CN108448123B - Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof - Google Patents

Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof Download PDF

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CN108448123B
CN108448123B CN201810242713.7A CN201810242713A CN108448123B CN 108448123 B CN108448123 B CN 108448123B CN 201810242713 A CN201810242713 A CN 201810242713A CN 108448123 B CN108448123 B CN 108448123B
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catalyst
gas shift
water gas
cerium
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CN108448123A (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

Abstract

The invention discloses a cerium-based catalyst for low-temperature water gas shift reaction and a preparation method thereof. Mixing cerium-based precursor with Cu (NO)3)2•3H2Carrying out hydrothermal reaction on O and precipitator urea together, heating, roasting, reducing, and then carrying out 20vol% CO2+2vol%H2+78vol% He atmosphere; finally, the mixture is treated with 10vol% of O2+90vol% Ar treatment gave the catalyst. The preparation method of the invention greatly improves the Cu/CeO content2Catalytic activity and stability of the catalyst in water gas shift reactions. After the activity of the catalyst at 350 ℃ is treated by formic acid, the water gas shift activity is increased from 47% to 86%, and the catalyst operates for 15-40 hours at 400 ℃, so that the catalytic activity is not obviously reduced, and the sizes of Cu and Ce nano particles are maintained before and after the reaction, thereby having obvious industrial application value.

Description

Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof
Technical Field
The invention belongs to the field of catalyst material preparation, and particularly relates to a cerium-based catalyst for low-temperature water gas shift reaction and a preparation method thereof.
Background
With the development of hydrogen energy economy, hydrogen fuel cells have become an important new energy application platform. To prevent poisoning of fuel cell catalysts by small amounts of carbon monoxide (CO) in the hydrogen fuel, the hydrogen fuel may be purified using the water gas shift reaction. As a low temperature favored reaction, the thermodynamic advantage of high catalytic activity while simultaneously achieving high efficiency water gas shift catalysts that can operate at lower temperatures would be desirable for effective integration with low temperature hydrogen fuel cells (operating temperatures 70-90 ℃). Therefore, it is of great interest to develop a water gas shift catalyst having both high catalytic activity and stability in a low temperature region.
With the continuous development of the basic theory of catalysis, H is basically determined2O dissociation adsorption and CO oxidation are two-step elementary reactions which are crucial to the shift reaction. Therefore, a shift catalyst with excellent performance should have both CO adsorption and CO desorption and H desorption2O, copper is for H2Metals having high activity in both O dissociation adsorption and CO oxidation, and few substances other than Cu can accomplish both processes at the same time, researchers have been devoted without any loss to the development of novel water gas shift catalysts having Cu as an active component. In addition, copper is less expensive than noble metal-based catalysts, so in recent years Cu/CeO2Research on water gas shift catalysts has been a hotspot.
The invention aims to further improve the Cu/CeO2Activity and stability of the catalyst by 20vol% CO2+2vol%H2+78vol% He treatment and changing the treatment temperature enhance the strong metal-support interaction (SMSI) of the supported catalyst to enhance the catalyst activity and stability in low temperature water gas shift reactions.
Disclosure of Invention
The invention provides a cerium-based catalyst for low-temperature water gas shift reaction and a preparation method thereof.
The cerium-based catalyst for the low-temperature water gas shift reaction is treated in special atmosphere, and the main component of the catalyst comprises CeO2A carrier and Cu supported on the carrier.
The cerium-based catalyst treated in the special atmosphere has a specific surface area of 39-49 m by utilizing nitrogen adsorption/desorption test at the liquid nitrogen temperature of-196 DEG C2The concentration of the catalyst is 2 times that of the catalyst which is not treated by the adsorbent.
Wherein the special atmosphere refers to that HCO is attached to the surface of the catalyst2 -And HCO3 -A mixed atmosphere of these two ions.
Wherein the special atmosphere is specifically 20vol% CO2、2vol%H2And 78vol% He.
The catalyst contains 10-30% Cu, preferably 16-24%, relative to the total weight of the catalyst.
The preparation method of the catalyst comprises the following steps: mixing cerium-based precursor with Cu (NO)3)2·3H2The O and the precipitator urea are subjected to hydrothermal reaction at 120 ℃ for 24 hours, then the temperature is raised to 400-500 ℃ at the speed of 1 ℃/min, the mixture is roasted for 3-5 hours, and the reaction is carried out in the presence of H2Reducing for 1-3h at the temperature of 350-400 ℃ in the atmosphere, and then passing through 20vol% CO2+2vol%H2Treating the mixture for 2 to 4 hours at the temperature of 250-400 ℃ in He atmosphere of +78vol percent; finally, the mixture is treated with 10vol% of O2+90vol% Ar treatment for 3-5 hours to obtain the catalyst.
The calcination temperature of the catalyst is 400-500 ℃, preferably 400-450 ℃, and the calcination time is 3-5 hours, preferably 3 hours.
The reduction temperature of the catalyst is 300-400 ℃, preferably 350-400 ℃, and the reduction time is 1-3 hours, preferably 3 hours.
The special atmosphere treatment temperature of the catalyst is 250-400 ℃, preferably 350-400 ℃, and the treatment time is 2-4 hours, preferably 4 hours.
The cerium-based catalyst obtained by the invention can be used for catalyzing low-temperature water gas shift reaction.
The invention has the following remarkable advantages:
the invention passes 20vol% CO2+2vol%H2+78vol% He treatment and treatment temperature selection to prepare Cu/CeO2-SMSI-250 ℃ and Cu/CeO2SMSI-400 ℃ two catalysts. The obtained catalyst has higher catalytic activity in a wider temperature range, such as: Cu/CeO2The CO catalytic conversion rate of-SMSI-400 ℃ at 300 ℃ reaches 87 percent compared with the traditional Cu/CeO2The CO conversion of the catalyst was only 46%.
The purification effect of the catalyst provided by the invention is superior to that of the traditional Cu/CeO2The water gas shift reaction catalyst has simple preparation process, convenient operation, low cost and high CO conversion rate,has obvious industrial application value.
The cerium-based catalyst is used for low-temperature water gas shift reaction, can be in a particle form, and can also be used as a coating to be loaded on honeycomb carriers such as cordierite and the like to prepare an integral porous catalyst.
Drawings
Fig. 1 is a graph showing CO conversion rates of cerium-based catalysts obtained in examples 1 to 3 at different temperature points.
FIG. 2 shows the stability of the catalysts obtained in examples 1 and 3 at 400 ℃.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
EXAMPLE 1 Cu/CeO2Preparation of-SMSI-250 deg.C
1.7369g Ce (NO) was weighed out3)3·6H2O (molecular weight 434.22), 0.6547g Cu (NO)3）2·3H2Adding O (molecular weight is 241.6016) and 42g urea into 120 mL deionized water, transferring into a hydrothermal kettle, performing hydrothermal reaction at 120 ℃ for 24H, centrifuging, washing with ethanol and water for 5-6 times, drying at 80 ℃ for 12H, introducing into a muffle furnace, heating to 400 ℃ at a speed of 1 ℃/min, roasting for 3H, and calcining in H2Reducing at 400 ℃ for 3h in an atmosphere and then 20vol% CO2+2vol%H2Treating at 250 deg.C for 4h in He atmosphere of +78vol%, and then treating with 10vol% O at 400 deg.C2+90vol% Ar for 4 hours.
EXAMPLE 2 Cu/CeO2Preparation of-SMSI-400 DEG C
1.7369g Ce (NO) was weighed out3)3·6H2O (molecular weight 434.22), 0.6547g Cu (NO)3）2·3H2Adding O (molecular weight 241.6016) and 42g urea into 120 mL deionized water, transferring into a hydrothermal kettle, performing hydrothermal reaction at 120 deg.C for 24h, centrifuging, washing with ethanol and water for 5-6 times, drying at 80 deg.C for 12 h, adding into a muffle furnace, heating to 400 deg.C at a rate of 1 deg.C/min, and calciningTreatment for 3H at H2Reducing at 400 ℃ for 3h in an atmosphere and then 20vol% CO2+2vol%H2Treating at 400 deg.C for 3h in He atmosphere of +78vol%, and then treating with 10vol% O at 400 deg.C2+90vol% Ar for 4 hours.
EXAMPLE 3 Cu/CeO2Preparation of
1.7369g Ce (NO) was weighed out3)3·6H2O (molecular weight 434.22), 0.6547g Cu (NO)3）2·3H2Adding O (molecular weight is 241.6016) and 42g urea into 120 mL deionized water, transferring into a hydrothermal kettle, performing hydrothermal reaction at 120 ℃ for 24H, centrifuging, washing with ethanol and water for 5-6 times, drying at 80 ℃ for 12H, introducing into a muffle furnace, heating to 400 ℃ at a speed of 1 ℃/min, roasting for 3H, and calcining in H2Reducing for 3h at 400 ℃ in the atmosphere.
Example 4 evaluation of catalyst Performance
The catalysts of examples 1 to 3 were used, respectively, at a mass space velocity of 6000 mL/(g.h), and CO conversion was measured on a CO low-temperature shift catalyst activity measuring apparatus (CO-CMAT9001), and the change in CO concentration in the exhaust gas was measured by gas chromatography, and the reaction gas composition was: 15vol% CO, 7 vol% CO2、55 vol%H2And N2Is the balance gas. The effect of the catalyst on CO conversion was determined at 150 ℃ and 400 ℃ and the results are shown in FIG. 1. The stability test of the catalyst was carried out at 400 ℃ and the test results are shown in FIG. 2.
As can be seen from FIG. 1, Cu/CeO2The conversion of CO of the catalyst-SMSI-400 ℃ at 350 ℃ reaches 86% without 20vol% CO2+2vol%H2+78vol% He treated Cu/CeO2The catalyst had a CO conversion of 47% at 400 ℃.
As can be seen from FIG. 2, Cu/CeO2The catalyst-SMSI-400 ℃ was stable at 400 ℃ for 15 hours with a slight decrease in CO conversion without 20vol% CO2+2vol%H2+78vol% He treated Cu/CeO2The CO conversion of the catalyst at 400 ℃ was reduced from 88% to 74%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (4)

1. A cerium-based catalyst for low temperature water gas shift reactions, characterized by: the catalyst is a copper-cerium catalyst treated in special atmosphere, and the main component of the catalyst comprises CeO2A carrier and Cu supported on the carrier; the specific preparation method comprises the following steps: mixing cerium-based precursor with Cu (NO)3)2·3H2The O and the precipitator urea are subjected to hydrothermal reaction together, then the temperature is raised to 400-500 ℃ at the speed of 1 ℃/min, the mixture is roasted for 3 to 5 hours, and the mixture is subjected to hydrothermal reaction in the presence of H2Reducing for 1-3h at the temperature of 350-400 ℃ in the atmosphere, and then passing through 20vol% CO2+2vol%H2Treating the mixture for 2 to 4 hours at the temperature of 250-400 ℃ in He atmosphere of +78vol percent; finally, the mixture is treated with 10vol% of O2+90vol% Ar treatment for 3-5 hours to obtain the catalyst.
2. The catalyst for low temperature water gas shift reaction according to claim 1, characterized in that: the Cu is an active component, and the weight of the active component is 10-30% of the total weight of the catalyst.
3. The catalyst for low temperature water gas shift reaction according to claim 1, characterized in that: the catalyst contains 70-90% of CeO relative to the total weight of the catalyst2。
4. The method of preparing a catalyst for low temperature water gas shift reaction according to claim 1, wherein: the hydrothermal reaction condition is that the reaction is carried out for 24 hours at 120 ℃.
CN201810242713.7A 2018-03-23 2018-03-23 Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof Active CN108448123B (en)

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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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