CN103752256A - Preparation method of nickel-modified calcium-based dual-functional particles - Google Patents
Preparation method of nickel-modified calcium-based dual-functional particles Download PDFInfo
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- CN103752256A CN103752256A CN201410015935.7A CN201410015935A CN103752256A CN 103752256 A CN103752256 A CN 103752256A CN 201410015935 A CN201410015935 A CN 201410015935A CN 103752256 A CN103752256 A CN 103752256A
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Abstract
The invention discloses a preparation method of nickel-modified calcium-based dual-functional particles, and belongs to the technical field of energy. The preparation method is characterized in that the sol-gel method is carried out, citric acid is added to enable ion complexing such as Ca<2+> as well as promote the formation of small holes in the particles during roasting, and thus the absorption efficiency and catalyzing effect are greatly improved. The preparation method is applied to absorption strengthened type steam reforming hydrogen production reaction of a biomass-derived compound, and also shows obvious effect on catalyzing ethanol.
Description
Technical field
The preparation method who the present invention relates to a kind of difunctional particle of calcium base of nickel modification, belongs to energy technology field, is specifically related to one for the reaction of Ethanol Adsorption enhanced vapor reforming hydrogen production, improves hydrogen yield.
Background technology
The extensive utilization of biomass energy, has produced a large amount of biomass derivatives, and wherein the utilization of bio-ethanol has obtained global attention.For bio-ethanol, be by microorganism, sugar to be converted into ethanol with fermentation method, then obtain by processes such as distillations.In ripe alcohol after fermentation, ethanol content is generally between 7% ~ 11%, and the impurity such as water, acids almost account for 90%.
Therefore,, in the production process of ethanol, distillation and dehydration account for 50% of cost, have expended a large amount of energy.So innovation also reasonably utilizes bio-ethanol, reduces the energy consumption in alcohol production, has important economic worth and social effect.
Ethanol reformation hydrogen production has not only well solved the problem of utilizing of ethanol, and can generate the hydrogen pollution-free, calorific value is high.The method of conventional reformation hydrogen production mainly contains: steam reforming, partial oxidation and oxidation and reformation.At present, the research of ethanol reformation hydrogen production mainly concentrates on vapor reforming hydrogen production.But ethanol reforming reaction system complexity, contingent side reaction has ethanol dehydration, alcohol dehydrogenase, ethanol decomposition, Water gas shift/WGS and CO and CO
2hydrogenation etc.At present, at ethanol, reform in system reaction, a kind of catalyst efficient, easy, that have feasibility of How to choose is key issue.
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.The catalyst of preparation can be to ethanol reforming reaction is played to catalytic action, and improve hydrogen yield, but experiment showed, that hydrogen yield is on the low side, and only in 30% left and right, and preparation technology is comparatively complicated.
Therefore, there is higher hydrogen gas relative amount, and the simple difunctional particle that also can be applied to ethanol steam reforming of preparation method is main research direction.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application of the difunctional particle of calcium base of nickel modification.
Realizing technical scheme of the present invention is:
A kind of preparation method of the difunctional particle of calcium base of nickel modification, described method is sol-gal process, comprise the following steps: calcium acetate, nickel nitrate and citric acid are mixed, adding a small amount of water stirring dissolves it completely, and constantly stir dryly, then Mechanical Crushing obtains the difunctional particle of calcium base of nickel modification after calcining.
Wherein, the mol ratio of citric acid and calcium acetate 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, 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 ℃, and calcium acetate becomes CaO, and nickel nitrate becomes NiO, and in the difunctional particle of calcium base of prepared nickel modification, the quality of Ni accounts for 10% ~ 20% of CaO quality.
Described calcined product, through Mechanical Crushing, through 24 ~ 50 eye mesh screen screenings, obtains required difunctional particle.
The difunctional particle of calcium base of above-mentioned nickel 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 ℃.Through experiment, record, 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 relative amount of ethanol can reach 98%.
The present invention compared with prior art, its significantly a little: the circulation absorption capacity of the difunctional particle of calcium base of the nickel 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 and the unmodified difunctional Particle Phase of routine adsorption time (4) of the present invention manufacture craft longer than having 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 difunctional particle of 15wt%Ni calcium base contains spirogram for the product of ethanol steam reforming.
Fig. 2 is that CaO particle contains spirogram for the product of ethanol steam reforming.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, further illustrate the present invention.
Embodiment 1
Take 9.42g calcium acetate, 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 ℃, after 900 ℃ of calcining 3h, fragmentation obtains the difunctional particle of calcium base of 24 ~ 50 object nickel modifications again, and wherein in the difunctional particle of calcium base of nickel modification, the quality of Ni accounts for 15% of CaO quality.In the reaction of absorption enhanced hydrogen production by ethanol steam reforming, use this difunctional particle of 1.19g 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 ℃.
Comparative example 1:
Take 9.42g calcium acetate, add distilled water to stir it is dissolved completely, solution is constantly stirred and is dried at 100 ℃, then fragmentation obtains 24 ~ 50 object calcium based catalysts after 900 ℃ of calcining 3h.In the reaction of absorption enhanced hydrogen production by ethanol steam reforming, use this catalyst of 1.19g, the air speed of ethanol is 20 h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and reaction temperature is 600 ℃.
By comparison diagram, 1 Fig. 2 can find out, H
2and CO
2content there is no significant change, all remain on 97% left and right, and the absorption of the difunctional particle of calcium base of nickel modification strengthen the stage than unmodified, increased by 250%, adsorption time obviously increases, thus improve hydrogen output.
Embodiment 2
Take 9.42g calcium acetate, 0.6g nickel nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 120 ℃, after 1100 ℃ of calcining 5h, fragmentation obtains the difunctional particle of calcium base of 24 ~ 50 object nickel modifications again, and wherein in the difunctional particle of calcium base of nickel modification, the quality of Ni accounts for 10% of CaO quality.In the reaction of absorption enhanced hydrogen production by ethanol steam reforming, use this difunctional particle of 1.19g as catalyst, the air speed of ethanol is 55 h
-1, steam/hydrocarbons ratio is 5:1, and reaction pressure is 0.2MPa, and prereduction temperature is 700 ℃, and reaction temperature is 500 ℃.
Embodiment 3
Take 9.42g calcium acetate, 0.3g nickel nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 80 ℃, after 700 ℃ of calcining 2h, fragmentation obtains the difunctional particle of calcium base of 24 ~ 50 object nickel modifications again, and wherein in the difunctional particle of calcium base of nickel modification, the quality of Ni accounts for 10% of CaO quality.In the reaction of absorption enhanced hydrogen production by ethanol steam reforming, use this difunctional particle of 1.19g as catalyst, the air speed of ethanol is 11 h
-1, steam/hydrocarbons ratio is 1.5:1, and reaction pressure is 0.3MPa, and prereduction temperature is 700 ℃, and reaction temperature is 500 ℃.
Claims (6)
1. the preparation method of the difunctional particle of calcium base of a nickel modification, it is characterized in that: described method is sol-gal process, comprise the following steps: calcium acetate, nickel nitrate and citric acid are mixed, adding a small amount of water stirring dissolves it completely, and constantly stir dryly, then Mechanical Crushing obtains the difunctional particle of calcium base of nickel modification after calcining.
2. the preparation method of the difunctional particle of calcium base of nickel 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 preparation method of the difunctional particle of calcium base of nickel modification according to claim 1, is characterized in that: the baking temperature of solution is between 80 ~ 120 ℃.
4. the preparation method of the difunctional particle of calcium base of nickel modification according to claim 1, is characterized in that: described calcining heat is between 700 ~ 1100 ℃, and calcination time is 2 ~ 5h.
5. the preparation method of the difunctional particle of calcium base of nickel modification according to claim 1, it is characterized in that: through calcining, calcium acetate becomes CaO, and nickel nitrate becomes NiO, and in the difunctional particle of calcium base of prepared nickel modification, the quality of Ni accounts for 10% ~ 20% of CaO quality.
6. the preparation method of the difunctional particle of calcium base of nickel 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.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557760A (en) * | 2018-05-23 | 2018-09-21 | 东华理工大学 | Ni is loaded using nano calcium oxide0The method that catalysis biomass/plastics are total to gasification hydrogen-producing |
Citations (3)
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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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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 |
Non-Patent Citations (2)
| Title |
|---|
| NARUEWAN CHANBURANASIRI ET AL: "Hydrogen production via sorption enhanced steam methane reforming process using Ni/CaO multifunctional catalyst", 《IND. ENG. CHEM. RES.,》, vol. 50, 7 November 2011 (2011-11-07) * |
| 马聪: "改性钙基CO2高温吸附剂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 9, 15 September 2010 (2010-09-15) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557760A (en) * | 2018-05-23 | 2018-09-21 | 东华理工大学 | Ni is loaded using nano calcium oxide0The method that catalysis biomass/plastics are total to gasification hydrogen-producing |
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Application publication date: 20140430 |