CN103785344A - Preparation method and application of double-functional composite Co modified particle - Google Patents
Preparation method and application of double-functional composite Co modified particle Download PDFInfo
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- CN103785344A CN103785344A CN201410015934.2A CN201410015934A CN103785344A CN 103785344 A CN103785344 A CN 103785344A CN 201410015934 A CN201410015934 A CN 201410015934A CN 103785344 A CN103785344 A CN 103785344A
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Abstract
The invention discloses a preparation method and an application of a double-functional composite Co modified particle, belonging to the technical field of energy. A calcium-based carrier is added with two non-noble metals Co and Ni, and ions including Ca<2+> and the like are complexed by utilizing a sol-gel method, so that the adsorption efficiency and the catalytic efficiency are remarkably improved. The preparation method and the application disclosed by the invention can be applied to ethanol adsorption reinforced vapor reformation hydrogen production reaction or applied to glycerinum and acetic acid adsorption reinforced vapor reformation hydrogen production reaction and the like.
Description
Technical field
The present invention relates to a kind of preparation method and application of Composite Double functional particulate of Co modification, belong to energy technology field, can act on biomass derivatives absorption enhanced reformation hydrogen production, there is the function of catalysis and absorption, thereby significantly improve the concentration that generates hydrogen.
Background technology
Hydrogen fuel cell due to pollution-free, calorific value is high, utilize the advantage of the uniqueness such as various informative to be subject to paying close attention to of people.For on-board hydrogen fuel cell, owing to being subject to the restriction of hydrogen storage system, application on a large scale not yet.For this problem, researcher has proposed to use liquid fuel to be directly restructured as the solution of on-vehicle fuel hydrogen supply.That the biomass derivatives such as ethanol, glycerine and acetic acid have is renewable, the feature of high specific energy and low carbon chain, is applicable to the fuel as fuel-cell vehicle.
Biomass derivatives comprises ethanol, acetic acid, glycerine etc., according to chemical reaction equilibrium shifting principle, if can be by the CO producing in reaction
2real-time absorption is removed, and the thermodynamic limitation of traditional steam reforming reaction is broken, and reforming reaction and water-gas shift will be to being conducive to H
2the direction producing moves, and has promoted reforming reaction, has improved the utilization rate of raw material, has increased output and the purity of hydrogen.
In biomass derivatives steam reforming reaction, main catalyst comprises noble metal catalyst, non-precious metal catalyst and oxide catalyst.The catalyst that experiment showed, carried noble metal has better catalytic effect, but because its preparation cost is higher, can not be used widely.
Chinese patent (CN101444737) discloses a kind of hydrogen production by ethanol steam reforming nickel-base catalyst and preparation method thereof, this catalyst formation comprises: take nanoporous silica aeroge as catalyst carrier, take metal simple-substance nickel nano wire as active component, with MgO or CaO or ZrO
2or TiO
2or CeO
2nano particle or the composite nanoparticle between them are auxiliary agent.Experiment showed, that this catalyst can play catalytic action to hydrogen production by ethanol steam reforming reaction, but hydrogen yield is in 30% left and right, and making step is comparatively complicated.
Therefore, there is the preparation of the difunctional particle that is applied to biomass derivatives absorption enhanced reformation hydrogen production of higher hydrogen gas productive rate, there is higher practical value.
Summary of the invention
The invention reside in preparation method and application that a kind of Composite Double of Co modification functional particulate is provided.
Realizing technical scheme of the present invention is:
A kind of Composite Double functional particulate of Co modification, described particle is prepared by following methods: calcium acetate, cabaltous nitrate hexahydrate, nickel nitrate and citric acid are mixed, adding water to stir dissolves it completely, solution is constantly stirred at a certain temperature and is dried, then after calcining the broken Composite Double functional particulate that obtains Co modification.
Wherein, the mol ratio of calcium acetate and citric acid is 0.5 ~ 3:1.Appropriate citric acid contributes to Ca
2+isoionic complexing, and in calcination process, promote the formation in the trickle duct of granule interior, be conducive to improve the carbon dioxide adsorption of CaO.
Described calcium acetate, cabaltous nitrate hexahydrate, nickel nitrate and lemon aqueous acid, baking temperature is between 80 ~ 120 ℃, and constantly stirring in dry process, makes each species distribution even.
The solid matter obtaining through super-dry is calcined 2 ~ 5h between 700 ~ 1100 ℃, calcium acetate becomes CaO, and cobalt nitrate becomes CoO, and nickel nitrate becomes NiO, in the Composite Double functional particulate of prepared Co modification, the quality of Ni accounts for 10% ~ 20% of CaO quality, and the quality of Co accounts for 1% ~ 10% of CaO quality.
Described calcined product, through Mechanical Crushing, through 24 ~ 50 eye mesh screen screenings, obtains required difunctional particle.
The Composite Double functional particulate of above-mentioned Co modification can be applied to the reaction of absorption enhanced biomass derivatives vapor reforming hydrogen production, and wherein, steam/hydrocarbons ratio is 1.5 ~ 5:1, and ethanol air speed is 11 ~ 55h
-1, reaction pressure is 0.1 ~ 0.3MPa, and prereduction temperature is 600 ~ 800 ℃, and reaction temperature is 500 ~ 600 ℃, and regeneration temperature is 700 ~ 900 ℃.Record through experiment, steam/hydrocarbons ratio is 3:1, and ethanol air speed is 20h
-1, reaction pressure is 0.1MPa, and prereduction temperature is 700 ℃, and reaction temperature is that under the condition of 600 ℃, the hydrogen yield of ethanol can reach 40%, and the hydrogen yield of glycerine can reach 38%, and the hydrogen yield of acetic acid can reach 35%.
Compared with prior art, its remarkable advantage is in the present invention: the circulation absorption capacity of the Composite Double functional particulate of the Co modification that (1) prepares the present invention, apparently higher than the difunctional particle of unmodified calcium base, has larger adsorption capacity.(2) the present invention is applied to absorption enhanced ethanol steam reforming to react the hydrogen relative amount obtaining higher.(3) the present invention's adsorption time longer than having with the unmodified difunctional Particle Phase of routine.(4) manufacture craft of the present invention is simple, not high to equipment requirement, can be used for large-scale production.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is that the Composite Double functional particulate of Co modification reacts each production concentration for ethanol steam reforming.
Fig. 2 is that the Composite Double functional particulate of Co modification is for the each production concentration of glycerol liquor steam reforming reaction.
Fig. 3 is that the Composite Double functional particulate of Co modification is for the each production concentration of acetic acid steam reforming reaction.
The specific embodiment
Further illustrate the present invention below in conjunction with the drawings and specific embodiments.
The application of the Composite Double functional particulate of Co modification
Embodiment 1:
Take 9.42g calcium acetate, 1.83g cabaltous nitrate hexahydrate, 0.45g nickel nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 100 ℃, then fragmentation obtains the Composite Double functional particulate of 24 ~ 50 object Co modifications after 900 ℃ of calcining 3h.In the reaction of absorption enhanced hydrogen production by ethanol steam reforming, use this difunctional particle of 1.24g as catalyst, the air speed of ethanol is 20 h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and prereduction temperature is 700 ℃, and reaction temperature is 600 ℃, as Fig. 1.
As shown in Fig. 1 (b), before 20min, density of hydrogen reaches 97%, after 15min, adsorbent absorption reaches capacity gradually, hydrogen relative amount reduces gradually, is finally stabilized in 73% left and right, and the Composite Double functional particulate of Co-Ni modification that hence one can see that has better absorption and effect than unmodified difunctional particle for the steam reforming reaction of ethanol.
Embodiment 2:
Take 9.42g calcium acetate, 1.83g cabaltous nitrate hexahydrate, 0.45g nickel nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 100 ℃, then fragmentation obtains the Composite Double functional particulate of 24 ~ 50 object Co modifications after 900 ℃ of calcining 3h.In the reaction of absorption enhanced glycerol liquor vapour reforming hydrogen producing, use this difunctional particle of 1.24g as catalyst, the air speed of glycerine is 20 h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and prereduction temperature is 700 ℃, and reaction temperature is 600 ℃, as Fig. 2.
As shown in Fig. 2 (b), before 13min, density of hydrogen reaches 97%, after 15min, adsorbent absorption reaches capacity gradually, hydrogen relative amount reduces gradually, is finally stabilized in 70% left and right, and the Composite Double functional particulate of Co-Ni modification that hence one can see that has better absorption and effect than unmodified difunctional particle for the steam reforming reaction of glycerine.
Embodiment 3:
Take 9.42g calcium acetate, 1.83g cabaltous nitrate hexahydrate, 0.45g nickel nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 100 ℃, then fragmentation obtains the Composite Double functional particulate of 24 ~ 50 object Co modifications after 900 ℃ of calcining 3h.In the reaction of absorption enhanced acetic acid vapor reforming hydrogen production, use this difunctional particle of 1.24g as catalyst, the air speed of acetic acid is 22 h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and prereduction temperature is 700 ℃, and reaction temperature is 600 ℃, as Fig. 3.
As shown in Figure 3 (b), before 13min, density of hydrogen reaches 98%, after 15min, adsorbent absorption reaches capacity gradually, hydrogen relative amount reduces gradually, is finally stabilized in 68% left and right, and the Composite Double functional particulate of Co-Ni modification that hence one can see that has better suction-operated than unmodified difunctional particle for the steam reforming reaction of acetic acid.
Claims (8)
1. the Composite Double functional particulate of a Co modification, it is characterized in that described particle prepared by following methods: calcium acetate, cabaltous nitrate hexahydrate, nickel nitrate and citric acid are mixed, adding water to stir dissolves it completely, solution is constantly stirred at a certain temperature and is dried, then after calcining the broken Composite Double functional particulate that obtains Co modification.
2. the Composite Double functional particulate of Co modification according to claim 1, is characterized in that: the mol ratio of citric acid and calcium acetate is 0.5 ~ 3:1.
3. the Composite Double functional particulate of Co modification according to claim 1, is characterized in that: the baking temperature of solution is between 80 ~ 120 ℃.
4. the Composite Double functional particulate of Co modification according to claim 1, is characterized in that: described calcining heat is between 700 ~ 1100 ℃, and calcination time is 2 ~ 5h.
5. the Composite Double functional particulate of Co modification according to claim 1, it is characterized in that: through calcining, calcium acetate becomes CaO, cerous nitrate becomes CoO, nickel nitrate becomes NiO, in the Composite Double functional particulate of prepared Co modification, the quality of Ni accounts for 10% ~ 20% of CaO quality, and the quality of Co accounts for 1% ~ 10% of CaO quality.
6. the Composite Double functional particulate of Co modification according to claim 1, is characterized in that: through Mechanical Crushing, the difunctional particle of gained is of a size of 24 ~ 50 orders.
7. an application for the Composite Double functional particulate of Co modification as claimed in claim 1, is characterized in that described particle can be applicable to adsorb the vapor reforming hydrogen production reaction of enhanced biomass derivatives.
8. the application of the Composite Double functional particulate of Co modification according to claim 7, it is characterized in that: described vapor reforming hydrogen production reaction is to carry out in fixed bed reactors, take the Composite Double functional particulate of Co modification as catalyst, steam/hydrocarbons ratio is 1.5 ~ 5:1, and ethanol air speed is 11 ~ 55h
-1, reaction pressure is 0.1 ~ 0.3MPa, and prereduction temperature is 600 ~ 800 ℃, and reaction temperature is 500 ~ 600 ℃, and regeneration temperature is 700 ~ 900 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098311A (en) * | 2017-03-16 | 2017-08-29 | 华南理工大学 | A kind of method of glycerine absorption enhancing reformation hydrogen production |
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| CN1903431A (en) * | 2006-08-01 | 2007-01-31 | 中国石油化工股份有限公司 | Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use |
| JP2007055849A (en) * | 2005-08-24 | 2007-03-08 | Murata Mfg Co Ltd | Carbon dioxide-absorbing material having function as steam reforming catalyst, its producing method, and fuel gas reforming method in hydrogen production system |
| CN101444737A (en) * | 2008-12-22 | 2009-06-03 | 长沙星纳气凝胶有限公司 | Nickel-based catalyst for hydrogen production by ethanol steam reforming and preparation method thereof |
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2014
- 2014-01-15 CN CN201410015934.2A patent/CN103785344A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055849A (en) * | 2005-08-24 | 2007-03-08 | Murata Mfg Co Ltd | Carbon dioxide-absorbing material having function as steam reforming catalyst, its producing method, and fuel gas reforming method in hydrogen production system |
| CN1903431A (en) * | 2006-08-01 | 2007-01-31 | 中国石油化工股份有限公司 | Composite catalyst used for reforming hydrogen prodn. using methane and water vapor as raw material, preparing process and use |
| CN101444737A (en) * | 2008-12-22 | 2009-06-03 | 长沙星纳气凝胶有限公司 | Nickel-based catalyst for hydrogen production by ethanol steam reforming and preparation method thereof |
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| HONGLU ET AL: "Flame-Made Durable Doped-CaO Nanosorbents for CO2 Capture", 《ENERGY&FUELS》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098311A (en) * | 2017-03-16 | 2017-08-29 | 华南理工大学 | A kind of method of glycerine absorption enhancing reformation hydrogen production |
| CN107098311B (en) * | 2017-03-16 | 2019-06-18 | 华南理工大学 | A kind of method of glycerol absorption enhancing reformation hydrogen production |
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Application publication date: 20140514 |