CN109847747B - Low-temperature water-vapor shift catalyst and preparation method thereof - Google Patents
Low-temperature water-vapor shift catalyst and preparation method thereof Download PDFInfo
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- CN109847747B CN109847747B CN201711241928.9A CN201711241928A CN109847747B CN 109847747 B CN109847747 B CN 109847747B CN 201711241928 A CN201711241928 A CN 201711241928A CN 109847747 B CN109847747 B CN 109847747B
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Abstract
The invention relates to a low-temperature water-vapor shift catalyst and a novel preparation method thereof. The catalyst carrier is Ce-Zr composite metal oxide, and the active component is Au. The molar ratio of Ce to Zr is 0.2-5, and the loading amount of Au is 0.5-2%. The catalyst is applied to low-temperature water vapor shift reaction, particularly shows excellent catalytic activity under the condition of high space velocity, and is superior to the traditional CuZn/Al 2 O 3 A catalyst.
Description
Technical Field
The invention relates to a low-temperature water-vapor shift catalyst and a novel preparation method thereof, in particular to a catalyst which takes Au as an active component and Ce-Zr composite metal oxide as a carrier and is used for CO and H at low temperature and high airspeed 2 Catalyst for producing hydrogen by O reaction.
Background
The current source of automotive power is still derived from the combustion of fossil fuels. However, the use of fossil fuels generates a large amount of toxic gases such as carbon monoxide, carbon dioxide, sulfur dioxide, and nitrogen oxides, which cause serious environmental problems. In order to reduce environmental pollution and efficiently utilize energy, hydrogen fuel cells have become a hot spot of research. The shift reaction plays an important role in the production of hydrogen, and over 15 trillion cubic feet of hydrogen are worth of shift reaction every year. In addition, the water-vapor transformation reaction can consume CO in the fuel cell and generate hydrogen, and the poisoning of CO to the electrode in the cell is effectively avoided while the hydrogen content is improved. Thus, efficient low temperature reactions were developedThe catalyst can reduce the CO content in the raw material gas to 0.5-1%, and is suitable for small reactor size (the space velocity is usually 100000 h) -1 ) Meeting the requirements of portability and mobility is a significant challenge.
Heretofore, iron-based (Fe-Cr) high-temperature shift catalysts and Cu-Zn low-temperature shift catalysts are still the most commonly used catalysts in the water-gas shift reaction. The Fe-Cr catalyst has the advantages of wide activity range, good thermal stability, long service life, certain resistance to poisoning, low cost, easy availability, good applicability and the like. However, low space velocity (about 3000 h) -1 ) Under the conditions, the conversion rate of CO on the iron-based catalyst is only about 70 percent. Through the development of many years, the Fe-Cr catalyst reaches the activity bottleneck and is difficult to further improve. The Cu-Zn low-temperature change catalyst is suitable for the reaction at the temperature of 150 ℃ and 300 ℃ and at the space velocity of less than 3000h -1 The reaction conditions (2) show that the conversion of CO is about 70%. At present, the iron-based and Cu-Zn conversion catalysts commonly used in industry are difficult to meet the requirements of fuel cells on reactor miniaturization and high CO conversion rate. Therefore, it is highly desirable to develop a high efficiency water gas shift catalyst that can meet the requirement of high CO conversion rate under the high space velocity condition required by fuel cell systems.
Disclosure of Invention
The invention aims to provide an efficient low-temperature water-vapor conversion catalyst, which adopts Au as an active component and Ce-Zr composite metal oxide as a carrier, and has a simple preparation process. The catalyst has a space velocity of 100000h -1 Under the conditions, the conversion rate of CO is up to 90 percent and is far higher than that of a commercial water-gas shift catalyst.
Based on the purpose, the invention adopts the technical scheme that:
a catalyst for low-temp water-gas shift reaction is composed of active component and oxide carrier. The catalyst is characterized in that the active component of the catalyst is one or more than two of compounds containing Au, Pt, Pd, Rh or Ru elements, and the oxide carrier is Ce-Zr metal composite oxide.
The catalyst is characterized in that the content of active components is as follows: 0.5-2 wt%, and the molar ratio of Ce to Zr is: 0.2 to 5.
A preparation method of a catalyst for low-temperature water-vapor shift reaction comprises the following steps:
(1) mixing n-butanol, nitric acid and a surfactant, and stirring to form a clear solution;
(2) adding a cerium source and a zirconium source into the solution obtained in the step (1), and continuously stirring for 2-24 hours to obtain sol;
(3) aging the sol obtained in the step (2) at 140 ℃ for 5-24 hours;
(4) roasting the solid substance obtained in the step (3) to obtain a carrier;
(5) mixing the carrier obtained in the step (4) with a chloroauric acid solution, and adding urea;
(6) violently stirring the mixed system in the step (5) for 5-12 hours at the temperature of 80-100 ℃;
(7) and (4) filtering out the solid of the mixed system in the step (6), washing for 3-5 times, drying for 12-24 hours at the temperature of 60-100 ℃, and roasting to obtain the catalyst.
In the step (1), the mol ratio of the n-butyl alcohol, the nitric acid and the surfactant is 300-400:50-80: 1; the surfactant is one or two of P123 and F127; the concentration of the nitric acid in the step (1) is 68 percent; the molar ratio of the cerium source to the zirconium source in the step (2) is 0.2-5; the molar ratio of the total addition amount of the cerium source and the zirconium source to the surfactant in the step (1) is 10-40:1, the cerium source is cerium nitrate, the zirconium source is one or two of zirconium nitrate and n-butyl zirconium, the mass of the carrier and Au in the chloroauric acid in the step (5) is 100-200:1, and the molar ratio of Au to urea in the chloroauric acid is 1: 20-50.
The stirring time in the step (3) is 2-24 hours, preferably 12-24 hours; the aging time is 5 to 24 hours, preferably 12 to 24 hours. In the step (6), the stirring time is 5-12 hours, preferably 9-12 hours; in the step (7), the temperature rise rate during roasting is 1-2 ℃/min, the temperature is raised from room temperature to the roasting temperature, the roasting temperature is 400-600 ℃, and the roasting time is 4-6 hours.
The Ce-Zr composite oxide carrier is prepared by adopting a reverse microemulsion method, and Au is loaded on the carrier by a uniform coprecipitation method. The preparation process of the catalyst is simple. The prepared catalyst shows better reaction activity than the traditional iron-based and Cu-Zn catalysts when being applied to the water-vapor shift reaction.
Detailed Description
To further illustrate the present invention, the following examples are set forth without limiting the scope of the invention as defined by the various appended claims.
Example 1
a. 14g of n-butanol, 2g of concentrated nitric acid and 3g P123 were weighed into a beaker and stirred vigorously to form a clear solution.
b. Weighing 4.34g of cerium nitrate and 3.84g of n-butyl zirconium (cerium-zirconium molar ratio is 1:1) into the solution in the step a, and stirring vigorously for 24 hours.
c. And c, aging the sol obtained in the step b at 120 ℃ for 24 hours.
d. And (c) washing with absolute ethyl alcohol for 3-5 times, filtering out the solid obtained in the step (c), heating to 500 ℃ at the heating rate of 1 ℃/min, and roasting for 6 hours to obtain the CeZr composite oxide carrier.
e. Weighing the oxide carrier in the step d into 150ml of water, adding chloroauric acid (the loading amount of Au is 1 wt%) and 30 times (the molar ratio of Au to chloroauric acid) of urea, heating to 90 ℃, and vigorously stirring for 7 hours.
f. And e, filtering out the solid of the mixed system in the step e, washing the solid for 3-5 times by using deionized water, drying the solid for 24 hours at the temperature of 80 ℃, raising the temperature to 500 ℃ at the heating rate of 1 ℃/min, and roasting the solid for 4 hours to obtain the catalyst.
Example 2
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 2:1 in step b.
Example 3
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 3:1 in step b.
Example 4
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 4:1 in step b.
Example 5
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 5:1 in step b.
Example 6
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 1:2 in step b.
Example 7
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 1:3 in step b.
Example 8
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 1:4 in step b.
Example 9
An Au catalyst was obtained in the same manner as described in example 1, except that the cerium-zirconium molar ratio was changed to 1:5 in step b.
Example 10
An Au catalyst was prepared in the same manner as described in example 1, except that the supporting amount of Au in step e was changed to 0.5 wt%.
Example 11
An Au catalyst was prepared in the same manner as described in example 1, except that the supporting amount of Au in step e was changed to 1.5 wt%.
Example 12
Prepared in the same manner as described in example 1 except that the loading amount of Au was changed to 2 wt% in step e, to obtain an Au catalyst.
Example 13
Mixing Au/CeZrO x Tabletting and crushing the catalyst, screening out 20-40 meshes, diluting 200mg of catalyst particles with quartz sand with the same mesh number as 200mg, placing the catalyst particles in a fixed bed reactor with the diameter of 6mm, and keeping the gas hourly space velocity of 100000h under normal pressure -1 Firstly, the catalyst is heated to 200 ℃ under the hydrogen atmosphere and reduced in situ for 1 hour, then the temperature is reduced to room temperature, and mixed gas (the composition of the mixed gas is 13 percent of CO and 20 percent of H) is introduced 2 And 67% N 2 ) And water vapor, and heating to 250 ℃ for reaction. H 2 And O is CO 3.5. Detecting gas composition in gas components by on-line gas chromatography, and detecting gas composition by CO variationCalculation of the conversion of the reaction, Au/CeZrO x The CO conversion on the catalyst was 90%.
Comparative example 1
The same as example 6 except that the catalyst was changed to a commercial Fe-Cr catalyst, the reaction temperature was 350 ℃ to obtain a CO conversion of 32%.
Comparative example 2
The same as example 6 except that the catalyst was changed to a commercial Cu-Zn catalyst, the reaction temperature was 250 ℃ to obtain a CO conversion of 35%.
Example 14
Same as example 15 except that the catalyst was changed to Au/CeZrO x (Au loading 0.5 wt%) catalyst gave a CO conversion of 76%.
Example 15
Same as example 13, except that the catalyst was changed to Au/CeZrO x (Au loading 1.5 wt%) catalyst gave a CO conversion of 92%.
Example 16
Same as example 13, except that the catalyst was changed to Au/CeZrO x Catalyst (Au loading 2 wt%) gave a CO conversion of 97%.
Claims (4)
1. The application of the catalyst for low-temperature water-vapor shift reaction in the low-temperature water-vapor shift reaction is characterized in that the catalyst consists of an active component and an oxide carrier and is characterized in that:
placing in a fixed bed reactor of 6mm under normal pressure at a gas hourly space velocity of 100000h -1 Under the condition, the conversion rate of CO is up to 90%, the active component of the catalyst is a compound containing Au element, and the oxide carrier is Ce-Zr metal composite oxide; the method comprises the following steps:
(1) mixing n-butanol, nitric acid and a surfactant, and stirring to form a clear solution;
(2) adding a cerium source and a zirconium source into the solution obtained in the step (1), and continuously stirring for 2-24 hours to obtain sol;
(3) dissolving the sol obtained in the step (2) in 120 o C, stirring and aging;
(4) roasting the solid substance obtained in the step (3) to obtain a carrier;
(5) mixing the carrier obtained in the step (4) with a chloroauric acid solution, and adding urea;
(6) mixing the system in the step (5) to obtain a mixed system 90 o C, stirring vigorously for 5-12 hours;
(7) filtering out the solid of the mixed system in the step (6), washing for 3-5 times, and 80 o C, drying for 12-24 hours, and roasting to obtain a catalyst; the stirring time in the step (3) is 2-24 hours; the aging time is 5-24 hours, and the stirring time in the step (6) is 5-12 hours; the temperature rise rate during roasting in the step (7) is 1-2 o C/min, raising the temperature from room temperature to the roasting temperature, wherein the roasting temperature is 400-600 DEG C o And C, roasting for 4-6 hours.
2. Use of a catalyst according to claim 1, characterized in that the active components are present in the following amounts: 0.5-2 wt%, and the molar ratio of Ce to Zr is: 0.2 to 5.
3. Use according to claim 1, characterized in that: in the step (1), the mol ratio of the n-butanol to the nitric acid to the surfactant is 370:65: 1; the surfactant is one of P123 and F127; in the step (2), the molar ratio of the cerium source to the zirconium source is 0.2-5; the cerium source is cerium nitrate, and the zirconium source is one of zirconium nitrate and n-butyl alcohol zirconium.
4. Use according to claim 1, characterized in that: the stirring time in the step (3) is 12-24 hours; the aging time is 12-24 hours, and the stirring time in the step (6) is 9-12 hours.
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| CN112916031B (en) * | 2019-12-06 | 2021-12-28 | 中国科学院大连化学物理研究所 | Pt/alpha-MoC1-xMolybdenum net catalyst, preparation method and application thereof |
| CN111139108B (en) * | 2020-01-10 | 2021-09-21 | 湘潭大学 | Carbon monoxide steam conversion reaction method using Pt-based catalyst |
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Non-Patent Citations (3)
| Title |
|---|
| A Mesoporous Ce0.5Zr0.5O2 Solid Solution Catalyst for CO Hydrogenation to iso-C4 Hydrocarbons;Shaohui Ge等;《Catal Lett》;20080903;第126卷;第193-199页 * |
| Au/Ce1-xZrxO2 催化剂的制备、表征及其在CO 氧化和水煤气变换反应中的催化性能;廖卫平等;《催化学报》;20080229;第29卷(第2期);第134-140页 * |
| 廖卫平等.Au/Ce1-xZrxO2 催化剂的制备、表征及其在CO 氧化和水煤气变换反应中的催化性能.《催化学报》.2008,第29卷(第2期),第134-140页. * |
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