CN103599779A - CuO/ZrO2 water-gas shift catalyst and preparation method thereof - Google Patents
CuO/ZrO2 water-gas shift catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a CuO/ZrO2 water-gas shift catalyst and a preparation method thereof, belonging to the technical fields of water-gas shift processes and catalysts. The preparation method of the CuO/ZrO2 water-gas shift catalyst comprises the following steps: firstly, dissolving copper salt, zirconium salt and urea into water to form mixed liquor; then, carrying out hydro-thermal treatment onto the mixed liquor; and washing, drying and roasting hydro-thermal products to prepare the CuO/ZrO2 water-gas shift catalyst. The preparation method disclosed by the invention is simple, convenient and easy to implement, and the prepared CuO/ZrO2 water-gas shift catalyst has advantages of being low in activating temperature, high in activity, wide in active temperature zone, high in selectivity and good in thermal stability, and is especially suitable for a hydrogen-rich reaction gas operation environment.
Description
Technical field
The invention belongs to Water gas shift/WGS technique and catalyst technical field, be specifically related to a kind of CuO/ZrO
2water gas converting catalyst and preparation method thereof.
Background technology
Water gas shift reaction (Water-Gas-Shift Reaction, CO+H
2o → CO+H
2) be extremely important course of reaction in chemical industry, ammonia synthesizing industry and hydrogen manufacturing industry that to be widely used in take coal, oil and natural gas be raw material.In recent years, along with the development of vehicle-mounted Proton Exchange Membrane Fuel Cells (PEMFC) technology, water gas shift reaction causes extensive concern again as the important step in the online hydrogen generating system of PEMFC.The at present industrial transformation catalyst generally using mainly contains Fe-Cr HTS high temperature conversion catalyst, copper zinc is that low temperature conversion catalyst and cobalt molybdenum are wide temperature sulfur-resistant transformation catalyst.Yet this three large serial transformation catalyst because its volume is large, meet air spontaneous combustion and pretreatment operation process is loaded down with trivial details etc. that defect all cannot meet the requirement of vehicle-mounted PEMFC.Therefore, the preparation method of the efficient water gas converting catalyst of development of new, design improvement catalyst become on-vehicle fuel technical development in the urgent need to.
Recent research shows the CuO/ZrO that adopts several different methods to prepare
2catalyst all can show excellent water gas shift reaction catalytic performance.Ko J. B. etc. (Catal. Lett. 2005,105,157) have first reported the CuO/ZrO that adopts coprecipitation to prepare
2the application of catalyst in low temperature water gas transformationreation, finds to show compared with business CuO-ZnO-Al at this catalyst below 200 ℃
2o
3the catalytic activity that catalyst is more excellent.Aguila etc. (Catal. Commun. 2008,9,2550) adopt infusion process to prepare with monoclinic phase ZrO
2with Tetragonal ZrO
2cuO/ZrO for carrier
2water gas converting catalyst, active testing result shows with Tetragonal ZrO
2for the catalyst activity of carrier better.Ruan Chunxiao etc. (CN 201010598698) find the highly active CuO/ZrO that adopts deposition-precipitation method more easily to make compared with coprecipitation
2water gas converting catalyst.But the equal Shortcomings part of above-mentioned preparation method: CuO/ZrO prepared by (1) precipitation method
2in catalyst, exist ZrO
2embedding to active CuO particle, makes part CuO not have catalytic action, and in addition, this legal system obtains catalyst hard aggregation very easily occurs in roasting process, causes growing up of particle size, thereby is unfavorable for the generation of catalytic reaction.(2) infusion process makes CuO/ZrO
2catalyst surface CuO particle is distributing inhomogeneity often, and high-temperature roasting easily causes the sintering of surface C uO particle to grow up, and is unfavorable for equally the carrying out of catalytic reaction.(3) deposition-precipitation method makes CuO/ZrO
2although catalyst surface CuO particle distribution homogeneous, CuO and ZrO
2between interaction often a little less than, in catalytic reaction process, be difficult to keep good thermal stability.In addition, this legal system Preparation Method process is loaded down with trivial details, need to first make ZrO
2carrier carries out the load of CuO again, and preparation process exists the unfavorable factors such as secondary washing, after baking.Therefore, be necessary to develop simple and easy to do and more suitable method and prepare CuO/ZrO
2water gas converting catalyst.
Summary of the invention
The object of the present invention is to provide a kind of CuO/ZrO
2water gas converting catalyst and preparation method thereof, preparation process is simple and easy to do, the CuO/ZrO making
2water gas converting catalyst has advantages of low, active high, the active wide temperature region of light-off temperature, selective high, Heat stability is good, is particularly useful for rich H-H reaction gas operating environment.
For achieving the above object, the present invention adopts following technical scheme:
A kind of CuO/ZrO
2the preparation method of water gas converting catalyst comprises the steps:
(1) soluble copper salt, solubility zirconates and urea are dissolved in and in deionized water, make mixed solution;
(2) mixed solution of step (1) is proceeded in water heating kettle, controlling hydrothermal temperature is 110～210 ℃, and the hydro-thermal time is 3～24 hours; Gained hydrothermal product after washing imurity-removal ion in 120 ℃ dry 8 hours, then within 4 hours, make CuO/ZrO in 200 ~ 500 ℃ of roastings
2water gas converting catalyst.
The described soluble copper salt of step (1) is a kind of in Schweinfurt green, copper nitrate, copper chloride.
The described solubility zirconates of step (1) is a kind of in zirconium nitrate, zirconyl nitrate, zirconium oxychloride.
In step (1), the mol ratio of soluble copper salt and solubility zirconates is 1:9～9:1; Soluble metallic salt (being mole summation of soluble copper salt and solubility zirconates) is 1:1～1:2 with the mol ratio of urea.
The present invention makes soluble copper salt, solubility zirconates and urea react under hydrothermal condition, by controlling hydrothermal temperature and hydro-thermal time, directly obtains CuO/ZrO
2composite oxides product, but not the prepared Cu of the common precipitation method (OH)
2with Zr (OH)
4hydroxide mixture, thereby avoided catalyst that the phenomenon of hard aggregation occurs in roasting process.Utilize harsh thermal and hydric environment, strengthened CuO-ZrO
2between interaction, thereby be conducive to CuO/ZrO
2the raising of catalyst heat endurance and water repelling property.Active testing result shows, the catalyst that adopts the inventive method to make just shows excellent catalytic performance at 200 ℃, and when CO conversion ratio can reach 85%, 250 ℃ and 300 ℃, CO conversion ratio is up to 92% and 90%.
Remarkable advantage of the present invention is: prepared hydrothermal product is directly oxide form, has avoided under roasting condition, and the phenomenon of hard aggregation occurs in the process that catalyst changes oxide into by hydroxide.Utilize harsh thermal and hydric environment, strengthened CuO-ZrO
2between interaction, and then improved CuO/ZrO
2the heat endurance of catalyst and water repelling property.Prepared CuO/ZrO
2catalyst light-off temperature is low, low temperature active is high, active wide temperature region, thermally-stabilised good, the fuel battery operation environment that is particularly useful for Fu Qing, for the development of fuel cell technology has brought new hope.The preparation method of this catalyst is simple and easy to do, has wide prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is CuO/ZrO in embodiment 2
2the X-ray diffractogram of water gas converting catalyst.
The specific embodiment
Below by embodiment, the present invention is further described, but the present invention is not limited in these embodiment.
Embodiment 1
By 0.877g CuCl
22H
2o, 15.081g ZrOCl
28H
2o and 3.120g urea are scattered in and in 65mL deionized water, make mixed solution [being n (Cu): n (Zr)=1:9, n (Cu+Zr): n (urea)=1:1].Above-mentioned mixed liquor is proceeded in the hydrothermal reaction kettle that volume is 100mL, and controlling hydrothermal temperature is 210 ℃, and the hydro-thermal time is 3 hours.Hydrothermal product after washing imurity-removal ion in 120 ℃ dry 8 hours, then within 4 hours, make CuO/ZrO in 500 ℃ of roastings
2water gas converting catalyst.
Embodiment 2
By 3.769g Cu (NO
3)
23H
2o, 11.730g ZrOCl
28H
2o and 3.744g urea are scattered in and in 65mL deionized water, make mixed solution [being n (Cu): n (Zr)=3:7, n (Cu+Zr): n (urea)=1:1.5].Above-mentioned mixed liquor is proceeded in the hydrothermal reaction kettle that volume is 100mL, and to control hydrothermal temperature be 180 ℃, the hydro-thermal time is 6 hours.Hydrothermal product after washing imurity-removal ion in 120 ℃ dry 8 hours, then within 4 hours, make CuO/ZrO in 400 ℃ of roastings
2water gas converting catalyst.Fig. 1 is CuO/ZrO in embodiment 2
2the X-ray diffractogram of water gas converting catalyst.As shown in Figure 1, CuO/ZrO in embodiment 2
2zrO in water gas converting catalyst
2there are two kinds of crystalline phases of Tetragonal and monoclinic phase simultaneously.And do not find the diffraction maximum of crystalline phase CuO, illustrate that CuO is high degree of dispersion state and has or mixed ZrO
2intracell, this may be to cause the present embodiment to have the reason of comparatively excellent Water gas shift/WGS catalytic activity.
Embodiment 3
By 5.191g Cu (Ac)
22H
2o, 11.162g Zr (NO
3)
45H
2o and 4.68g urea are scattered in and in 65mL deionized water, make mixed solution [being n (Cu): n (Zr)=5:5, n (Cu+Zr): n (urea)=1:2].Above-mentioned mixed liquor is proceeded in the hydrothermal reaction kettle that volume is 100mL, and to control hydrothermal temperature be 150 ℃, the hydro-thermal time is 24 hours.Hydrothermal product after washing imurity-removal ion in 120 ℃ dry 8 hours, then within 4 hours, make CuO/ZrO in 300 ℃ of roastings
2water gas converting catalyst.
Embodiment 4
By 11.307g Cu (NO
3)
23H
2o, 1.390g ZrO (NO
3)
22H
2o and 3.43g urea are scattered in and in 65mL deionized water, make mixed solution [being n (Cu): n (Zr)=9:1, n (Cu+Zr): n (urea)=1:1.1].Above-mentioned mixed liquor is proceeded in the hydrothermal reaction kettle that volume is 100mL, and to control hydrothermal temperature be 110 ℃, the hydro-thermal time is 3 hours.Hydrothermal product after washing imurity-removal ion in 120 ℃ dry 8 hours, then within 4 hours, make CuO/ZrO in 200 ℃ of roastings
2water gas converting catalyst.
Activity rating
The activity rating of catalyst carries out on atmospheric fixed bed reactor, appreciation condition: unstripped gas is simulation methane reforming gas, and its volumn concentration consists of 15% CO, 55% H
2, 7% CO
2, 23% N
2; Catalyst amount is 0.5g; Active testing warm area is 200～300 ℃; Air speed is 2000cm
3g
-1h
-1, steam-to-gas ratio is 1:1.Before activity rating, catalyst is first at H
2under atmosphere, activate, activation temperature is 200 ℃, and soak time is 0.5 hour.
With CO conversion ratio, represent catalytic activity, the activity rating result of embodiment is as table 1:
The activity rating result of table 1 embodiment
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. a CuO/ZrO
2the preparation method of water gas converting catalyst, is characterized in that: comprise the steps:
(1) soluble copper salt, solubility zirconates and urea are dissolved in and in deionized water, make mixed solution;
(2) mixed solution of step (1) is proceeded in water heating kettle, controlling hydrothermal temperature is 110～210 ℃, and the hydro-thermal time is 3～24 hours; Gained hydrothermal product after washing imurity-removal ion in 120 ℃ dry 8 hours, then within 4 hours, make CuO/ZrO in 200 ~ 500 ℃ of roastings
2water gas converting catalyst.
2. CuO/ZrO according to claim 1
2the preparation method of water gas converting catalyst, is characterized in that: the described soluble copper salt of step (1) is a kind of in Schweinfurt green, copper nitrate, copper chloride.
3. CuO/ZrO according to claim 1
2the preparation method of water gas converting catalyst, is characterized in that: the described solubility zirconates of step (1) is a kind of in zirconium nitrate, zirconyl nitrate, zirconium oxychloride.
4. CuO/ZrO according to claim 1
2the preparation method of water gas converting catalyst, is characterized in that: in step (1), the mol ratio of soluble copper salt and solubility zirconates is 1:9～9:1; The mol ratio of soluble metallic salt and urea is 1:1～1:2.
5. the CuO/ZrO that the method for claim 1 makes
2water gas converting catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799261A (en) * | 2017-01-25 | 2017-06-06 | 闽江学院 | A kind of Al doping ZrO2It is situated between and sees crystal and its preparation method and application |
| CN107096532A (en) * | 2017-05-16 | 2017-08-29 | 嘉兴学院 | A kind of Au ZrO2Catalyst and its application |
| CN110387598A (en) * | 2018-04-17 | 2019-10-29 | 南通纺织丝绸产业技术研究院 | A kind of antibacterial ultraviolet-resistannanofiber multifunctional chemical fiber |
| CN113398937A (en) * | 2021-06-01 | 2021-09-17 | 厦门大学 | Preparation method and application of catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035116A1 (en) * | 2003-09-17 | 2005-04-21 | Engelhard Corporation | Operating conditions for copper-based water-gas shift catalysts |
-
2013
- 2013-11-13 CN CN201310561908.5A patent/CN103599779B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035116A1 (en) * | 2003-09-17 | 2005-04-21 | Engelhard Corporation | Operating conditions for copper-based water-gas shift catalysts |
Non-Patent Citations (3)
| Title |
|---|
| G. AVGOUROPOULOS等: "Influence of the preparation method on the performance of CuO-CeO2 catalysts for the selective oxidation of CO", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 王晶等: "水热法制备球形二氧化锆粉体的研究", 《硅酸盐通报》 * |
| 阮春晓等: "低温水煤气变换催化剂CuO/ZrO2的制备、表征与性能", 《催化学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799261A (en) * | 2017-01-25 | 2017-06-06 | 闽江学院 | A kind of Al doping ZrO2It is situated between and sees crystal and its preparation method and application |
| CN106799261B (en) * | 2017-01-25 | 2018-07-17 | 闽江学院 | A kind of Al doping ZrO2It is situated between and sees crystal and its preparation method and application |
| CN107096532A (en) * | 2017-05-16 | 2017-08-29 | 嘉兴学院 | A kind of Au ZrO2Catalyst and its application |
| CN107096532B (en) * | 2017-05-16 | 2019-12-10 | 嘉兴学院 | Au-ZrO 2 catalyst and application thereof |
| CN110387598A (en) * | 2018-04-17 | 2019-10-29 | 南通纺织丝绸产业技术研究院 | A kind of antibacterial ultraviolet-resistannanofiber multifunctional chemical fiber |
| CN113398937A (en) * | 2021-06-01 | 2021-09-17 | 厦门大学 | Preparation method and application of catalyst |
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