CN110252291A - A kind of Pt base catalyst and preparation method for preferential oxidation CO under hydrogen-rich - Google Patents

A kind of Pt base catalyst and preparation method for preferential oxidation CO under hydrogen-rich Download PDF

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CN110252291A
CN110252291A CN201910547854.4A CN201910547854A CN110252291A CN 110252291 A CN110252291 A CN 110252291A CN 201910547854 A CN201910547854 A CN 201910547854A CN 110252291 A CN110252291 A CN 110252291A
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catalyst
solution
under
hydrogen
oxidation
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王丽
宋绍飞
郭耘
赵瑞玲
张�诚
王筠松
詹望成
郭杨龙
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East China University of Science and Technology
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Abstract

CO oxidation is preferentially selected to generate CO under a kind of hydrogen-rich atmosphere2Catalyst PtxMy/Al2O3, wherein x is 0.5-5.0 wt%；Y is 0.1-3.0 wt%.M be one of Fe, Co, Ni, Cu, Zn, Mn, Pd, Au, Ag and more than one；Selected aluminium oxide is Alpha-alumina.Pt and M exists in the form of alloy, and exists in alloy surface M with the oxide of 1-2 atomic layer level thickness, hydroxide form.Catalyst of the present invention can in wide temperature window (0~160 DEG C) by hydrogen CO preference oxidation generate carbon dioxide (CO2), and in steam (H2) and CO O2In the presence of in the case of, still there is catalyst good selective oxidation CO to generate CO2Performance and stability.

Description

A kind of Pt base catalyst and preparation method for preferential oxidation CO under hydrogen-rich
Technical field
The present invention relates to for the preparation method of the Pt based alloy catalyst of preferential oxidation carbon monoxide under rich hydrogen condition and Using.
Background technique
For alleviating energy crisis and environmental pollution, the whole world all replaces traditional stone actively finding some new energy Change fuel, including solar energy, wind energy, Hydrogen Energy, geothermal energy, ocean energy, biomass energy, nuclear energy and is derived by renewable energy The bio-fuel etc. come.Wherein, Hydrogen Energy is most clean fuel, can accomplish to zero environmental with recycle;And hydrogen It is one of the most abundant element in earth environment, therefore hydrogen is the fuel that can replace traditional energy in a kind of future.
It is the Proton Exchange Membrane Fuel Cells (PEMFCs) of fuel with H using High Purity Hydrogen+As exchange carrier, with volume The advantages that small, operating temperature low (80-110 DEG C), power density are high, the high and low startup temperature of energy conversion efficiency is fast, so as to cause Worldwide extensive concern.These can mean that the coming of Hydrogen Energy and Proton Exchange Membrane Fuel Cells epoch.It is existing Stage, the approach of hydrogen manufacturing mainly include three kinds: 1) biomass ferment hydrogen；2) water electrolysis hydrogen production gas；3) fossil feedstock Hydrogen.
Currently, the hydrogen that proton exchange fuel cell needs largely comes from hydrocarbon (such as methanol, ethyl alcohol, natural Gas etc.) reforming reaction or partial oxidation obtain enriched gas source, then pass through water gas shift reaction (CO+H2O→CO2+ H2) removal wherein most remnants CO, the reformation gas bag finally obtained is containing 45%~75%H2, 15%~25%CO2, 0.5%~2% CO, a small amount of vapor and nitrogen.However, the Pt electrode material of fuel cell is extremely sensitive to CO, it is easy to be poisoned, and CO molecule Tend to take up catalyst surface adsorption potential, influence the working efficiency of electrode, thus in hydrogen-rich gas carbon monoxide concentration it is necessary Control is in 100 ppm or less.The method of laboratory and industrial depth removal carbon monoxide mainly has at present: CO is preferentially catalyzed oxygen Change method, CO selective methanation method, pressure swing adsorption method and membrane separation process etc..Wherein, membrane separation process cost is excessively high, pressure swing adsorption method System complex is not suitable for fuel cell system both.
CO preferential oxidation under rich hydrogen condition generates CO2Be remove a small amount of CO in hydrogen be most have application prospect method it One.The committed step of this method is to be passed through a small amount of oxygen or air in hydrogen-rich reformed gas, and CO is aoxidized and generated by selectivity CO2Its concentration is set to drop to ppm rank.Au catalyst has high CO low temperature oxidation, but due to H under high temperature2Competition oxygen Change, causes the selectivity of CO to reduce, therefore Au catalyst is difficult to remove CO to 10 ppm or less at 80~180 DEG C.In addition, The stability of Au base catalyst and the sensibility of preparation process also limit its practical application.Cu base catalyst, especially CuO- CeO2Although cheap, its low temperature active is poor, usually just active at 100 DEG C or more, and water resistant and CO2Performance it is poor (ACS Catal. 2016,6 (3), 1723-1731).
Pt base catalyst has better stability and water-fast and resistance to CO2Property, but its low temperature active is not high.In order to improve Pt The low temperature active of base catalyst generallys use in a manner of bimetallic alloy or addition auxiliary agent.Chinese patent application CN 101856621 propose a kind of utilization equi-volume impregnating addition Fe, Co, and the transition metal such as Ni are the Pt base catalyst of auxiliary agent, It can be within the temperature range of 60~100 DEG C by CO complete oxidation in hydrogen.Qiao directly uses iron oxide to be catalyzed as Pt The carrier of agent, the Pt sub-nanometer cluster and single atom being dispersed on Iron oxide support by Co deposited synthesis are catalyzed Agent.With standard Au/Fe2O3Catalyst is compared, and Pt/Fe catalyst shows quite outstanding low temperature active, in 20-70 DEG C of window The full conversion (ACS Catal. 2014,4 (7), 2113-2117) of CO may be implemented in range.Although these transition metal Introduce the low temperature active for effectively increasing Pt base catalyst, but under the rich hydrogen condition of temperature even lower at room temperature difficult to realize CO selective oxidation.In addition, the operating temperature window of CO complete oxidation is narrow, then it is unable to satisfy the requirement of practical application, limited It has been made to apply in fuel system.Therefore, there is an urgent need to a kind of low temperature active height, CO complete oxidations in fuel cell industries field Generate CO2Temperature window mouth width, water-fast and CO2Catalyst.
Summary of the invention
It is an object of the invention to prepare to have a high low temperature active for selective oxidation CO under rich hydrogen condition, wide CO is complete Oxidized temperature window, in vapor and CO2In the presence of catalyst still there is good CO preferential oxidation to generate CO2It is anti- Answer performance and stability.
To achieve the goals above, the technical solution adopted by the present invention is;
1) presoma that platinum and metal are weighed in required ratio, is added in organic alcohol solvent；
2) alkaline solution is added dropwise in Xiang Shangshu solution, adjusts pH value in 7-14；
3) solution of the above-mentioned gained containing Nano sol is spare after centrifugation, washing；
4) by suitable α-Al2O3It is dried after being added to above-mentioned Nano sol solution；
The present invention has the advantages that
1) the PtM particle size that the method for the present invention is prepared is uniform, high dispersive is in α-Al2O3On；
2) method for preparing catalyst of the present invention is simple and easy；
Specific embodiment
Below by example, the present invention is further described, but the present invention is not limited to subordinate's embodiments.
For the catalyst performance for evaluating prepared catalyst, catalyst is carried out using atmospheric fixed bed quartz tube reactor CO Selective Oxidation performance test under hydrogen-rich atmosphere.Test condition are as follows: gas composition 1%CO+1%O2+20%H2+ Ar, quality 75 000ml g of air speed-1 h-1.Activity rating is carried out to catalyst in -50~200 DEG C of sections.It is detected and is reacted using chromatography Device exit gas composition, and calculate conversion ratio and selectivity.
CO conversion ratio and CO2Selective calculation method is as follows:
Wherein: [CO]inlet[O2]inletRespectively feed CO and O2Chromatography area, [CO]outlet[O2]outletRespectively Export CO and O2Chromatography area.
Embodiment 1
The cobalt nitrate of the platinum nitrate of 0.85 g and 0.12 g is added in the propylene glycol solution of 50 ml, stirs 30 min, stirring Under the sodium hydroxide solution of 0.5 mol/L is added dropwise, adjusting pH value is 13, is warming up to 160 DEG C of 3 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and after stirring 12h at room temperature, filters, deionized water washing, and 120 DEG C of 3 h of vacuum drying are prepared and urge Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 50~150 DEG C It is oxidized.
Embodiment 2
The cobalt nitrate of the platinum nitrate of 0.85 g and 0.12 g is added in the ethylene glycol solution of 50 ml, stirs 30 min, stirring Under be added dropwise ammonia spirit, adjusting pH value is 9, is warming up to 140 DEG C of 5 h of reflux.After being cooled to room temperature, by colloidal solution from It is dispersed in after the heart, deionized water washing spare in 25 ml ethyl alcohol.By 10 g γ-Al2O3It is mixed with the solution of Nanoalloy particle It closes, after stirring 12 h at room temperature, filters, deionized water washing, be dried in vacuo 6 h at 100 DEG C and catalyst is prepared.Upper Active testing is carried out under the conditions of stating to it, prepared catalyst can realize the preferential complete oxidation of CO at 85~145 DEG C.
Embodiment 3
The cobalt nitrate of the platinum nitrate of 0.85 g and 0.05 g is added in the glycerin solution of 50 ml, stirs 30 min, stirring Under the sodium hydroxide solution of 0.7 mol/L is added dropwise, adjust pH value and be 9, be warming up to 120 DEG C of 5 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 6 h at 120 DEG C and is prepared and urges Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 45~155 DEG C It is oxidized.
Embodiment 4
The cobalt nitrate of the platinum nitrate of 0.85 g and 0.54 g is added in the glycerin solution of 50 ml, stirs 30 min, stirring Under the sodium hydroxide solution of 0.5 mol/L is added dropwise, adjust pH value and be 9, be warming up to 120 DEG C of 5 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 3 h at 60 DEG C and is prepared and urges Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 0~160 DEG C Oxidation.
Embodiment 5
The cobalt nitrate of the platinum nitrate of 0.42 g and 0.35 g is added in the glycerin solution of 50 ml, stirs 30 min, stirring Under the sodium carbonate liquor of 0.5 mol/L is added dropwise, adjust pH value and be 7, be warming up to 140 DEG C of 5 h of reflux.After being cooled to room temperature, It is spare in 25 ml ethyl alcohol by being dispersed in after colloidal solution centrifugation, deionized water washing.By 10 g α-Al2O3With Nanoalloy The solution mixing of grain, stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 9 h at 60 DEG C and catalysis is prepared Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize the preferential complete oxygen of CO at 25~150 DEG C Change.
Embodiment 6
The nickel nitrate of the platinum nitrate of 0.35 g and 0.26 g is added in the propylene glycol solution of 50 ml, stirs 30 min, stirring Under the potassium hydroxide solution of 1.0 mol/L is added dropwise, adjust pH value and be 11, be warming up to 140 DEG C of 3 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 9 h at 60 DEG C and is prepared and urges Agent.It can realize that CO's is preferential complete at 45~125 DEG C to active testing, prepared catalyst is carried out under the above conditions It is oxidized.
Embodiment 7
The copper nitrate of the platinum nitrate of 0.35 g and 0.25 g is added in the propylene glycol solution of 50 ml, stirs 30 min, stirring Under be added dropwise ammonia spirit, adjust pH value and be 9, be warming up to 160 DEG C of 3 h of reflux.After being cooled to room temperature, by colloidal solution from It is dispersed in after the heart, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3It is mixed with the solution of Nanoalloy particle, 12 h are stirred at room temperature, are filtered, deionized water washing, are dried in vacuo 3 h at 120 DEG C and catalyst is prepared.In above-mentioned condition Under carry out active testing to it, prepared catalyst can realize the preferential complete oxidation of CO at 40~140 DEG C.
Embodiment 8
The zinc nitrate of the platinum nitrate of 0.56 g and 0.42 g is added in the propylene glycol solution of 50 ml, stirs 30 min, stirring Under the sodium hydroxide solution of 0.3mol/L is added dropwise, adjust pH value and be 9, be warming up to 120 DEG C of 6 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 9 h at 60 DEG C and is prepared and urges Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 75~145 DEG C It is oxidized.
Embodiment 9
The ferric nitrate of the platinum nitrate of 0.17 g and 0.30 g is added in the propylene glycol solution of 50 ml, stirs 30min, stirring Under the sodium hydroxide solution of 1.0 mol/L is added dropwise, adjust pH value and be 11, be warming up to 120 DEG C of 6 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 9 h at 60 DEG C and is prepared and urges Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 35~150 DEG C It is oxidized.
Embodiment 10
The manganese nitrate of the platinum nitrate of 0.29 g and 0.25 g is added in the ethylene glycol solution of 50 ml, stirs 30min, stirring Under the sodium hydroxide solution of 0.7 mol/L is added dropwise, adjust pH value and be 10, be warming up to 120 DEG C of 3 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 6 h at 90 DEG C and is prepared and urges Agent.It can realize that CO's is preferential complete at 75~120 DEG C to active testing, prepared catalyst is carried out under the above conditions It is oxidized.
Embodiment 11
The palladium nitrate of the platinum nitrate of 0.34 g and 0.15 g is added in the propylene glycol solution of 50 ml, stirs 30min, stirring Under be added dropwise ammonia spirit, adjust pH value and be 10, be warming up to 120 DEG C of 5 h of reflux.After being cooled to room temperature, by colloidal solution from It is dispersed in after the heart, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3It is mixed with the solution of Nanoalloy particle, 12 h are stirred at room temperature, are dried in vacuo 3 h at suction filtration, 120 DEG C of deionized water washing and catalyst is prepared.In above-mentioned condition Under carry out active testing to it, prepared catalyst can realize the preferential complete oxidation of CO at 25~130 DEG C.
Embodiment 12
The silver nitrate of the platinum nitrate of 0.34 g and 0.28 g is added in the glycerin solution of 50 ml, stirs 30min, stirring Under the potassium hydroxide solution of 1.0 mol/L is added dropwise, adjust pH value and be 11, be warming up to 160 DEG C of 3 h of reflux.It is cooled to room temperature Afterwards, it will be dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy The solution of particle mixes, and stirs 12 h at room temperature, filters, deionized water washing, is dried in vacuo 9 h at 60 DEG C and is prepared and urges Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 70~130 DEG C It is oxidized.
Embodiment 13
The platinum nitrate of 0.42 g, the cobalt nitrate of 0.35g and 0.30 g ferric nitrate are added in the propylene glycol solution of 50 ml, stirred 30min is mixed, the potassium hydroxide solution of 1.0 mol/L is added dropwise under stirring, pH value is adjusted and is 9, is warming up to 140 DEG C of reflux 5 h.It is spare in 25 ml ethyl alcohol by being dispersed in after colloidal solution centrifugation, deionized water washing after being cooled to room temperature.By 10 g α- Al2O3It is mixed with the solution of Nanoalloy particle, stirs 12 h at room temperature, filtered, deionized water washing, vacuum is dry at 120 DEG C Catalyst is prepared in dry 3 h.Active testing is carried out to it under the above conditions, prepared catalyst can be at 35~130 DEG C Realize the preferential complete oxidation of CO.
Embodiment 14
The platinum nitrate of 0.42 g, the manganese nitrate of 0.25 g and 0.26 nickel nitrate are added in the glycerin solution of 50 ml, stirred The potassium hydroxide solution of 0.5 mol/L is added dropwise in 30min under stirring, adjust pH value and be 11, be warming up to 160 DEG C of 3 h of reflux. It is spare in 25 ml ethyl alcohol by being dispersed in after colloidal solution centrifugation, deionized water washing after being cooled to room temperature.By 10 g α-Al2O3 It is mixed with the solution of Nanoalloy particle, stirs 12 h at room temperature, filtered, deionized water washing, be dried in vacuo 6 h at 90 DEG C Catalyst is prepared.Active testing is carried out to it under the above conditions, prepared catalyst can be realized at 45~135 DEG C The preferential complete oxidation of CO.
Embodiment 15
The platinum nitrate of 0.25 g, the ferric nitrate of 0.30 g and 0.26 nickel nitrate are added in the ethylene glycol solution of 50 ml, stirred Ammonia spirit is added dropwise in 30min under stirring, adjust pH value and be 9, be warming up to 120 DEG C of 5 h of reflux.It, will after being cooled to room temperature It is dispersed in after colloidal solution centrifugation, deionized water washing spare in 25 ml ethyl alcohol.By 10 g α-Al2O3With Nanoalloy particle Solution mixing, stir 12 h at room temperature, filter, deionized water washing, be dried in vacuo 3 h at 120 DEG C and catalysis is prepared Agent.Active testing is carried out to it under the above conditions, prepared catalyst can realize that CO's is preferential complete at 40~135 DEG C Oxidation.

Claims (6)

1. CO oxidation is preferentially selected to generate CO under a kind of hydrogen-rich2Catalyst PtxMy/Al2O3, wherein x is 0.5-5.0 wt %；Y is 0.1-3.0 wt %。
2. according to catalyst described in claim 1, it is characterised in that: one in M Fe, Co, Ni, Cu, Zn, Mn, Pd, Au, Ag Kind or two kinds；Selected aluminium oxide is Alpha-alumina.
3. according to catalyst described in claim 1, it is characterised in that: Pt and M exists in the form of alloy, and in alloy surface M exists with the oxide of 1-2 atomic layer level thickness or hydroxide form.
4. a kind of preparation method of catalyst described in claim 1, it is characterised in that: by platinum presoma and transition metal precursor It is added in organic solvent；It states then up and precipitating reagent is added dropwise in mixed liquor, adjust solution ph and heat to obtain Nanoalloy Grain, catalyst can be made by loading to Alpha-alumina.
5. according to catalyst described in claim 1, it is characterised in that: the organic solvent is organic alcohol solvent, such as methanol, second More than alcohol, butanol, ethylene glycol, propylene glycol, glycerine are one or two kinds of；Precipitating reagent is alkaline precipitating agent, such as potassium hydroxide, ammonia Water, sodium carbonate, sodium hydroxide solution it is one or two kinds of more than.
6. according to catalyst described in claim 1, it is characterised in that: prepared under the conditions of alkaline solution.
CN201910547854.4A 2019-06-24 2019-06-24 A kind of Pt base catalyst and preparation method for preferential oxidation CO under hydrogen-rich Pending CN110252291A (en)

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