CN102443454B - 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 PDF

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CN102443454B
CN102443454B CN201010511217.0A CN201010511217A CN102443454B CN 102443454 B CN102443454 B CN 102443454B CN 201010511217 A CN201010511217 A CN 201010511217A CN 102443454 B CN102443454 B CN 102443454B
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oxygen carrier
ceo
preparation
active component
carrier
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CN102443454A (en
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梁皓
张舒冬
倪向前
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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

Oxygen carrier of a kind of burning chemistry chains and its preparation method and application
Technical field
The present invention relates to oxygen carrier of a kind of burning chemistry chains and its preparation method and application, specifically relate to three-dimensional ordered macroporous oxide oxygen carrier of a kind of burning chemistry chains and its preparation method and application, belong to the catalyst technology in burning chemistry chains field.
Background technology
Carbon dioxide (CO 2) be a kind of main greenhouse gases, in combustion process, reduce discharging CO 2become study hotspot.Thermoelectricity technology all be take air as oxidant, 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 process, generate the CO of high concentration 2or be convenient to CO 2separated gas phase mixture is as (CO 2+ H 2o), eliminate the generation discharge (as NOx, SOx and Hg etc.) of other pollutants, be an effective approach simultaneously, selects pure oxygen to make oxidant, gains universal acceptance.But produce pure oxygen or oxygen enrichment and need to consume a large amount of energy, for power plant, the more than 10% of electric power Ke Zhanquan factory of its consumption, has limited the application of this technology.Before fuel combustion, carry out carbonization treatment, can reduce CO 2discharge, as fuel is gasified, reformed, isolate clean Hydrogen Energy, use Hydrogen Energy and can realize zero-emission, but need to develop the CO of high efficiency, low cost 2, H 2the correlation techniques such as diffusion barrier.
Burning chemistry chains (chemical looping combustion, CLC) be a kind of combustion system of novelty, fuel does not directly contact with air, take metal oxide as oxygen carrier, oxygen carrier carries out oxidation reaction in air at a certain temperature, in conjunction with oxygen; Then carry out reduction reaction with fuel gas, discharge oxygen.Gas-phase reaction product only has CO 2and H 2o (gas), the water outlet of condensing, obtains high-purity CO 2.CO in burning chemistry chains process 2can be by airborne nitrogen dilution, therefore can there is no to realize CO under the precondition of energy loss 2separated.The complete description of relevant chemical recirculation combustion process is found in french patent application 02-14, and 071 and 04-08,549.
Oxygen carrier, as medium, circulates between two reactors, ceaselessly the heat of the oxygen in air reactor and reaction generation is delivered to fuel reactor and carries out reduction reaction, so the character of oxygen carrier has directly affected the operation of whole burning chemistry chains.At present, the oxygen carrier of main research is 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 small amount of nonmetal oxide as CaSO 4deng.In burning chemistry chains process, oxygen carrier is in continuous oxygen loss-get oxygen condition, so the activity of oxygen is very important in 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. combination property is better, but exist, reaction bed pressure drop is large, oxygen carrier aperture is little, oxygen carrier rate is limited, circular response is lower, cannot bear the not high deficiency of higher reaction temperature, metal oxide decentralization in oxygen carrier.
Three-dimensional ordered macroporous oxide is because tool well-regulated duct arrangement, the feature of aperture between hundreds of nanometer to tens micron, so obtain extensive concern in recent years aspect catalysis, but the oxygen carrier that the active component carrier in chemical chain burning technology makes using three-dimensional ordered macroporous material have not been reported.
Summary of the invention
For the deficiencies in the prior art, the invention provides oxygen carrier of a kind of burning chemistry chains and its preparation method and application.Macroporous structure, the active component that this oxygen carrier has a three-dimensional order be uniformly dispersed and preparation method simple, the advantage such as it is low, active high that this oxygen carrier has reaction bed pressure drop in burning chemistry chains reaction, and diffusion effect is good.
The oxygen carrier of a kind of burning chemistry chains of the present invention, described oxygen carrier is with CeO 2for carrier, with Fe 2o 3for active component, active component 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:
Take styrene as monomer, and adding quality is 0.1～2% sodium peroxydisulfate initator of monomer mass, and in 50～80 ℃ of water-baths, polymerization, after 8～24 hours, is put into drying box dry 12～24 hours polymer.By template heat treatment at 90～120 ℃, strengthen the mechanical strength of template.
2) macropore CeO 2preparation:
With Ce (NO 3) 36H 2o is cerium source, add mole is that the citric acid of 0.2～0.4 times of cerium mole is intercalating agent, joins in absolute ethyl alcohol, is stirred to and is transparent color.By step 1) polystyrene moulding that makes is immersed in this solution, dipping 5～20min final vacuum pumping rate, dry, then repeat above-mentioned dipping-pumping rate-dry run 3～6 times, then in tubular type Muffle furnace, the heating rate with 0.1～5 ℃/min is warming up to 500～900 ℃, 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, by step 2) the three-dimensional ordered macroporous CeO for preparing 2incipient impregnation is in iron nitrate solution, then at room temperature dry, then in 70～100 ℃ dry 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 reaction temperature in air reactor is 500～1000 ℃, and the reaction temperature in fuel reactor is 500～1000 ℃, and reaction pressure is all normal pressure.
Compared with prior art tool of the present invention has the following advantages:
1, Fe of the present invention 2o 3/ CeO 2oxygen carrier has the macroporous structure of three-dimensional order, is conducive to fuel gas and oxygen at Fe 2o 3/ CeO 2diffusion in oxygen carrier, improves the efficiency of fuel gas burning, reduces the pressure drop of reaction bed, improves the stability of oxygen carrier.
2, Fe of the present invention 2o 3/ CeO 2ceO in oxygen carrier 2there is a large amount of oxygen rooms, in air reactor, CeO 2oxygen room can adsorb oxygen molecule, improve Fe 2o 3/ CeO 2the concentration of oxygen molecule activate oxygen molecule on oxygen carrier inner surface, is conducive to the oxidation reaction of active component, improves the recycle chemistry chain required circulation oxygen amount of burning; At combustion reactor CeO 2can make Fe with the synergy of iron 2o 3/ CeO 2oxygen in oxygen carrier reacts rapidly and thoroughly with fuel, improves the utilization rate of circulation oxygen, in addition CeO 2adsorb oxygen on oxygen room also can promote combustion reaction.
3, Fe of the present invention 2o 3/ CeO 2oxygen carrier preparation method is simple; CeO 2oxygen room be conducive to iron at being uniformly distributed of its surface, the Fe of preparation 2o 3/ CeO 2oxygen carrier active component decentralization is high, Heat stability is good.
Accompanying drawing explanation
Fig. 1 is the prepared macropore Fe of the embodiment of the present invention 1 2o 3/ CeO 2scanning electron microscope (SEM) photograph.
The specific embodiment
Below in conjunction with embodiment, further illustrate process and the effect of the inventive method.
Embodiment 1
Get 20ml styrene, be added drop-wise in 110mL deionized water and 60mL ethanol solution, stir on dropping limit, limit, evenly after, add 10mL initator, in initator, sodium peroxydisulfate concentration is 0.068mol/L.At 70 ℃, stir after 24 hours, put into drying box dry 12 hours.By template heat treatment 10 minutes at 110 ℃, strengthen the mechanical strength of template.
Get 18.31gCe (NO 3) 36H 2o, joins in 40mL absolute ethyl alcohol, then adds 4.4g citric acid, is stirred to and is transparent color.Polystyrene moulding is flooded to this solution, and 5 minutes final vacuum pumping rates are dried 2 hours in 70 ℃ of drying boxes.Then repeat above-mentioned dipping-pumping rate-dry run 4 times, then in tubular type Muffle 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, by the macropore CeO of above-mentioned preparation 2incipient impregnation is in iron nitrate solution, and the mass content of iron oxide is 6wt%, 20 ℃ dry, again in 75 ℃ dry more than 12 hours in temperature, be then 800 ℃ of roastings 3 hours, obtain Fe 2o 3/ CeO 2oxygen carrier.
By the above-mentioned oxygen carrier screening making, getting granularity is 40～80 object oxygen carrier 0.5g, carries out performance test on fixed bed quartz tube reactor.Quartz ampoule specification is φ 8 * 2, and unstripped gas consists of: 30%H 2, 60%CO, 10%N 2.Sample rises to 700 ℃ from room temperature, with air oxidation 30 minutes, then passes into nitrogen blowing 10 minutes, passes into unstripped gas and reacts.React after 30 minutes, then pass into nitrogen blowing 10 minutes, then switch to air and be oxidized, after 10 minutes, pass into nitrogen blowing, complete like this once oxidation-reduction circulation.Adopt Agilent 7820 gas-chromatography on-line analyses, TCD detects, 5A molecular sieve column and Porapak Q post.H 2conversion ratio is that 98%, CO conversion ratio is 93%.
Embodiment 2
Press the preparation process in embodiment 1, change iron nitrate concentration is 1mol/L, and the mass content of iron oxide is 11.6wt%.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 99%, CO conversion ratio is 96%.
Embodiment 3
Press the preparation process in embodiment 1, change iron nitrate concentration is 2mol/L, and the mass content of iron oxide is 20.9wt%.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 98%, CO conversion ratio is 96%.
Embodiment 4
Pressing the preparation process in embodiment 1, change the sintering temperature after macropore dipping ferric nitrate, is 700 ℃.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 95%, CO conversion ratio is 91%.
Embodiment 5
Pressing the preparation process in embodiment 1, change the sintering temperature after macropore dipping ferric nitrate, is 750 ℃.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 97%, CO conversion ratio is 93%.
Embodiment 6
Press the preparation process in embodiment 1, get 20ml styrene, be added drop-wise in 80mL deionized water and 40mL ethanol solution, stir on dropping limit, limit.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 93%, CO conversion ratio is 90%.
Embodiment 7
Press the preparation process in embodiment 1, change macropore CeO 2sintering temperature, be 700 ℃.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 91%, CO conversion ratio is 88%.
Embodiment 8
Press the preparation process in embodiment 1, change macropore CeO 2sintering temperature, be 900 ℃.With this catalyst, carry out the test of burning chemistry chains reactivity worth, test condition is with embodiment 1.H 2conversion ratio is that 94%, CO conversion ratio is 91%.
Comparative example
Adopt conventional coprecipitation to prepare Fe 2o 3/ CeO 2particle, roasting condition, performance test condition are with embodiment 1.H 2conversion ratio is that 83%, CO conversion ratio is 79%.

Claims (1)

1. the application of oxygen carrier in burning chemistry chains, is characterized in that: described oxygen carrier is with CeO 2for carrier, with Fe 2o 3for active component, active component Fe 2o 3weight content in oxygen carrier is 5～30%, and the aperture of oxygen carrier is 500nm～50um; Described oxygen carrier preparation method comprises the steps:
1) adopt emulsion polymerization to prepare template:
Take styrene as monomer, adding quality is 0.1～2% sodium peroxydisulfate initator of monomer mass, and in 50～80 ℃ of water-baths, polymerization, after 8～24 hours, is put into drying box dry 12～24 hours polymer, by template heat treatment at 90～120 ℃, strengthen the mechanical strength of template;
2) macropore CeO 2preparation:
With Ce (NO 3) 36H 2o is cerium source, add mole is that the citric acid of 0.2～0.4 times of cerium mole is intercalating agent, join in absolute ethyl alcohol, be stirred to and be transparent color, by step 1) polystyrene moulding that makes is immersed in this solution, dipping 5～20min final vacuum suction filtration, dry, then repeats above-mentioned dipping-suction filtration-dry run 3～6 times, and then in tubular type Muffle furnace, the heating rate with 0.1～5 ℃/min is warming up to 500～900 ℃, 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, by step 2) the three-dimensional ordered macroporous CeO for preparing 2incipient impregnation is in iron nitrate solution, then at room temperature dry, then in 70～100 ℃ dry 8～20 hours then 400～800 ℃ of roastings, obtain Fe 2o 3/ CeO 2oxygen carrier;
The reaction temperature of described oxygen carrier in air reactor is 500～1000 ℃, and the reaction temperature in fuel reactor is 500～1000 ℃.
CN201010511217.0A 2010-10-12 2010-10-12 Oxygen carrier of chemical-looping combustion and preparation method and application thereof Active CN102443454B (en)

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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
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
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
CN110872445B (en) * 2018-08-30 2022-03-04 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
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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CN100540139C (en) * 2007-12-24 2009-09-16 天津大学 Macroporous Pt/the CeO that is used for water gas shift reaction 2Catalysts and its preparation method

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