CN103599779B - A kind of CuO/ZrO 2water gas converting catalyst and preparation method thereof - Google Patents
A kind of CuO/ZrO 2water gas converting catalyst and preparation method thereof Download PDFInfo
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- CN103599779B CN103599779B CN201310561908.5A CN201310561908A CN103599779B CN 103599779 B CN103599779 B CN 103599779B CN 201310561908 A CN201310561908 A CN 201310561908A CN 103599779 B CN103599779 B CN 103599779B
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Abstract
The invention discloses a kind of CuO/ZrO
2water gas converting catalyst and preparation method thereof, belongs to Water gas shift/WGS technique and catalyst technical field.Mantoquita, zirconates and urea are first dissolved in the water formation mixed solution by the present invention, then carry out hydrothermal treatment consists to it, and hydrothermal product obtains CuO/ZrO through washing, dry, roasting
2water gas converting catalyst.Preparation method of the present invention is simple and easy to do, obtained CuO/ZrO
2water gas converting catalyst has the advantage of low, active high, the active wide temperature region of light-off temperature, selective height, Heat stability is good, is particularly useful for rich H-H reaction gas operating 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-ShiftReaction, CO+H
2o → CO+H
2) be extremely important course of reaction in chemical industry, be widely used in coal, oil and natural gas be raw material ammonia synthesizing industry and industries.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 industrial transformation catalyst generally used mainly contains Fe-Cr HTS high temperature conversion catalyst, the wide temperature sulfur-resistant transformation catalyst of copper zinc system's low temperature conversion catalyst and cobalt molybdenum system at present.But this three large series of transformations catalyst because its volume is large, meet air spontaneous combustion and the requirement of defect all cannot the meet vehicle-mounted PEMFC such as pretreatment operation process is loaded down with trivial details.Therefore, the efficient water gas converting catalyst of development of new, design improve the preparation method of catalyst become on-vehicle fuel technical development in the urgent need to.
Recent research shows the CuO/ZrO adopting multiple method to prepare
2catalyst all can show excellent water gas shift reaction catalytic performance.KoJ.B. (Catal.Lett.2005,105,157) are waited to first reported the CuO/ZrO adopting coprecipitation to prepare
2the application of catalyst in low-temperature water gas shift reaction, finds that this catalyst shows comparatively business CuO-ZnO-Al below 200 DEG C
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
2for the CuO/ZrO of carrier
2water gas converting catalyst, active testing result shows with Tetragonal ZrO
2for the catalyst activity of carrier is better.Ruan Chunxiao etc. (CN201010598698) find the highly active CuO/ZrO adopting deposition-precipitation method more obtained compared with coprecipitation
2water gas converting catalyst.But the equal Shortcomings part of above-mentioned preparation method: CuO/ZrO prepared by (1) precipitation method
2zrO is there is in catalyst
2to the embedding of active CuO particle, make part CuO not have catalytic action, in addition, this legal system obtains catalyst and very easily hard aggregation occurs in roasting process, causes growing up of particle size, thus is unfavorable for the generation of catalytic reaction.(2) infusion process obtains CuO/ZrO
2catalyst surface CuO particle often distributing inhomogeneity, high-temperature roasting easily causes the sintering of surface C uO particle to grow up, and is unfavorable for the carrying out of catalytic reaction equally.(3) deposition-precipitation method obtains CuO/ZrO
2although catalyst surface CuO particle distributes homogeneous, CuO and ZrO
2between interaction often more weak, be difficult in catalytic reaction process keep good thermal stability.In addition, this legal system Preparation Method process is loaded down with trivial details, needs first to obtain ZrO
2carrier carries out the load of CuO again, and preparation process exists the unfavorable factor such as secondary washing, after baking.Therefore, be necessary to develop simple and easy to do and more suitable method to 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, obtained CuO/ZrO
2water gas converting catalyst has the advantage of low, active high, the active wide temperature region of light-off temperature, selective height, 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 obtained mixed solution in deionized water;
(2) proceed in water heating kettle by the mixed solution of step (1), controlling hydrothermal temperature is 110 ~ 210 DEG C, and the hydro-thermal time is 3 ~ 24 hours; Gained hydrothermal product after washing imurity-removal ion in 120 DEG C of dryings 8 hours, then in 200 ~ 500 DEG C of roastings, 4 hours obtained CuO/ZrO
2water gas converting catalyst.
Soluble copper salt described in step (1) is the one in Schweinfurt green, copper nitrate, copper chloride.
Solubility zirconates described in step (1) is the one 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 (i.e. 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 conditions, by controlling hydrothermal temperature and hydro-thermal time, directly obtains CuO/ZrO
2complex oxide products, but not the Cu (OH) obtained by ordinary precipitation process
2with Zr (OH)
4hydroxide mixture, thus avoid the phenomenon that hard aggregation occurs catalyst in roasting process.Utilize harsh thermal and hydric environment, enhance CuO-ZrO
2between interaction, thus be conducive to CuO/ZrO
2the raising of catalyst heat endurance and water repelling property.Active testing result shows, adopt the catalyst that obtains of the inventive method just to show excellent catalytic performance at 200 DEG C, CO conversion ratio can reach 85%, 250 DEG C and 300 DEG C time CO conversion ratio up to 92% and 90%.
Remarkable advantage of the present invention is: obtained hydrothermal product is directly oxide form, and avoid under roasting condition, catalyst is changed into the phenomenon that hard aggregation occurs in the process of oxide by hydroxide.Utilize harsh thermal and hydric environment, enhance CuO-ZrO
2between interaction, and then improve 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 operating fuel cell environment that is particularly useful for Fu Qing, and the development for fuel cell technology brings 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.
Detailed description of the invention
Below by embodiment, the present invention is further described, but the present invention is not limited in these embodiments.
Embodiment 1
By 0.877gCuCl
22H
2o, 15.081gZrOCl
28H
2o and 3.120g urea is scattered in obtained mixed solution [i.e. n (Cu): n (Zr)=1:9, n (Cu+Zr): n (urea)=1:1] in 65mL deionized water.Above-mentioned mixed liquor being proceeded to volume is in the hydrothermal reaction kettle of 100mL, and controlling hydrothermal temperature is 210 DEG C, and the hydro-thermal time is 3 hours.Hydrothermal product after washing imurity-removal ion in 120 DEG C of dryings 8 hours, then in 500 DEG C of roastings, 4 hours obtained CuO/ZrO
2water gas converting catalyst.
Embodiment 2
By 3.769gCu (NO
3)
23H
2o, 11.730gZrOCl
28H
2o and 3.744g urea is scattered in obtained mixed solution [i.e. n (Cu): n (Zr)=3:7, n (Cu+Zr): n (urea)=1:1.5] in 65mL deionized water.Above-mentioned mixed liquor being proceeded to volume is in the hydrothermal reaction kettle of 100mL, and to control hydrothermal temperature be 180 DEG C, and the hydro-thermal time is 6 hours.Hydrothermal product after washing imurity-removal ion in 120 DEG C of dryings 8 hours, then in 400 DEG C of roastings, 4 hours obtained CuO/ZrO
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 Tetragonal and monoclinic phase two kinds of crystalline phases simultaneously.And do not find the diffraction maximum of crystalline phase CuO, illustrate that CuO is that high degree of dispersion state exists or mixed ZrO
2intracell, this may be the reason causing the present embodiment to have comparatively excellent Water gas shift/WGS catalytic activity.
Embodiment 3
By 5.191gCu (Ac)
22H
2o, 11.162gZr (NO
3)
45H
2o and 4.68g urea is scattered in obtained mixed solution [i.e. n (Cu): n (Zr)=5:5, n (Cu+Zr): n (urea)=1:2] in 65mL deionized water.Above-mentioned mixed liquor being proceeded to volume is in the hydrothermal reaction kettle of 100mL, and to control hydrothermal temperature be 150 DEG C, and the hydro-thermal time is 24 hours.Hydrothermal product after washing imurity-removal ion in 120 DEG C of dryings 8 hours, then in 300 DEG C of roastings, 4 hours obtained CuO/ZrO
2water gas converting catalyst.
Embodiment 4
By 11.307gCu (NO
3)
23H
2o, 1.390gZrO (NO
3)
22H
2o and 3.43g urea is scattered in obtained mixed solution [i.e. n (Cu): n (Zr)=9:1, n (Cu+Zr): n (urea)=1:1.1] in 65mL deionized water.Above-mentioned mixed liquor being proceeded to volume is in the hydrothermal reaction kettle of 100mL, and to control hydrothermal temperature be 110 DEG C, and the hydro-thermal time is 3 hours.Hydrothermal product after washing imurity-removal ion in 120 DEG C of dryings 8 hours, then in 200 DEG C of roastings, 4 hours obtained CuO/ZrO
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 DEG C; Air speed is 2000cm
3g
-1h
-1, steam-to-gas ratio is 1:1.Before activity rating, catalyst is first at H
2activate under atmosphere, activation temperature is 200 DEG C, and soak time is 0.5 hour.
Represent catalytic activity with CO conversion ratio, the Activity evaluation of embodiment is as table 1:
The Activity evaluation of table 1 embodiment
The foregoing is only preferred embodiment of the present invention, all equalizations done 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 obtained mixed solution in deionized water;
(2) proceed in water heating kettle by the mixed solution of step (1), controlling hydrothermal temperature is 110 ~ 210 DEG C, and the hydro-thermal time is 3 ~ 24 hours; Gained hydrothermal product after washing imurity-removal ion in 120 DEG C of dryings 8 hours, then in 200 ~ 500 DEG C of roastings, 4 hours obtained CuO/ZrO
2water gas converting catalyst.
2. CuO/ZrO according to claim 1
2the preparation method of water gas converting catalyst, is characterized in that: the soluble copper salt described in step (1) is the one 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 solubility zirconates described in step (1) is the one 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 summation of soluble copper salt and solubility zirconates and the mol ratio of urea are 1:1 ~ 1:2.
5. the CuO/ZrO that the method for claim 1 is obtained
2water gas converting catalyst.
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| CN107096532B (en) * | 2017-05-16 | 2019-12-10 | 嘉兴学院 | Au-ZrO 2 catalyst and application thereof |
| CN110387598B (en) * | 2018-04-17 | 2022-06-14 | 南通纺织丝绸产业技术研究院 | Antibacterial anti-ultraviolet multifunctional chemical fiber |
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Non-Patent Citations (4)
| Title |
|---|
| G. Avgouropoulos等.Infl * |
| uence of the preparation method on the performance of CuO-CeO2 catalysts for the selective oxidation of CO.《Applied Catalysis B: Environmental》.2004,第56卷 * |
| 低温水煤气变换催化剂CuO/ZrO2的制备、表征与性能;阮春晓等;《催化学报》;20121231;第33卷(第5期);第842-849页 * |
| 水热法制备球形二氧化锆粉体的研究;王晶等;《硅酸盐通报》;20130531;第32卷(第5期);第936-940页 * |
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