparation: cerous nitrate is dissolved in the deionized water, the aqueous solution of precipitating reagent is dropwise added wherein to pH to 8-14, form colloidal sol, when the precipitating reagent aqueous solution dropwises after, continue stirring 1-3 hour, leave standstill aging 20-24h under the room temperature, form gel,, use absolute ethanol washing 4-6 time gel deionized water filtering and washing 4-6 time, 75-85 ℃ of dry 4-6h under air atmosphere, 110-120 ℃ of dry 10-20h, 400-600 ℃ of roasting 4-6h makes CeO
2Nano-oxide, sieves and makes 40-60 purpose carrier at compressing tablet;
(2) mol ratio of pressing copper nitrate and concentrated ammonia liquor or organic amine is 1: in the 4-20 scope, copper nitrate is dissolved in concentrated ammonia liquor or the organic amine, is heated to the copper nitrate dissolving at 60-80 ℃, make the complex solution of cupric;
(3) to satisfy the requirement of CuO load capacity 2-15wt% by the amount of copper complex solution, with step
(2) Zhi Bei cupric complex solution is impregnated into the CeO of step (1) preparation
2On the carrier, dry 12-20h under the room temperature, 110-120 ℃ of dry 10-20h is that 1-8 ℃/min is warmed up to 400-750 ℃ of roasting 4-6h then with the heating rate.
2. the preparation method of a kind of water-resistant carbon-dioxide-resistant CO low-temperature oxidation catalyst as claimed in claim 1 is characterized in that described precipitating reagent is NaOH, ammonium carbonate, sodium carbonate or ammoniacal liquor.
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TWI600468B (en) * | 2012-01-13 | 2017-10-01 | 國立中央大學 | Preparation of copper oxide-cerium oxide-supported nano-gold catalysts and its application in removal of carbon monoxide in hydrogen stream |
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CN101733129B (en) * | 2009-12-07 | 2013-04-17 | 中国科学院山西煤炭化学研究所 | Aurum-copper bimetallic catalyst for oxidating CO at low temperature under rich hydrogen condition and preparation method thereof |
GB201002677D0 (en) * | 2010-02-17 | 2010-04-07 | Johnson Matthey Plc | Supported metal catalysts |
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CN1554480A (en) * | 2003-12-29 | 2004-12-15 | 南开大学 | Preparation of CuO/CeO2 catalyst and use in CO oxidation |
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