CN102443454A - Oxygen carrier of chemical-looping combustion and preparation method and application thereof - Google Patents
Oxygen carrier of chemical-looping combustion and preparation method and application thereof Download PDFInfo
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- CN102443454A CN102443454A CN2010105112170A CN201010511217A CN102443454A CN 102443454 A CN102443454 A CN 102443454A CN 2010105112170 A CN2010105112170 A CN 2010105112170A CN 201010511217 A CN201010511217 A CN 201010511217A CN 102443454 A CN102443454 A CN 102443454A
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Abstract
The invention discloses an oxygen carrier of chemical-looping combustion and preparation method and application thereof; the oxygen carrier uses CeO2 as carrier and Fe2O3 as active component; the weight percentage of the active component Fe2O3 in the oxygen carrier is 5-30%; and the aperture of the oxygen carrier is 500nm-50um. The preparation method of the oxygen carrier comprises the following processes of: preparing template by emulsion polymerization method, preparing the macroporous CeO2 and loading the active component and the like. The oxygen carrier is applied to the chemical-looping combustion, wherein the reaction temperature in the air reactor is 500-1000 DEG C, the reaction temperature of the fuel reactor is 500-1000 DEG C, and the reaction pressure is constant pressure. The oxygen carrier of the invention has three-dimension ordered macroporous structure, uniform distribution of the active component and simple preparation method; and the oxygen carrier in the chemical-looping combustion has the advantages that the lamination of the reaction bed is reduced, the activity of the reaction bed is high and the diffusion effect of the reaction bed is good and the like.
Description
Technical field
The present invention relates to a kind of oxygen carrier of burning chemistry chains, specifically relate to a kind of three-dimensional ordered macroporous oxide oxygen carrier of burning chemistry chains, belong to the catalyst technology in burning chemistry chains field.
Background technology
Carbonic acid gas (CO
2) be a kind of main greenhouse gases, reduce discharging CO in the combustion processes
2Become the research focus.The thermoelectricity technology all is oxygenant with the air, CO in the flue gas of generation
2Only account for 10%～20%, CO
2Subsequent treatment cost too high, be difficult to carry out.In combustion processes, generate the CO of high density
2Or be convenient to CO
2Isolating gas phase mixture is like (CO
2+ H
2O), eliminating the generation discharging (like NOx, SOx and Hg etc.) of other pollutents simultaneously, is a valid approach, selects pure oxygen to make oxygenant, gains universal acceptance.But produce pure oxygen or oxygen enrichment and need consume lot of energy, for the power station, the electric power of its consumption can account for more than 10% of full factory, has limited this The Application of Technology.Before fuel combustion, carry out carbonization treatment, can reduce CO
2Discharging, as fuel is gasified, reforms, isolate the Hydrogen Energy of cleaning, use Hydrogen Energy and can realize zero release, but need develop the CO of high efficiency, low cost
2, H
2Correlation techniques such as separatory membrane.
(chemical looping combustion CLC) is a kind of combustion system of novelty to burning chemistry chains, and fuel does not directly contact with air, is oxygen carrier with the MOX, and oxygen carrier carries out oxidizing reaction in air at a certain temperature, in conjunction with oxygen; Carry out reduction reaction, release oxygen with fuel gas then.The gas-phase reaction product has only CO
2And H
2O (gas), the water outlet of condensing obtains high-purity CO
2CO in the burning chemistry chains process
2Can be by airborne nitrogen dilution, so can not have to realize CO under the precondition of power loss
2Separate.The complete description of relevant chemical-looping combustion method is found in french patent application 02-14, and 071 and 04-08,549.
Oxygen carrier circulates between two reactor drums as media, and the heat that ceaselessly generates oxygen in the air reactor and reaction is delivered to the fuel reaction device and carries out reduction reaction, so the character of oxygen carrier has directly influenced the operation of whole burning chemistry chains.At present, the oxygen carrier of main research is the metal oxygen carrier, comprises Fe, Ni, Co, Cu, Mn, Cd etc., and carrier mainly contains: Al
2O
3, TiO
2, MgO, SiO
2, YSZ etc., also have a spot of nonmetal oxide such as CaSO
4Deng.In the burning chemistry chains process, oxygen carrier is in continuous oxygen loss-De oxygen condition, so the activity of oxygen is very important in the oxygen carrier.Comparatively speaking, oxygen carrier NiO/NiAl
2O
4(CHO P etc.Fuel, 2004,83 (9)), Fe
2O
3/ Al
2O
3(MATTISSONT etc.Fuel; 2001; 80 (13)) and CoO-NiO/YSZ (JIN H G etc.Energy Fuels; 1998,12 (6)) etc. over-all properties is better, and the reaction bed pressure drop is big, the oxygen carrier aperture is little, the oxygen carrier rate is limited, circulating reaction property is lower, can't bear the not high deficiency of higher temperature of reaction, MOX dispersity in oxygen carrier but exist.
Three-dimensional ordered macroporous oxide is arranged because have the duct of rule; The characteristics of aperture between hundreds of nanometer to tens micron; So aspect catalysis, obtain extensive concern in recent years, but also do not appear in the newspapers three-dimensional ordered macroporous material as the oxygen carrier that the active ingredient carrier in the chemical chain burning technology makes.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of oxygen carrier of burning chemistry chains.Macroporous structure, the active ingredient that this oxygen carrier has a three-dimensional order be uniformly dispersed and the preparation method simple, this oxygen carrier has advantages such as the reaction bed pressure drop is low, active high, and diffusion effect is good in the burning chemistry chains reaction.
The oxygen carrier of a kind of burning chemistry chains of the present invention, described oxygen carrier is with CeO
2Be carrier, with Fe
2O
3Be active ingredient, active ingredient Fe
2O
3Weight content in oxygen carrier is 5～30%, and the aperture of oxygen carrier is 500nm～50um.
The preparation method of the oxygen carrier of a kind of burning chemistry chains of the present invention comprises following process:
1) adopt emulsion polymerization to prepare template:
With vinylbenzene is monomer, adds quality and be 0.1～2% Sodium Persulfate initiator of monomer mass, and polymerization was put into loft drier to polymkeric substance dry 12～24 hours after 8～24 hours in 50～80 ℃ of water-baths.Template 90～120 ℃ of following thermal treatments, is strengthened the physical strength of template.
2) macropore CeO
2Preparation:
With Ce (NO
3)
36H
2O is the cerium source, add molar weight is that 0.2～0.4 times Hydrocerol A of cerium molar weight is an intercalating agent, joins in the absolute ethyl alcohol, is stirred to be transparent color.The polystyrene moulding that step 1) is made is immersed in this solution; Dipping 5～20min final vacuum is taken out rate, drying; Repeat above-mentioned dipping-take out rate-drying process 3～6 times then; Temperature rise rate with 0.1～5 ℃/min is warming up to 500～900 ℃ in the tubular type retort furnace then, and constant temperature calcining 2～4 hours obtains three-dimensional ordered macroporous CeO
2
3) load active component:
Get the iron nitrate solution that concentration is 0.2～2.0mol/L, with step 2) preparation three-dimensional ordered macroporous CeO
2Incipient impregnation is in iron nitrate solution, and is at room temperature dry then, again in 70～100 ℃ of dryings 8～20 hours then 400～800 ℃ of roastings, obtain Fe
2O
3/ CeO
2Oxygen carrier.
Fe of the present invention
2O
3/ CeO
2The application of oxygen carrier in chemical chain burning technology, wherein the temperature of reaction in air reactor is 500～1000 ℃, and the temperature of reaction in the fuel reaction device is 500～1000 ℃, and reaction pressure all is a normal pressure.
Compared with prior art the present invention has following advantage:
1, Fe of the present invention
2O
3/ CeO
2Oxygen carrier has the macroporous structure of three-dimensional order, helps fuel gas and oxygen at Fe
2O
3/ CeO
2The intravital diffusion of oxygen carrier improves fuel gas incendiary efficient, reduces the pressure drop of reaction bed, improves the stability of oxygen carrier.
2, Fe of the present invention
2O
3/ CeO
2CeO in the oxygen carrier
2Have a large amount of oxygen rooms, in air reactor, CeO
2The oxygen room can the adsorb oxygen molecule, improve Fe
2O
3/ CeO
2The concentration of oxygen molecule and activation oxygen molecule on the oxygen carrier internal surface help the oxidizing reaction of active ingredient, improve the required circulation oxygen of chemical chain circulating combustion amount; At combustion reactor CeO
2Can make Fe with the synergy of iron
2O
3/ CeO
2Oxygen and fuel in the oxygen carrier react rapidly and thoroughly, improve the utilization ratio of circulation oxygen, in addition CeO
2Adsorb oxygen on the oxygen room also can promote combustion reactions.
3, Fe of the present invention
2O
3/ CeO
2The oxygen carrier preparation method is simple; CeO
2The oxygen room help iron at its surperficial uniform distribution, the Fe of preparation
2O
3/ CeO
2Oxygen carrier active ingredient dispersity is high, Heat stability is good.
Description of drawings
Fig. 1 is the embodiment of the invention 1 prepared macropore Fe
2O
3/ CeO
2Sem photograph.
Embodiment
Further specify the process and the effect of the inventive method below in conjunction with embodiment.
Get 20ml vinylbenzene, be added drop-wise in 110mL deionized water and the 60mL ethanol solution, stir while dripping, evenly after, add the 10mL initiator, Sodium Persulfate concentration is 0.068mol/L in the initiator.After stirring 24 hours under 70 ℃, put into loft drier dry 12 hours.Template 110 ℃ of following thermal treatments 10 minutes, is strengthened the physical strength of template.
Get 18.31gCe (NO
3)
36H
2O joins in the 40mL absolute ethyl alcohol, adds the 4.4g Hydrocerol A again, is stirred to be transparent color.Polystyrene moulding is flooded this solution, and final vacuum was taken out rate in 5 minutes, and drying is 2 hours in 70 ℃ of loft drier.Repeat above-mentioned dipping-take out rate-drying process 4 times then, then in the tubular type retort furnace with 2 ℃/min temperature programming to 800 ℃, constant temperature calcining 4 hours obtains three-dimensional ordered macroporous CeO
2
Configuration concentration is the iron nitrate solution 6ml of 0.5mol/L, with the macropore CeO of above-mentioned preparation
2Incipient impregnation is in iron nitrate solution, and the mass content of red stone is 6wt%, 20 ℃ of dryings, more than 12 hours, is 800 ℃ roastings 3 hour in temperature then in 75 ℃ of dryings again, obtains Fe
2O
3/ CeO
2Oxygen carrier.
With the above-mentioned oxygen carrier screening that makes, getting granularity is 40～80 purpose oxygen carrier 0.5g, on the fixed bed quartz tube reactor, carries out performance test.The silica tube specification is φ 8 * 2, and virgin gas consists of: 30%H
2, 60%CO, 10%N
2Sample rises to 700 ℃ from room temperature, with atmospheric oxidation 30 minutes, feeds nitrogen purging then 10 minutes, feeds virgin gas and reacts.React after 30 minutes, fed nitrogen purging again 10 minutes, switch to air again and carry out oxidation, feed nitrogen purging after 10 minutes, accomplish once oxidation-reduction circulation like this.Adopt Agilent 7820 gc on-line analyses, TCD detects, 5A molecular sieve column and Porapak Q post.H
2Transformation efficiency is 98%, and the CO transformation efficiency is 93%.
Embodiment 2
Press the preparation process among the embodiment 1, the change iron nitrate concentration is 1mol/L, and the mass content of red stone is 11.6wt%.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 99%, and the CO transformation efficiency is 96%.
Embodiment 3
Press the preparation process among the embodiment 1, the change iron nitrate concentration is 2mol/L, and the mass content of red stone is 20.9wt%.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 98%, and the CO transformation efficiency is 96%.
Embodiment 4
Pressing the preparation process among the embodiment 1, change the maturing temperature after macropore floods iron nitrate, is 700 ℃.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 95%, and the CO transformation efficiency is 91%.
Pressing the preparation process among the embodiment 1, change the maturing temperature after macropore floods iron nitrate, is 750 ℃.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 97%, and the CO transformation efficiency is 93%.
Embodiment 6
Press the preparation process among the embodiment 1, get 20ml vinylbenzene, be added drop-wise in 80mL deionized water and the 40mL ethanol solution, stir while dripping.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 93%, and the CO transformation efficiency is 90%.
Embodiment 7
Press the preparation process among the embodiment 1, change macropore CeO
2Maturing temperature, be 700 ℃.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 91%, and the CO transformation efficiency is 88%.
Embodiment 8
Press the preparation process among the embodiment 1, change macropore CeO
2Maturing temperature, be 900 ℃.Carry out the test of burning chemistry chains reactivity worth with this catalyzer, test condition is with embodiment 1.H
2Transformation efficiency is 94%, and the CO transformation efficiency is 91%.
Comparative Examples
Adopt conventional coprecipitation method to prepare Fe
2O
3/ CeO
2Particle, roasting condition, performance test condition are with embodiment 1.H
2Transformation efficiency is 83%, and the CO transformation efficiency is 79%.
Claims (3)
1. the oxygen carrier of a burning chemistry chains is characterized in that described oxygen carrier is with CeO
2Be carrier, with Fe
2O
3Be active ingredient, active ingredient Fe
2O
3Weight content in oxygen carrier is 5～30%, and the aperture of oxygen carrier is 500nm～50um.
2. according to the oxygen carrier preparation method of the described burning chemistry chains of claim 1, it is characterized in that comprising the steps:
1) adopt emulsion polymerization to prepare template:
With vinylbenzene is monomer, adds quality and be 0.1～2% Sodium Persulfate initiator of monomer mass, and polymerization was put into loft drier to polymkeric substance dry 12～24 hours after 8～24 hours in 50～80 ℃ of water-baths.Template 90～120 ℃ of following thermal treatments, is strengthened the physical strength of template.
2) macropore CeO
2Preparation:
With Ce (NO
3)
36H
2O is the cerium source, add molar weight is that 0.2～0.4 times Hydrocerol A of cerium molar weight is an intercalating agent, joins in the absolute ethyl alcohol, is stirred to be transparent color.The polystyrene moulding that step 1) is made is immersed in this solution; Dipping 5～20min final vacuum is taken out rate, drying; Repeat above-mentioned dipping-take out rate-drying process 3～6 times then; Temperature rise rate with 0.1～5 ℃/min is warming up to 500～900 ℃ in the tubular type retort furnace then, and constant temperature calcining 2～4 hours obtains three-dimensional ordered macroporous CeO
2
3) load active component:
Get the iron nitrate solution that concentration is 0.2～2.0mol/L, with step 2) preparation three-dimensional ordered macroporous CeO
2Incipient impregnation is in iron nitrate solution, and is at room temperature dry then, again in 70～100 ℃ of dryings 8～20 hours then 400～800 ℃ of roastings, obtain Fe
2O
3/ CeO
2Oxygen carrier.
3. according to claim 1 or 2 application of described oxygen carrier in burning chemistry chains, wherein the temperature of reaction in air reactor is 500～1000 ℃, and the temperature of reaction in the fuel reaction device is 500～1000 ℃.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387865A (en) * | 2012-05-10 | 2013-11-13 | 清华大学 | High-performance double-core iron-based oxygen carrier particle and preparation method thereof |
| CN103480404A (en) * | 2013-09-26 | 2014-01-01 | 中国石油大学(北京) | Macroporous iron carbide catalyst, and preparation method and application thereof |
| CN109054755A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the heat accumulating type carrier of oxygen |
| CN109054756A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the high temperature composite phase-change heat-storage carrier of oxygen |
| CN110872445A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Asphalt modifier for purifying automobile exhaust, asphalt material and preparation method thereof |
| CN111704949A (en) * | 2020-07-06 | 2020-09-25 | 山西恒投环保节能科技有限公司 | Oxygen carrier composition and preparation method thereof |
| CN114735649A (en) * | 2021-01-07 | 2022-07-12 | 中国石油化工股份有限公司 | Iron-based oxygen carrier and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103387865A (en) * | 2012-05-10 | 2013-11-13 | 清华大学 | High-performance double-core iron-based oxygen carrier particle and preparation method thereof |
| CN103387865B (en) * | 2012-05-10 | 2015-07-22 | 清华大学 | High-performance double-core iron-based oxygen carrier particle and preparation method thereof |
| CN103480404A (en) * | 2013-09-26 | 2014-01-01 | 中国石油大学(北京) | Macroporous iron carbide catalyst, and preparation method and application thereof |
| CN103480404B (en) * | 2013-09-26 | 2015-05-06 | 中国石油大学(北京) | Macroporous iron carbide catalyst, and preparation method and application thereof |
| CN109054755A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the heat accumulating type carrier of oxygen |
| CN109054756A (en) * | 2018-06-21 | 2018-12-21 | 昆明理工大学 | A kind of core-shell structure Fe2O3-CeO2The preparation method of/(Al@C) the high temperature composite phase-change heat-storage carrier of oxygen |
| CN109054755B (en) * | 2018-06-21 | 2020-10-27 | 昆明理工大学 | Core-shell structure Fe2O3-CeO2Preparation method of heat storage type oxygen carrier |
| CN109054756B (en) * | 2018-06-21 | 2020-10-27 | 昆明理工大学 | Core-shell structure Fe2O3-CeO2Preparation method of (Al @ C) high-temperature composite phase-change heat-storage oxygen carrier |
| CN110872445A (en) * | 2018-08-30 | 2020-03-10 | 中国石油化工股份有限公司 | Asphalt modifier for purifying automobile exhaust, asphalt material and preparation method thereof |
| CN111704949A (en) * | 2020-07-06 | 2020-09-25 | 山西恒投环保节能科技有限公司 | Oxygen carrier composition and preparation method thereof |
| CN114735649A (en) * | 2021-01-07 | 2022-07-12 | 中国石油化工股份有限公司 | Iron-based oxygen carrier and preparation method and application thereof |
| CN114735649B (en) * | 2021-01-07 | 2023-10-10 | 中国石油化工股份有限公司 | Iron-based oxygen carrier and preparation method and application thereof |
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| CN102443454B (en) | 2014-03-05 |
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