CN103769107A - Biomass hydrogen production composite difunctional particle and preparation method and application thereof - Google Patents
Biomass hydrogen production composite difunctional particle and preparation method and application thereof Download PDFInfo
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- CN103769107A CN103769107A CN201410061099.6A CN201410061099A CN103769107A CN 103769107 A CN103769107 A CN 103769107A CN 201410061099 A CN201410061099 A CN 201410061099A CN 103769107 A CN103769107 A CN 103769107A
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Abstract
The invention discloses a biomass hydrogen production composite difunctional particle and a preparation method and application thereof. The composite difunctional particle comprises CaO, FeO and NiO, wherein the mass of NiO accounts for 10-20 percent of mass of CaO, and the mass of FeO in accounts for 1-10 percent of the mass of CaO. The cyclic adsorption capacity of the biomass hydrogen production composite difunctional particle prepared by the preparation method disclosed by the invention is obviously higher than that of a non-modified calcium-based difunctonal particle and the prepared biomass hydrogen production composite difunctional particle has high adsorption capacity; hydrogen obtained by application of the biomass hydrogen production composite difunctional particle in reforming reaction between adsorption enhanced type glycerinum and acetic acid vapor is relatively high; compared with the conventional non-modified difunctional particle, the biomass hydrogen production composite difunctional particle disclosed by the invention has long adsorption time; the manufacturing time is simple; the requirement on equipment is low; the biomass hydrogen production composite difunctional particle can be applied to large-scale production.
Description
Technical field
The present invention relates to a kind of biomass derivatives steam reforming Composite Double functional particulate, preparation method and application, belong to energy technology field.
Background technology
Fuel cell have pollute little, calorific value is high, utilize the advantages such as various informative.For on-board hydrogen fuel cell, owing to being subject to hydrogen storage system restriction, not yet obtain practical application.Based on this, propose to use liquid fuel to be directly restructured as the solution of on-vehicle fuel hydrogen supply.That the biomass derivatives such as glycerine and acetic acid has is renewable, the feature of high specific energy and low carbon chain, is suitable as the fuel of on-vehicle fuel car.
Biomass derivatives comprises 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 steam reforming reaction is broken, and reforming reaction and water gas shift reation will be to being conducive to H
2the direction producing moves, and improves the utilization rate of acetic acid and glycerine, increases output and the purity of hydrogen.Steam reforming catalyst mainly comprises noble metal catalyst, non-precious metal catalyst and oxide catalyst.Previous experiments proves, noble metal catalyst catalytic effect is better, but its cost is higher, is not yet used widely.
Chinese patent (CN201110327458.4) discloses a kind of for ethanol steam reforming reaction NiO/Ce-xPrxO
2catalyst and preparation method, belong to the load type metal catalyst technology that hydrocarbon is reformed.Described catalyst is with Ce1-xPrxO
2for carrier, Ni is active component, and the mass ratio of NiO and carrier is between 0.01～0.2.Biomass derivatives is numerous, wherein wraps ethanol, acetic acid and glycerine, and effect is relative less with the vapor reforming hydrogen production catalyst of acetic acid and glycerine, therefore has certain researching value for the preparation method of the catalyst of acetic acid and glycerol liquor steam reforming reaction.
Summary of the invention
The invention reside in a kind of biomass hydrogen preparation Composite Double functional particulate, preparation method and application are provided.
Realizing technical scheme of the present invention is: a kind of biomass hydrogen preparation Composite Double functional particulate, and described Composite Double functional particulate comprises CaO, FeO and NiO, and wherein the quality of NiO accounts for 10%～20% of CaO quality, and the quality of FeO accounts for 1%～10% of CaO quality.
A kind of preparation method of biomass hydrogen preparation Composite Double functional particulate, described particle is prepared by following methods: calcium acetate, ferric nitrate, nickel nitrate and citric acid are mixed by a certain percentage, adding water to stir dissolves it completely, solution is stirred to the dry solid particle that obtains mixing at a certain temperature, again solid particle is calcined in Muffle furnace, obtain corresponding CaO, FeO and NiO, product, through Mechanical Crushing and screening, is obtained to a kind of biomass hydrogen preparation Composite Double functional particulate of specific order number.
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.
The baking temperature of described calcium acetate, ferric nitrate, nickel nitrate and citric acid mixed solution is between 80～120 ℃.
Described calcining heat is 700～1100 ℃, and calcination time is 2～5h.
Described nickel nitrate quality accounts for 17.57%～35.14% of calcium acetate quality, and the quality of ferric nitrate accounts for 1.53%～15.32% of calcium acetate quality.
Described calcined product, through Mechanical Crushing, through 24～50 eye mesh screen screenings, obtains required difunctional particle.
Above-mentioned a kind of biomass hydrogen preparation Composite Double functional particulate 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 glycerine or acetic acid air speed are 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.℃
Compared with prior art, its remarkable advantage is in the present invention: the circulation absorption capacity of a kind of biomass hydrogen preparation Composite Double functional particulate that (1) prepares the present invention, apparently higher than the difunctional particle of unmodified calcium base, has larger adsorption capacity.(2) to be applied to the hydrogen relative amount that absorption enhanced glycerine and acetic acid steam reforming reaction obtain higher in the present invention.(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 absolute content (a) and the relative amount (b) of the embodiment of the present invention 1 biomass hydrogen preparation Composite Double functional particulate for the each production concentration of glycerol liquor steam reforming reaction.
Fig. 2 is absolute content (a) and the relative amounts (b) of the embodiment of the present invention 2 biomass hydrogen preparation Composite Double functional particulates 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.
Embodiment 1:
Take 9.42g calcium acetate, 3.46g nickel nitrate, 0.45g ferric 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 a kind of biomass hydrogen preparation Composite Double of 24～50 objects functional particulate 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 22h
-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 Figure 1, before 18min, density of hydrogen reaches 98%, after 18min, adsorbent absorption reaches capacity gradually, hydrogen relative amount reduces gradually, is finally stabilized in 63% left and right, and the Composite Double functional particulate of Fe-Ni modification that hence one can see that has better absorption and effect than unmodified difunctional particle for the steam reforming reaction of glycerine.
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 22h
-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 Figure 2, before 13min, density of hydrogen reaches 99%, after 13min, adsorbent absorption reaches capacity gradually, and hydrogen relative amount reduces gradually, is finally stabilized in 63% left and right, the Composite Double functional particulate of Fe-Ni modification that hence one can see that is more difunctional than unmodified, and particle has better suction-operated for the steam reforming reaction of acetic acid.
Embodiment 2:
Take 9.42g calcium acetate, 3.46g nickel nitrate, 0.45g ferric nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 80 ℃, then fragmentation obtains a kind of biomass hydrogen preparation Composite Double of 24～50 objects functional particulate after 700 ℃ of calcining 2h.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 11h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and prereduction temperature is 600 ℃, and reaction temperature is 500 ℃.Experiment is surveyed, and the Composite Double functional particulate of preparing under this condition acts on the reaction of acetic acid vapor reforming hydrogen production, and gained density of hydrogen is a little less than the density of hydrogen in embodiment 1.
Embodiment 3:
Take 9.42g calcium acetate, 3.46g nickel nitrate, 0.45g ferric nitrate and 5.62g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 120 ℃, then fragmentation obtains a kind of biomass hydrogen preparation Composite Double of 24～50 objects functional particulate after 1100 ℃ of calcining 5h.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 55h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.3MPa, and prereduction temperature is 800 ℃, and reaction temperature is 600 ℃.Experiment is surveyed, and the Composite Double functional particulate of preparing under this condition acts on the reaction of acetic acid vapor reforming hydrogen production, and gained density of hydrogen is a little more than the density of hydrogen in embodiment 1.
Embodiment 4:
Take 9.42g calcium acetate, 4.67g nickel nitrate, 0.41g ferric nitrate and 3.75g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 100 ℃, then fragmentation obtains a kind of biomass hydrogen preparation Composite Double of 24～50 objects functional particulate 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 22h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and prereduction temperature is 700 ℃, and reaction temperature is 600 ℃.Experiment is surveyed, and the Composite Double functional particulate of preparing under this condition acts on the reaction of acetic acid vapor reforming hydrogen production, the dense density of hydrogen being starkly lower than in embodiment 1 of gained hydrogen.
Embodiment 5:
Take 9.42g calcium acetate, 9.34g nickel nitrate, 4.07g ferric nitrate and 7.5g citric acid, adding distilled water to stir dissolves it completely, solution is constantly stirred and is dried at 100 ℃, then fragmentation obtains a kind of biomass hydrogen preparation Composite Double of 24～50 objects functional particulate 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 22h
-1, steam/hydrocarbons ratio is 3:1, and reaction pressure is 0.1MPa, and prereduction temperature is 700 ℃, and reaction temperature is 600 ℃.Experiment is surveyed, and the Composite Double functional particulate of preparing under this condition acts on the reaction of acetic acid vapor reforming hydrogen production, and gained density of hydrogen is a little more than the density of hydrogen in embodiment 1.
Claims (9)
1. a biomass hydrogen preparation Composite Double functional particulate, is characterized in that described Composite Double functional particulate comprises CaO, FeO and NiO, and wherein the quality of NiO accounts for 10%～20% of CaO quality, and the quality of FeO accounts for 1%～10% of CaO quality.
2. the preparation method of a biomass hydrogen preparation Composite Double functional particulate, it is characterized in that described particle prepared by following methods: calcium acetate, ferric nitrate, nickel nitrate and citric acid are mixed, adding water to stir dissolves it completely, solution is stirred to the dry solid particle that obtains mixing, calcine in Muffle furnace through solid particle again, obtain corresponding CaO, FeO and NiO, product, through Mechanical Crushing and screening, is obtained to biomass hydrogen preparation Composite Double functional particulate.
3. the preparation method of biomass hydrogen preparation Composite Double functional particulate according to claim 2, is characterized in that described calcium acetate and the mol ratio of citric acid are 0.5～3:1.
4. the preparation method of biomass hydrogen preparation Composite Double functional particulate according to claim 2, is characterized in that the baking temperature of described calcium acetate, ferric nitrate, nickel nitrate and aqueous citric acid solution is between 80～120 ℃.
5. the preparation method of biomass hydrogen preparation Composite Double functional particulate according to claim 2, is characterized in that described calcining heat is 700～1100 ℃, and calcination time is 2～5h.
6. the preparation method of biomass hydrogen preparation Composite Double functional particulate according to claim 2, is characterized in that described nickel nitrate quality accounts for 17.57%～35.14% of calcium acetate quality, and the quality of ferric nitrate accounts for 1.53%～15.32% of calcium acetate quality.
7. the preparation method of biomass hydrogen preparation Composite Double functional particulate according to claim 2, is characterized in that described calcined product is through Mechanical Crushing, through 24～50 eye mesh screen screenings, obtains required difunctional particle.
8. an application for biomass hydrogen preparation Composite Double functional particulate, is characterized in that difunctional particle claimed in claim 1 to be applied to the reaction of absorption enhanced biomass derivatives vapor reforming hydrogen production.
9. the application of biomass hydrogen preparation Composite Double functional particulate according to claim 8, is characterized in that described technique for applying condition is: steam/hydrocarbons ratio is 1.5～5:1, and glycerine or acetic acid air speed are 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110562916A (en) * | 2019-09-25 | 2019-12-13 | 华南理工大学 | Method for producing hydrogen by adsorption and enhancement of lignin black liquor through reforming |
| CN112844397A (en) * | 2021-01-22 | 2021-05-28 | 成都理工大学 | Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
Citations (3)
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| WO1999003566A1 (en) * | 1997-07-15 | 1999-01-28 | The University Of Queensland | Catalytic conversion of gases via cation-exchangeable alumino-silicate materials |
| CN102225744A (en) * | 2011-04-02 | 2011-10-26 | 东南大学 | Method and device for preparing hydrogen and separating CO2 based on Fe2O3-NiO mixture |
| CN103521162A (en) * | 2013-10-11 | 2014-01-22 | 南京理工大学 | Cerium modified calcium-based bifunctional particle, and preparation method and application thereof |
-
2014
- 2014-02-24 CN CN201410061099.6A patent/CN103769107A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999003566A1 (en) * | 1997-07-15 | 1999-01-28 | The University Of Queensland | Catalytic conversion of gases via cation-exchangeable alumino-silicate materials |
| CN102225744A (en) * | 2011-04-02 | 2011-10-26 | 东南大学 | Method and device for preparing hydrogen and separating CO2 based on Fe2O3-NiO mixture |
| CN103521162A (en) * | 2013-10-11 | 2014-01-22 | 南京理工大学 | Cerium modified calcium-based bifunctional particle, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| SHAWN DECKER ET.AL.: "Enhancing Effect of Fe2O3 on the Ability of Nanocrystalline Calcium Oxide to Adsorb SO2", 《J.AM.CHEM.SOC.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110562916A (en) * | 2019-09-25 | 2019-12-13 | 华南理工大学 | Method for producing hydrogen by adsorption and enhancement of lignin black liquor through reforming |
| CN112844397A (en) * | 2021-01-22 | 2021-05-28 | 成都理工大学 | Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
| CN112844397B (en) * | 2021-01-22 | 2023-02-10 | 成都理工大学 | Cerium-samarium solid solution nickel-based catalyst for autothermal reforming of acetic acid to produce hydrogen |
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Application publication date: 20140507 |