CN108448123A - A kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction - Google Patents

A kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction Download PDF

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CN108448123A
CN108448123A CN201810242713.7A CN201810242713A CN108448123A CN 108448123 A CN108448123 A CN 108448123A CN 201810242713 A CN201810242713 A CN 201810242713A CN 108448123 A CN108448123 A CN 108448123A
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catalyst
water gas
gas shift
low
temperature water
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CN108448123B (en
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江莉龙
刘毅
王秀云
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Fuzhou University
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Fuzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

The invention discloses a kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction.By cerium base presoma and Cu (NO3)2•3H2O and precipitating reagent urea are jointly in hydro-thermal reaction, then the roasting that heats up, then 20vol%CO is passed through in reduction2+2vol%H2It is handled in+78vol%He atmosphere；Most afterwards through 10vol%O2+ 90vol%Ar handles to obtain catalyst.Preparation method of the present invention greatly improves Cu/CeO2Catalytic activity and stability of the catalyst in water gas shift reaction.Catalyst activity 350 DEG C activity after performic acid is handled, Water gas shift/WGS activity increases to 86% from 47%, and is run 15 40 hours at 400 DEG C, and catalytic activity is without being substantially reduced, the size of Cu and Ce nano particles is kept afterwards before the reaction simultaneously, has apparent industrial application value.

Description

A kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction
Technical field
The invention belongs to catalyst material preparation fields, and in particular to a kind of cerium base for low-temperature water gas shift reaction Catalyst and preparation method thereof.
Background technology
With the development of hydrogen economy, hydrogen fuel cell becomes important new energy application platform.To prevent in hydrogen fuel A small amount of carbon monoxide（CO）Fuel-cell catalyst is poisoned, water gas shift reaction can be used, hydrogen fuel is purified. It is reacted as a favors low temperature, it can be in the efficient water gas converting catalyst that lower temperature works, energy if can find Thermodynamic (al) advantage is obtained while obtaining high catalytic activity, this is also and low temperature hydrogen fuel cell（Operating temperature 70-90 ℃）The needs effectively integrated.Therefore, exploitation has the Water gas shift/WGS of high catalytic activity and stability catalysis simultaneously in low-temperature space Agent is of great significance.
With the continuous development of catalytic base theory, H is determined substantially2O Dissociatives and CO oxidations are that transformationreation is extremely closed Two important step elementary reactions.Therefore the transformation catalyst haveing excellent performance should have adsorption and oxidation CO and Dissociative simultaneously H2Both functions of O, copper are to H2O Dissociatives and CO oxidations while the metal with high activity, and other than Cu almost There is no substance that can be completed at the same time the two processes, therefore researcher spares no effort to be dedicated to using Cu as active component always The exploitation of novel water gas converting catalyst.In addition, compared with noble metal adorns base catalyst, the price of copper is more cheap, therefore In recent years, Cu/CeO2The research of water gas converting catalyst is always hot spot.
The present invention is further to promote Cu/CeO2The activity and stability of catalyst, pass through 20vol%CO2+2vol%H2+ 78vol%He handles and changes treatment temperature, enhances the strong interaction between the Metal-Support of carried catalyst（SMSI）, with strong Change catalyst catalytic activity and stability in low-temperature water gas shift reaction.
Invention content
The present invention provides a kind of cerium base catalyst and preparation method thereof for low-temperature water gas shift reaction.
It is described for low-temperature water gas shift reaction cerium base catalyst, handled by special atmosphere, catalyst it is main Ingredient includes CeO2The Cu of carrier and load on this carrier.
It is described by special atmosphere treated cerium base catalyst, at being -196 DEG C in liquid nitrogen temperature using nitrogen adsorption/ Desorption test specific surface area is 39-49 m2/ g is 2 times that catalyst is handled without adsorbent.
Wherein special atmosphere refers to so that catalyst surface has HCO2 -And HCO3 -The mixed atmosphere of both ions.
Wherein special atmosphere is specially 20vol%CO2、2vol%H2And the mixed gas of 78vol%He.
The catalyst contains the Cu relative to total catalyst weight 10-30 %, preferably 16-24 %.
The preparation method of the catalyst includes the following steps：By cerium base presoma and Cu (NO3)2·3H2O and precipitation Agent urea jointly at 120 DEG C hydro-thermal reaction for 24 hours after, be warming up to 400-500 DEG C by the speed of 1 DEG C/min, roast 3-5h, H21-3h is restored in atmosphere at 350-400 DEG C, then passes through 20vol%CO2+2vol%H2In 250- in+78vol%He atmosphere It is obtained after handling 2-4h at 400 DEG C；Most afterwards through 10vol%O2+ 90vol%Ar is handled 3-5 hours and is obtained catalyst.
The calcination temperature of the catalyst is 400-500 DEG C, and preferably 400-450 DEG C, roasting time is 3-5 hours, excellent It selects 3 hours.
The reduction temperature of the catalyst is 300-400 DEG C, and preferably 350-400 DEG C, the recovery time is 1-3 hours, excellent It selects 3 hours.
The special atmosphere treatment temperature of the catalyst be 250-400 DEG C, preferably 350-400 DEG C, processing time 2-4 Hour, preferably 4 hours.
Gained cerium base catalyst of the invention is used equally for catalysis low-temperature water gas shift reaction.
The remarkable advantage of the present invention is：
The present invention passes through 20vol%CO2+2vol%H2+ 78vol%He processing and the selection for the treatment of temperature, have been prepared Cu/ CeO2- SMSI-250 DEG C and Cu/CeO2- SMSI-400 DEG C of two catalyst.Gained catalyst is equal within the scope of wider temperature Higher catalytic activity is showed, such as：Cu/CeO2- SMSI-400 DEG C have reached 87% in 300 DEG C of CO catalytic conversions, and Traditional Cu/CeO2The CO conversion ratios of catalyst are only 46%.
The clean-up effect of catalyst provided by the invention is better than traditional Cu/CeO2Water-gas shift reaction catalyst, and Its preparation process is simple, easy to operate, at low cost, CO high conversion rates, has apparent industrial application value.
Cerium base catalyst of the present invention is reacted for low-temperature water gas shift, can also be used as coating in granular form It is carried on the honeycomb supports such as cordierite, is prepared into monolithic porous formula catalyst.
Description of the drawings
Fig. 1 is cerium base catalyst obtained by embodiment 1-3 in the CO conversion ratios of different temperature points.
Fig. 2 is the stability of embodiment 1 and 3 gained catalyst of embodiment at 400 DEG C.
Specific implementation mode
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
1 Cu/CeO of embodiment2- SMSI-250 DEG C of preparation
Weigh 1.7369g Ce (NO3)3·6H2O（Molecular weight 434.22）、0.6547g Cu（NO3）2·3H2O（Molecular weight 241.6016）And 42g urea, it adds it in 120 mL deionized waters, is then transferred in water heating kettle, at 120 DEG C For 24 hours, centrifugation, ethyl alcohol and washing 5-6 times, 80 DEG C of 12 h of drying then enter Muffle furnace, with the rate of 1 DEG C/min to hydro-thermal reaction 400 DEG C are raised to, 3 h of calcination process, in H23h is restored at 400 DEG C in atmosphere, then in 20vol%CO2+2vol%H2+ 4h is handled at 250 DEG C in 78vol%He atmosphere, using at 400 DEG C, 10vol%O2+ 90vol%Ar is handled 4 hours.
2 Cu/CeO of embodiment2- SMSI-400 DEG C of preparation
Weigh 1.7369g Ce (NO3)3·6H2O（Molecular weight 434.22）、0.6547g Cu（NO3）2·3H2O（Molecular weight 241.6016）And 42g urea, it adds it in 120 mL deionized waters, is then transferred in water heating kettle, at 120 DEG C For 24 hours, centrifugation, ethyl alcohol and washing 5-6 times, 80 DEG C of 12 h of drying then enter Muffle furnace, with the rate of 1 DEG C/min to hydro-thermal reaction 400 DEG C are raised to, 3 h of calcination process, in H23h is restored at 400 DEG C in atmosphere, then in 20vol%CO2+2vol%H2+ 3h is handled at 400 DEG C in 78vol%He atmosphere, using at 400 DEG C, 10vol%O2+ 90vol%Ar is handled 4 hours.
3 Cu/CeO of embodiment2Preparation
Weigh 1.7369g Ce (NO3)3·6H2O（Molecular weight 434.22）、0.6547g Cu（NO3）2·3H2O（Molecular weight 241.6016）And 42g urea, it adds it in 120 mL deionized waters, is then transferred in water heating kettle, at 120 DEG C For 24 hours, centrifugation, ethyl alcohol and washing 5-6 times, 80 DEG C of 12 h of drying then enter Muffle furnace, with the rate of 1 DEG C/min to hydro-thermal reaction 400 DEG C are raised to, 3 h of calcination process, in H2In atmosphere 3h is restored at 400 DEG C.
4 catalyst performance evaluation of embodiment
Catalyst each 0.5 g, 6000 mL/ of mass space velocity (gh) of embodiment 1-3 is respectively adopted, is catalyzed in CO low-temperature conversions CO conversion ratio measurement is carried out on agent Microactivity Test Unit (CO-CMAT9001), in tail gas the variation of CO concentration pass through gas-chromatography survey Fixed, reaction gas group becomes：15vol%CO、7 vol%CO2、55 vol%H2And N2For Balance Air.It is measured at 150-400 DEG C Catalyst is shown in Fig. 1 to the changing effect of CO, test result.The stability test of catalyst carries out at 400 DEG C, test result See Fig. 2.
It will be seen from figure 1 that Cu/CeO2- SMSI-400 DEG C of catalyst in 350 DEG C of CO conversion ratios up to 86%, and without 20vol%CO2+2vol%H2The Cu/CeO of+78vol%He processing2Catalyst is converted into 47% in 400 DEG C of CO.
Figure it is seen that Cu/CeO2- SMSI-400 DEG C of catalyst are stablized 15 hours at 400 DEG C, CO conversion ratios Slightly reduce, and without 20vol%CO2+2vol%H2The Cu/CeO of+78vol%He processing2Catalyst is converted in 400 DEG C of CO To be reduced to 74% from 88%.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification should all belong to the covering scope of the present invention.

Claims (7)

1. a kind of cerium base catalyst for low-temperature water gas shift reaction, it is characterised in that：The catalyst is by special gas The copper cerium catalyst of atmosphere processing, which includes CeO2The Cu of carrier and load on this carrier.
2. according to the catalyst for low-temperature water gas shift reaction described in claim 1, it is characterised in that：The spy Different atmosphere refers to so that catalyst surface has HCO2 -And HCO3 -The mixed atmosphere of both ions.
3. the catalyst according to claim 2 for low-temperature water gas shift reaction, it is characterised in that：It is described special Atmosphere is specially 20vol%CO2、2vol%H2And the mixed gas of 78vol%He.
4. according to the catalyst for low-temperature water gas shift reaction described in claim 1, it is characterised in that：Described Cu is active component, and the weight of the active component is the 10-30% of the total catalyst weight.
5. according to the catalyst for low-temperature water gas shift reaction described in claim 1, it is characterised in that：It is described to urge Agent contains the CeO of the 70-90% relative to total catalyst weight2。
6. a kind of method preparing the catalyst as described in claim 1 for low-temperature water gas shift reaction, feature exist In：By cerium base presoma and Cu (NO3)2·3H2Then O and the common hydro-thermal reaction of precipitating reagent urea press the speed of 1 DEG C/min It is warming up to 400-500 DEG C, 3-5h is roasted, in H21-3h is restored in atmosphere at 350-400 DEG C, then passes through 20vol%CO2+ 2vol%H2It is obtained after handling 2-4h at 250-400 DEG C in+78vol%He atmosphere；Most afterwards through 10vol%O2+ 90vol%Ar processing Obtain catalyst within 3-5 hours.
7. the preparation method of the catalyst according to claim 6 for low-temperature water gas shift reaction, it is characterised in that： Hydrothermal reaction condition is to be reacted for 24 hours at 120 DEG C.
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Cited By (2)

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CN111282601A (en) * 2020-04-09 2020-06-16 福州大学 Activation method and application of copper-based water gas shift catalyst
CN114733525A (en) * 2022-03-07 2022-07-12 国网综合能源服务集团有限公司 Nickel-cobalt alloy catalyst with bimetal synergistic effect and application of nickel-cobalt alloy catalyst in catalyzing water gas shift reaction

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111282601A (en) * 2020-04-09 2020-06-16 福州大学 Activation method and application of copper-based water gas shift catalyst
CN111282601B (en) * 2020-04-09 2022-06-03 福州大学 Activation method and application of copper-based water gas shift catalyst
CN114733525A (en) * 2022-03-07 2022-07-12 国网综合能源服务集团有限公司 Nickel-cobalt alloy catalyst with bimetal synergistic effect and application of nickel-cobalt alloy catalyst in catalyzing water gas shift reaction

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