CN111215065A - Water-gas shift catalyst, preparation and application thereof - Google Patents
Water-gas shift catalyst, preparation and application thereof Download PDFInfo
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- CN111215065A CN111215065A CN201811421723.3A CN201811421723A CN111215065A CN 111215065 A CN111215065 A CN 111215065A CN 201811421723 A CN201811421723 A CN 201811421723A CN 111215065 A CN111215065 A CN 111215065A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a water-gas shift catalyst and a novel preparation method thereof. The catalyst comprises noble metal/CeO2Aluminum oxide, noble metal loading 0.1-1 wt% of the total weight, CeO2The mass ratio of the aluminum oxide to the aluminum oxide is 1: 9-3: 7, and the aluminum oxide is amorphous alumina. The preparation method comprises the steps of firstly synthesizing aluminum oxide by adopting a sol-gel evaporation self-assembly method, then depositing a cerium precursor on the aluminum oxide by adopting a rotary evaporation method, and roasting to obtain CeO2A carrier of aluminum oxide, and finally loading noble metal on CeO by adopting an impregnation method2On an aluminum oxide support. The catalyst is applied to water vapor shift reaction, shows catalytic activity superior to that of the traditional CuZn catalyst under the condition of high space velocity, and has good stability.
Description
Technical Field
The present invention relates to a water-gas shift catalyst and its preparation method. In particular, the invention relates to a composition of noble metal/CeO2Use of aluminum oxide for fuel cellCatalyst for water-gas shift reaction in hydrogen production process. The catalyst shows better catalytic activity than commercial catalysts under high space velocity conditions and has good stability.
Background
Hydrogen source technology has become one of the technological bottlenecks that limit large-scale commercial use of fuel cell vehicles. The hydrogen can be obtained by hydrogen production by fossil fuel, hydrogen extracted from chemical byproducts, hydrogen production by biological methanol and methane, hydrogen production by natural energy such as solar energy and wind energy, and the like. However, it is difficult to liquefy hydrogen because of its low melting point. In addition, liquid hydrogen can react with a metal container to generate hydride, so that the purity of the hydrogen is reduced, and higher potential safety hazard exists. Therefore, the storage and transport of hydrogen gas restricts the supply of hydrogen source to the fuel cell. The hydrogen can also be prepared from hydrocarbons such as gasoline and diesel oil, natural gas, methanol and the like through reforming reaction on site. The hydrogen production mode has the advantages of high energy density, high energy conversion rate and the like. In addition, the liquid fuel is convenient to store and transport, and has advantages in terms of economy, safety, and the like, compared with hydrogen gas. At present, the on-site hydrogen production technology of fuel cells is actively developed at home and abroad. A large amount of CO is inevitably generated in the process of reforming hydrocarbon fuel to produce hydrogen. CO can cause irreversible poisoning of the platinum electrode in the fuel cell and its concentration must be reduced below acceptable limits before it can enter the cell system. In addition, CO can be converted into hydrogen through a water-vapor shift reaction, and the energy utilization efficiency is further improved.
The hydrogen production system in the fuel cell is a miniaturized and unstable process, so that the process requires that the catalyst has high activity and stability, and can adapt to temperature and atmosphere changes brought by different working conditions such as high airspeed, multiple starting and stopping and the like. The traditional water vapor shift catalyst is CuZn series low-temperature shift catalyst (the use temperature is 180-450 ℃) and FeCr series high-temperature shift catalyst (the use temperature is 350-450 ℃), and is mainly used for the space velocity of 2000-3000 h--1And stable operation conditions in industrial process. The two catalysts are required to be subjected to strict and complicated pre-reduction treatment before use, and the reduced catalysts are easy to generate nature when meeting air, so that active components are sintered and catalyzeThe agent is deactivated. Therefore, the low-temperature shift catalyst and the high-temperature shift catalyst which are used in industry are difficult to be applied to a hydrogen production system of a fuel cell with high space velocity and unsteady state. Therefore, the development of a high-activity and high-stability water-vapor shift catalyst is one of the keys in the field hydrogen production process of the fuel cell. The supported noble metal catalysts such as platinum and gold have stronger CO activation capability and become the key point of the development and research of the water-gas shift catalyst (D.Miao, et al., ACS Catal.2016,6,775; S.Yao, et al., Science 2017,357,389; X.Sun, et al., AIChEJ.2017,63,4022).
Disclosure of Invention
The invention aims to provide a catalyst for steam shift reaction in a hydrogen production system of a fuel cell, which shows excellent CO shift activity and stability under the working conditions of high airspeed and multiple starting and stopping.
Based on the purpose, the invention adopts the technical scheme that:
a catalyst for the water-gas shift reaction in preparing hydrogen source of fuel cell is composed of noble metal/CeO2Aluminum oxide, wherein the aluminum oxide is amorphous alumina; the noble metal is platinum, palladium, gold or/and rhodium.
The loading amount of the noble metal active component is 0.1-1 wt% of the total weight; CeO (CeO)2The mass ratio of the aluminum oxide to the aluminum oxide is 1:9 to 3: 7.
A method for preparing a catalyst for a water-gas shift reaction, comprising:
(1) preparing an aluminum source, a surfactant and acid into an ethanol solution;
(2) stirring the ethanol solution in the step (1) for 4-12 hours at room temperature;
(3) evaporating the ethanol solvent from the solution obtained in the step (2), and then aging for 36-72 hours;
(4) roasting the solid substance obtained in the step (3) to obtain aluminum oxide;
(5) dissolving cerium nitrate in ethanol to prepare an ethanol solution;
(6) mixing the ethanol solution obtained in the step (5) with the aluminum oxide obtained in the step (4), and rotationally evaporating ethanol at 40-60 ℃;
(7) taking out the solid in the step (6)Roasting the substance to obtain CeO2Aluminum oxide;
(8) the noble metal component is loaded on CeO by an impregnation method2Drying and roasting on aluminum oxide to obtain noble metal/CeO2An aluminum oxide catalyst.
In the step (1), the aluminum source is one of aluminum isopropoxide, aluminum sec-butoxide, aluminum nitrate and aluminum chloride; the surfactant is one of P123 and F127; the acid was 68 wt% nitric acid. In the step (8), the precursor of the noble metal active component is one or a mixture of more of tetraammineplatinum chloride, tetraammineplatinum nitrate, chloroplatinic acid, hydroxyammineplatinum, tetraamminepalladium chloride, tetraamminepalladium nitrate, palladium chloride, palladium nitrate, chloroauric acid and rhodium chloride.
The stirring time in the step (2) is 4-12 hours, preferably 6-8 hours; in the step (3), the evaporation and aging temperature of the ethanol is 50-80 ℃, preferably 60 ℃, and the aging time is 36-72 hours, preferably 48 hours.
The temperature rise rate in the roasting in the step (4) and the step (7) is 0.5-2 ℃/min, the temperature is raised from room temperature to the roasting temperature, the roasting temperature is 400-600 ℃, and the roasting time is 4-8 hours; in the step (8), the drying temperature is 80-120 ℃, the drying time is 12-24 hours, the roasting temperature is 200-500 ℃, and the roasting time is 6-12 hours.
The noble metal/CeO prepared by the invention2The noble metal is loaded on the composite carrier in an atomic dispersion scale, the utilization rate of the active component of the noble metal is close to 100%, and the catalyst shows more excellent water vapor shift reaction activity and stability compared with an industrial catalyst under the conditions of high space velocity and unsteady state.
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. Weighing 2.0g P123 and dissolving in 20ml absolute ethyl alcohol, dripping 3.2ml concentrated nitric acid, adding 4.08g aluminium isopropoxide under vigorous stirring until complete dissolution.
b. The ethanol solution in step a was stirred at room temperature for 6 hours.
c. And c, placing the ethanol solution obtained in the step b in an oven at 60 ℃, evaporating the dry ethanol solvent, and continuing aging for 48 hours.
d. And c, heating the solid obtained in the step c to 400 ℃ at the heating rate of 1 ℃/min, and roasting for 4 hours to obtain the aluminum oxide.
e. 0.50g of cerium nitrate was weighed out and dissolved in 30ml of absolute ethanol, and 0.8g of the aluminum oxide prepared in step d was added.
f.rotary evaporation of ethanol from the mixed system of step e at 50 ℃.
g. The solid obtained in step f was dried in an oven at 60 ℃ for 12 hours.
h. G, heating the solid obtained in the step g to 450 ℃ at the heating rate of 1 ℃/min, and roasting for 4 hours to obtain CeO2Aluminum oxide.
i. Weighing 8.6mg of tetrammineplatinum chloride, dissolving in 0.5ml of ultrapure water, and adding 1g of CeO obtained in the step h2Aluminum oxide, stirring uniformly and standing for 24 hours.
j. And (3) drying the solid obtained in the step i in an oven at 100 ℃ for 12 hours.
k. Heating the solid obtained in the step j to 350 ℃ at the heating rate of 1 ℃/min, and roasting for 8 hours to obtain Pt/CeO2Aluminum oxide (Pt loading 0.5 wt%).
Example 2
Pt/CeO was obtained in the same manner as described in example 1, except that the amount of tetraamineplatinum chloride used was changed to 1.7mg in step i2Aluminum oxide (Pt loading 0.1 wt%).
Example 3
Pt/CeO was obtained in the same manner as described in example 1, except that the amount of tetraamineplatinum chloride used was changed to 17.2mg in step i2Aluminum oxide (Pt loading 1 wt%).
Example 4
Prepared in the same manner as described in example 1 except that 8.6mg of tetraammineplatinum chloride was changed to 10.5mg of chloroauric acid in step i to give Au/CeO2Aluminum oxide (Au loading 0.5 wt%).
Example 5
Prepared in the same manner as described in example 1 except that 8.6mg of tetraammineplatinum chloride was changed to 11.5mg of tetraamminepalladium chloride in step i to obtain Pd/CeO2Aluminum oxide (Pd loading 0.5 wt%).
Example 6
Rh/CeO obtained in the same manner as described in example 1, except that in step i, 8.6mg of tetraammineplatinum chloride was changed to 10.2mg of rhodium chloride2Aluminum oxide (Rh loading 0.5 wt%).
Example 7
Mixing the above Pt/CeO2Tabletting and crushing the catalyst/aluminum oxide (Pt loading 0.5 wt%) and screening to obtain 40-60 meshes, placing 100mg of catalyst particles in a fixed bed reactor with the thickness of 6mm, and keeping the gas hourly space velocity at 30000h under normal pressure-1The catalyst is first mixed with the gas mixture (the volume composition of the gas mixture is 15% H)2And 85% N2) Heating to 350 ℃ in the atmosphere, reducing for 1 hour, and then switching to raw material gas (the volume of the raw material gas is 11% CO and 10.5% CO)2、23％H2And 55.5% N2) Introducing water vapor, and heating to 350 ℃ for reaction. Molar ratio, H2And O is CO 3.5. The gas composition in the gas component is detected by on-line gas chromatography, and the conversion rate of the reaction, Pt/CeO, is calculated by the variation of CO2CO conversion on alumina oxide (Pt loading 0.5 wt%) catalyst was 96%.
Comparative example 1
The same as example 7 except that the catalyst was changed to a commercial high temperature Fe-Cr catalyst, the conversion of CO was 34%.
Comparative example 2
The same as example 7 except that the catalyst was changed to a commercial low temperature CuZn catalyst, the CO conversion was 78%.
Example 8
The same procedure as in example 7, except that the reaction temperature was changed to 325 ℃ gave a CO conversion of 90%.
Example 9
The same procedure as in example 7, except that the reaction temperature was changed to 375 ℃ gave a CO conversion of 92%.
Example 10
Same as example 7, except that the catalyst was changed to the Pt/CeO catalyst2Aluminum oxide (Pt loading 0.1 wt%) gave a CO conversion of 82%.
Example 11
Same as example 7, except that the catalyst was changed to the Pt/CeO catalyst2Aluminum oxide (Pt loading 1 wt%) gave a CO conversion of 98%.
Example 12
Same as example 7, except that the catalyst was changed to Au/CeO2The reaction temperature was changed to 250 ℃ to obtain a CO conversion of 90% based on the weight of Au supported on 0.5% by weight.
Example 13
Same as example 7, except that the catalyst was changed to Pd/CeO2Aluminum oxide (Pd loading 0.5 wt%) gave a CO conversion of 86%.
Example 14
Same as example 7, except that the catalyst was changed to Rh/CeO2Aluminum oxide (Rh loading 0.5 wt%) gave a CO conversion of 81%.
Example 15
After the reaction time was 2 hours as in example 7, the reaction was stopped, cooled to room temperature, and the feed gas and steam were cut off; then the temperature is raised to 350 ℃ for reaction. The above operations were repeated 5 times, and the conversion rates of CO were 96%, 95%, 96%, and 94%, respectively.
Example 16
In the same manner as in example 7, the reaction was continued for 100 hours, and the conversion of CO was about 96% by sampling and analyzing.
Claims (8)
1. A catalyst for water-gas shift reaction in the preparation process of a hydrogen source of a fuel cell is characterized in that: consists of noble metal/CeO2Aluminum oxide, wherein the aluminum oxide is amorphous alumina; the noble metal is one or more than two of platinum, palladium, gold and/or rhodium.
2. The catalyst according to claim 1, which isIs characterized in that: the loading amount of the noble metal active component is 0.1-1 wt% of the total weight of the catalyst; CeO (CeO)2The mass ratio of the aluminum oxide to the aluminum oxide is 1:9 to 3: 7.
3. A method for preparing the catalyst for water-gas shift reaction according to claim 1 or 2, wherein: the method comprises the following steps:
(1) preparing an aluminum source, a surfactant and acid into an ethanol solution;
(2) stirring the ethanol solution in the step (1) for 4-12 hours at room temperature;
(3) evaporating the ethanol solvent from the solution obtained in the step (2), and then aging for 36-72 hours;
(4) roasting the solid substance obtained in the step (3) to obtain aluminum oxide;
(5) dissolving cerium nitrate in ethanol to prepare an ethanol solution;
(6) mixing the ethanol solution obtained in the step (5) with the aluminum oxide obtained in the step (4), and rotationally evaporating ethanol at 40-60 ℃;
(7) roasting the solid substance obtained in the step (6) to obtain CeO2Aluminum oxide;
(8) the noble metal component is loaded on CeO by an impregnation method2Drying and roasting on aluminum oxide to obtain noble metal/CeO2An aluminum oxide catalyst.
4. The method of claim 3, wherein: in the step (1), the aluminum source is one or more than two of aluminum isopropoxide, aluminum sec-butoxide, aluminum nitrate and aluminum chloride; the surfactant is one or two of P123 and F127; the acid is 65-68 wt% of nitric acid; in the step (8), the precursor of the noble metal active component is one or a mixture of more of tetraammineplatinum chloride, tetraammineplatinum nitrate, chloroplatinic acid, hydroxyammineplatinum, tetraamminepalladium chloride, tetraamminepalladium nitrate, palladium chloride, palladium nitrate, chloroauric acid and rhodium chloride.
5. The production method as claimed in claim 3 or 4, wherein: in the step (1), the mass ratio of the aluminum source to the surfactant to the acid is 2-2.5: 1: 1.5-16.
6. The method of claim 3, wherein: the stirring time in the step (2) is 4-12 hours, preferably 6-8 hours; in the step (3), the evaporation and aging temperature of the ethanol is 50-80 ℃, preferably 60 ℃, and the aging time is 36-72 hours, preferably 48 hours.
7. The method of claim 3, wherein: the temperature rise rate in the roasting in the step (4) and the step (7) is 0.5-2 ℃/min, the temperature is raised from room temperature to the roasting temperature, the roasting temperature is 400-600 ℃, and the roasting time is 4-8 hours; in the step (8), the drying temperature is 80-120 ℃, the drying time is 12-24 hours, the roasting temperature is 200-500 ℃, and the roasting time is 6-12 hours.
8. A precious metal/CeO according to claim 1 or 22Aluminum oxide or noble metal/CeO prepared by the preparation method of any one of claims 3 to 62Use of aluminum oxide as a catalyst for the water-gas shift reaction.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654319A (en) * | 1983-01-26 | 1987-03-31 | W. R. Grace & Co. | Doubly promoted platinum group metal catalysts for emission control and method for making the catalysts |
| US4708946A (en) * | 1985-05-23 | 1987-11-24 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Catalyst for purifying exhaust gas |
| JP2003275588A (en) * | 2002-03-20 | 2003-09-30 | Toyota Central Res & Dev Lab Inc | Co shift reaction catalyst |
| CN102039126A (en) * | 2009-10-21 | 2011-05-04 | 中国科学院大连化学物理研究所 | Platinum-based sulfur-tolerant catalyst for water-gas shift for carbon monoxide |
-
2018
- 2018-11-26 CN CN201811421723.3A patent/CN111215065B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654319A (en) * | 1983-01-26 | 1987-03-31 | W. R. Grace & Co. | Doubly promoted platinum group metal catalysts for emission control and method for making the catalysts |
| US4708946A (en) * | 1985-05-23 | 1987-11-24 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Catalyst for purifying exhaust gas |
| JP2003275588A (en) * | 2002-03-20 | 2003-09-30 | Toyota Central Res & Dev Lab Inc | Co shift reaction catalyst |
| CN102039126A (en) * | 2009-10-21 | 2011-05-04 | 中国科学院大连化学物理研究所 | Platinum-based sulfur-tolerant catalyst for water-gas shift for carbon monoxide |
Non-Patent Citations (1)
| Title |
|---|
| 刘欢: "Pt/CeO2-Al2O3催化剂的制备及其加氢脱氧性能的研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
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