CN102861587A - Chemical-looping combustion composite oxide oxygen carrier and preparation method and application thereof - Google Patents
Chemical-looping combustion composite oxide oxygen carrier and preparation method and application thereof Download PDFInfo
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- CN102861587A CN102861587A CN2011101884010A CN201110188401A CN102861587A CN 102861587 A CN102861587 A CN 102861587A CN 2011101884010 A CN2011101884010 A CN 2011101884010A CN 201110188401 A CN201110188401 A CN 201110188401A CN 102861587 A CN102861587 A CN 102861587A
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Abstract
The invention discloses a chemical-looping combustion composite oxide oxygen carrier and a preparation method and application thereof. The oxygen carrier is a composite metal oxide with a perovskite ABO3 structure, wherein the A-position is rare earth metal lanthanum, and the B-position is transition metal cobalt. When the oxygen carrier is applied to a chemical-looping combustion technology, the combustion temperature in the air is 500-1000 DEG C, and the reduced temperature in fuel is 500-1000 DEG C. The preparation method of the oxygen carrier uses cobalt nitrate and lanthanum nitrate as precursors, uses citric acid or ethylene glycol as complexing agents and comprises the steps of preparing a solution, performing even mixing by stirring, then performing moisture evaporation, so as to convert the solution from transparent colloidal sol into thick gel, performing drying and finally performing calcinations, and a calcined sample is the composite metal oxide oxygen carrier with the perovskite structure. The oxygen carrier is high in oxygen carrying rate, high in activity and good in stability.
Description
Technical field
The present invention relates to a kind of oxygen carrier take composite oxides as chemical chain burning technology and its preparation method and application, belong to the catalyst technology in burning chemistry chains field.
Background technology
Since the industrial revolution, because a large amount of uses of fossil fuel, the human carbon dioxide (CO that enters in the atmosphere
2) sharp increase of isothermal chamber gas, the greenhouse effects of generation have caused a series of serious environmental problems such as global warming, sea level rise, directly threaten environment for human survival.Therefore, reduce discharging CO
2Become the study hotspot of sustainable development.CO in the flue gas that the traditional combustion mode produces
2Concentration only accounts for 10%-14%, at present the CO of main flow
2Emission-reduction technology is as catching after burning and rich foster burning, at CO
2Separation process need to consume a large amount of energy, and it is too high to cause reducing discharging cost.Burning chemistry chains is a kind of novel combustion system based on the zero-emission theory, and it can be under the prerequisite that does not substantially have energy loss, in combustion process with CO
2Separate.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 is the research emphasis in the burning chemistry chains always.Oxygen carrier circulates between two reactors as medium, ceaselessly the heat of the oxygen in the 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 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 small amount 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(MATTISSON T etc. Fuel, 2001,80 (13)) and CoO-NiO/YSZ(JIN H G etc. Energy Fuels, 1998,12 (6)) etc. combination property is better, and the oxygen carrier rate is limited, circular response is lower, can't bear the not high deficiency of higher reaction temperature, metal oxide decentralization in oxygen carrier but exist.
Summary of the invention
For the deficiencies in the prior art, the invention provides oxygen carrier that is used for chemical chain burning technology of high, the active height of a kind of oxygen carrier rate, good stability and its preparation method and application.
The oxygen carrier of chemical chain burning technology of the present invention is to have perovskite ABO
3The composite metal oxide of structure, A position are rare earth lanthanum, and the B position is transition metals cobalt.
The application of the composite metal oxide of the above-mentioned perovskite structure of the present invention in chemical chain burning technology, wherein composite metal oxide is 500～1000 ℃ in the temperature of combustion synthesis in air, the temperature of reducing in fuel after the burning is 500～1000 ℃, and reaction pressure all is normal pressure.
Above-mentioned composite metal oxide oxygen carrier can be the suitable shape such as sphere, bar shaped, microballoon or abnormity, and particle size is generally 10 μ m-2000 μ m, and preferred particle size is 50 μ m-500 μ m.Can add other suitable inorganic refractory component during use, as aluminium oxide, titanium oxide, magnesia, silica etc. one or more.
The composite metal oxide of perovskite structure of the present invention adopts the complexometry preparation.Detailed process is as follows: take cobalt nitrate, lanthanum nitrate as presoma, citric acid or ethylene glycol are complexing agent, wiring solution-forming and mixing and stirring.Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, and is then dry, last roasting, and the sample after the roasting is the perovskite structure composite metal oxide.
In the method for preparing catalyst of the present invention, complexing agent can be citric acid or ethylene glycol, and complexing agent and metal ion mol ratio are 1:1～5:1, are preferably 1:1～3:1.Preparation and agitating solution are preferably under 50～80 ℃ and carry out at 30～90 ℃.Stir speed (S.S.) is 100～500rpm, is preferably 300～400rpm.Mixing time is 3～8 hours, is preferably 4～6 hours.Baking temperature is 60～200 ℃, is preferably 80～150 ℃.Be 1～36 hour drying time, is preferably 8～24 hours.Roasting is at 400～1000 ℃ of lower roasting 2-15 hours, preferably 600～900 ℃ of lower roastings 3～8 hours.
Chemical chain burning technology oxygen carrier of the present invention is the composite metal oxide of perovskite structure, and its general formula is ABO
3, A is generally the larger rare earth ion of radius, and B is the less transition metal ions of radius.Usually B position metal is the active component of this oxygen carrier, can change this oxygen carrier activity by changing B position metal, and A position metal is not active component usually, just plays the effect that forms perovskite structure and rock-steady structure.Perovskite structure oxide has the advantage of Heat stability is good, in addition, the composite oxides of perovskite structure form the oxygen room easily in roasting process, and the adsorb oxygen on the oxygen room is more active, can oxygenated fuel gas, Lattice Oxygen can be replenished the adsorb oxygen of continuous consumption simultaneously; After entering air reactor, air provides oxygen to perovskite again, so perovskite is a suitable carrier of oxygen.
Compared with prior art, chemical chain burning technology oxygen carrier of the present invention has the advantages such as the preparation method is simple, high, the lasting circulation ability of stability is strong.
Description of drawings
Fig. 1 is the embodiment of the invention 1 prepared perovskite ABO
3The X-ray diffractogram of structure composite metal oxide.
Fig. 2 is the embodiment of the invention 2 prepared perovskite ABO
3The temperature programmed reduction figure of structure composite metal oxide.
The specific embodiment
Further specify process and the effect of the inventive method below in conjunction with embodiment.Among burning chemistry chains oxygen carrier of the present invention and the preparation method, the mol ratio of metal and citric acid is a key factor that whether can form perovskite structure.
Embodiment 1
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Embodiment 2
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 67g citric acid, citric acid and metal ion total amount mol ratio are 2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Embodiment 3
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, then beaker is placed 80 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 100g citric acid, citric acid and metal ion total amount mol ratio are 3:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Embodiment 4
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 80mL, then beaker is placed 40 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Embodiment 5
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 80mL, then beaker is placed 60 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Embodiment 6
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, then beaker is placed 40 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 700 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Embodiment 7
Get 23g Co (NO
3)
26H
2O puts into the beaker of 500mL, adds the distilled water of 100mL, then beaker is placed 60 ℃ water-bath, and mixing speed is 400rpm.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Then lanthanum nitrate hexahydrate is added drop-wise in the cobalt nitrate solution, stirs while dripping.Get the 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, and the beaker of putting into 100mL is stirred to whole dissolvings, after above-mentioned mixed solution stirs 30 minutes, add slowly citric acid solution, stir while dripping.Stir after 5 hours, red tan solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Then take out dried perovskite predecessor, place Muffle furnace, rise to 400 ℃ with the heating rate of 3 ℃/min from room temperature, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 900 ℃ again, and constant temperature calcining 3 hours obtains the composite metal oxide oxygen carrier.
Comparative example
Adopt conventional sol-gel process to prepare cobalt oxide particle, sintering temperature is with embodiment 1.
Embodiment 8
Catalyst performance evaluation prepared in above-described embodiment and the comparative example is carried out as follows.Evaluating catalyst test is carried out in continuous fixed bed reactor, gets catalyst 5ml, with count with order quartz sand by volume 1:1 mix.Fuel gas is carbon monoxide (10 vol %CO, 90 vol %N
2), flow is 100ml/min, and reaction temperature is 500 ℃, and reaction pressure is normal pressure.Reduce after 5 minutes, switch to nitrogen, temperature remains on 500 ℃, keeps 20 minutes.Then pass into air, flow is 20ml/min, and temperature remains on 500 ℃.React after 10 minutes, switch to nitrogen again, temperature remains unchanged.Pass into fuel gas, reaction condition is consistent with above-mentioned reduction reaction conditions again.Adopt 6890 type gas-chromatography on-line analyses, 5A molecular sieve column and Porapak Q post, TCD detects.Evaluation results sees Table 1.
The reactivity worth of table 1 catalyst.
| Catalyst | CO conversion ratio (%) |
| Embodiment 1 | 100 |
| Embodiment 2 | 99 |
| Embodiment 3 | 97 |
| Embodiment 4 | 98 |
| Embodiment 5 | 99 |
| Embodiment 6 | 100 |
| Embodiment 7 | 99 |
| Comparative example | 87 |
The CO conversion ratio is 30 times mean value of circulation.
Claims (6)
1. the oxygen carrier of a chemical chain burning technology, it is characterized in that: oxygen carrier is to have perovskite ABO
3The composite metal oxide of structure, A position are rare earth lanthanum, and the B position is transition metals cobalt.
2. according to oxygen carrier claimed in claim 1, it is characterized in that: the composite metal oxide oxygen carrier is sphere, bar shaped, microballoon or abnormity, and particle size is 10 μ m-2000 μ m.
3. claim 1 or 2 application of described oxygen carrier in chemical chain burning technology, wherein composite metal oxide is 400～1000 ℃ in the temperature of combustion synthesis in air, and the temperature of reducing in fuel after the burning is 400～1000 ℃, and reaction pressure is normal pressure.
4. the preparation method of the oxygen carrier of the described chemical chain burning technology of claim 1, take cobalt nitrate, lanthanum nitrate as presoma, take citric acid or ethylene glycol as complexing agent, wiring solution-forming and mixing and stirring, then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, and is then dry, last roasting, the sample after the roasting is perovskite structure composite metal oxide oxygen carrier.
5. in accordance with the method for claim 4, it is characterized in that: complexing agent and metal ion mol ratio are 1:1～5:1, preparation and agitating solution carry out under 30～90 ℃, mixing time is 3～8 hours, baking temperature is 60～200 ℃, be 1～36 hour drying time, and roasting was at 400～1000 ℃ of lower roasting 2-15 hours.
6. in accordance with the method for claim 5, it is characterized in that: complexing agent and metal ion mol ratio are 1:1～3:1, preparation and agitating solution carry out under 50～80 ℃, mixing time is 4～6 hours, baking temperature is 80～150 ℃, be 8～24 hours drying time, and roasting is 600～900 ℃ of lower roastings 3～8 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599788A (en) * | 2013-11-01 | 2014-02-26 | 中国石油化工股份有限公司 | Cobalt-based catalyst for CO hydrogenation and preparation method and application thereof |
| CN105597767A (en) * | 2015-11-24 | 2016-05-25 | 西安科技大学 | Low temperature plasma method for preparation of perovskite denitration catalyst |
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2011
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| US4255602A (en) * | 1979-12-10 | 1981-03-10 | Monsanto Company | Stilbene formation by means of toluene dehydrocoupling using a cobalt-lanthanide catalyst |
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Non-Patent Citations (4)
| Title |
|---|
| 《《催化学报》网站》 20110623 DAI Xiaoping et al， "Nano-Perovskite-Based (LaMO3) Oxygen Carrier for Syngas Generation by Chemical-Looping Reforming of Methane" 英文摘要 1-3 , * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103599788A (en) * | 2013-11-01 | 2014-02-26 | 中国石油化工股份有限公司 | Cobalt-based catalyst for CO hydrogenation and preparation method and application thereof |
| CN103599788B (en) * | 2013-11-01 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of cobalt-base catalyst for CO hydrogenation and its preparation method and application |
| CN105597767A (en) * | 2015-11-24 | 2016-05-25 | 西安科技大学 | Low temperature plasma method for preparation of perovskite denitration catalyst |
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Application publication date: 20130109 |