CN102862954B - Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production - Google Patents
Application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production Download PDFInfo
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- CN102862954B CN102862954B CN201110188403.XA CN201110188403A CN102862954B CN 102862954 B CN102862954 B CN 102862954B CN 201110188403 A CN201110188403 A CN 201110188403A CN 102862954 B CN102862954 B CN 102862954B
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Abstract
The invention discloses application and preparation of perovskite structure composite oxide in chemical looping circulation hydrogen production. The perovskite structure composite oxide is composite metallic oxide provided with a perovskite ABO3 structure, an A grade is rare earth metal lanthanum, and a B grade is transition metal cobalt; and the reaction temperature of the oxygen carrier in fuel is 600-1200 DEG C, and the reaction temperature of the oxygen carrier in steam is 600-1200 DEG C. The preparation process comprises the following steps: taking cobalt nitrate and lanthanum nitrate as a precursor, and taking citric acid as a complexing agent to prepare into a solution; evenly mixing and stirring; carrying out water evaporation, so that the solution is changed from transparent sol to thick gel; and drying and finally roasting, wherein the roasted sample is the perovskite structure composite metal oxide. The oxygen carrier is high in oxygen carrying rate, high in activity and good in stability.
Description
Technical field
The present invention relates to application and the preparation method of a kind of perovskite structure composite oxide in recycle chemistry chain hydrogen production technology, belong to hydrogen production of chemical chain field.
Background technology
In order to control, take CO in the electric power generative process that coal is fuel
2discharge, and improve generating efficiency and use fuel that other C/H is lower and the CO such as renewable resource
2control route is compared, CO in the fossil fuel power production processes such as coal
2recovery and storage (CCS) be unique effective mode, can reach in a short time effective reduction of discharging CO
2but target CCS under three kinds of CO
2discharge-reducing method (comprise before burning, pure oxygen burning and burning after) although and relevant technology can reach CO
2recovery target, but can cause that system effectiveness reduces and CO
2the increase of cost recovery, makes CO
2recovery technology apply and be subject to great obstruction.Therefore explore and study novel CO
2recovery technology is for CO in combustion of fossil fuel process
2reduction of discharging be significant.
Nineteen eighty-three, Germany scientist Richter and Knoche propose the concept of burning chemistry chains (chemical looping combustion, CLC) first.The difference of this combustion technology and common combustion technology maximum is directly not use airborne oxygen molecule, but with the oxygen atom in oxygen carrier, completes the combustion process of fuel, and combustion product (is mainly CO
2and steam) can be by airborne nitrogen dilution and very high concentrations can obtain almost pure CO by simple condensation
2, realized to simple and low energy consumption CO
2separated and trapping; In addition, because the running temperature of fuel reactor and air reactor is relatively low, in air reactor, almost without thermal NO x and Quick-type NOx, generate, and in fuel reactor, owing to not contacting with oxygen, do not have fuel type NOx to generate.
Hydrogen has received close concern as pollution-free, the eco-friendly economy energy, has purposes widely.CO in view of burning chemistry chains method
2interior separation characteristic, the hydrogen manufacturing of applied chemistry chain combustion method also becomes a current study hotspot.Similar with CLC process, the steam of usining replaces air to introduce as oxidant the regeneration that air reactor completes oxygen carrier, and steam is also reduced generation hydrogen simultaneously.Current, a lot of seminar comprise that Japanese Hatano is to take the solid waste such as polyethylene as fuel NiO and Fe in the world
2o
3deng being the people such as oxygen carrier, Korea S Son to CH
4for fuel NiO and Fe
2o
3for the Fan L-S professor seminar of oxygen carrier, the U.S. is to take the Fe that coal is fuel
2o
3for the CLC hydrogen production process of oxygen carrier etc. is studied.
Oxygen carrier is as medium, between two reactors, circulate, ceaselessly the heat of the oxygen in air (steam) 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/hydrogen manufacturing.Therefore, high-performance oxygen carrier is to realize having CO
2the key of the burning chemistry chains/hydrogen producing technology of enriched character.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/hydrogen production 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(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, but exist, 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.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of by the composite metal oxide of perovskite structure for oxygen carrier of recycle chemistry chain hydrogen production and preparation method thereof, the oxygen carrier rate of this oxygen carrier is high, oxygen cycle ability strong, good stability.
The present invention is applied in recycle chemistry chain hydrogen production with perovskite structure composite oxide, and perovskite structure composite oxide is to have perovskite ABO
3the composite metal oxide of structure, A position is rare earth lanthanum, B position is transition metals cobalt.
In the present invention's application, with perovskite ABO
3the composite metal oxide of structure is oxygen carrier, and the reaction temperature of oxygen carrier in fuel is 600 ~ 1200 ℃, and the reaction temperature of oxygen carrier in steam is 600 ~ 1200 ℃, and the fuel of use can be that solid fuel can be also fuel gas, preferably the latter.
Above-mentioned composite metal oxide oxygen carrier can be the suitable shape such as spherical, 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.During use, can add other suitable inorganic refractory component, as aluminium oxide, titanium oxide, magnesia, silica etc. one or more.
The preparation process of above-mentioned composite metal oxide oxygen carrier is: take cobalt nitrate, lanthanum nitrate is presoma, take citric acid as complexing agent, wiring solution-forming mixing and stirring.Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, then dry, last roasting, and the sample after roasting is perovskite structure composite metal oxide.
In above-mentioned preparation process, complexing agent and metal ion mol ratio are 1:1～5:1, are preferably 1:1～3:1.The temperature of preparation and agitating solution is 30～90 ℃, is preferably 50～80 ℃.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 roasting 2-15 hour at 400～1000 ℃, preferably roasting 3～8 hours at 600～900 ℃.
The present invention is by the composite metal oxide of perovskite structure for recycle chemistry chain hydrogen production, and the general formula of perovskite structure composite metal oxide is ABO
3a is generally the rare earth ion that radius is larger, B is the transition metal ions that radius is less, conventionally 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 conventionally, just play the effect that forms perovskite structure rock-steady structure.Perovskite structure oxide has advantages of Heat stability is good, and in addition, perovskite can form the oxygen room of some in roasting process, and the adsorb oxygen on oxygen room is more active, can oxygenated fuel, and Lattice Oxygen can be supplemented the adsorb oxygen of continuous consumption simultaneously; Enter after hydrogen-manufacturing reactor, steam can provide oxygen to perovskite again, and while releasing hydrogen gas, so perovskite is a suitable carrier of oxygen.
Compared with prior art, hydrogen production of chemical chain oxygen carrier of the present invention has the advantages such as preparation method is simple, stability is high, lasting circulation ability is strong.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the obtained composite metal oxide oxygen carrier of the embodiment of the present invention 1.
Fig. 2 is the temperature programmed reduction figure of the obtained composite metal oxide oxygen carrier of the embodiment of the present invention 2.
The specific embodiment
Below in conjunction with embodiment, further illustrate process and the effect of the inventive method.In hydrogen production of chemical chain oxygen carrier of the present invention and 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 in to the water-bath of 80 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours, obtains 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 in to the water-bath of 80 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours, obtains 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 in to the water-bath of 80 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours, obtains 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 in to the water-bath of 40 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours, obtains 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 in to the water-bath of 60 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours, obtains 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 in to the water-bath of 40 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 700 ℃ again, and constant temperature calcining 3 hours, obtains 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 in to the water-bath of 60 ℃, 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 cobalt nitrate solution, stir on dropping limit, limit.Get 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, until above-mentioned mixed solution, stir after 30 minutes, add slowly citric acid solution, and stir on dropping limit, limit.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 ℃ to dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, with the heating rate of 3 ℃/min, from room temperature, rise to 400 ℃, constant temperature calcining 2 hours, heating rate with 10 ℃/min rises to 900 ℃ again, and constant temperature calcining 3 hours, obtains 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 comparative example is carried out as follows.Evaluating catalyst test is carried out in continuous fixed bed reactor, gets catalyst 5ml, with same order count 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 650 ℃, and reaction pressure is normal pressure.Reduce after 5 minutes, switch to nitrogen, simultaneous temperature is down to 650 ℃, keeps 20 minutes.Then use syringe pump injected water, flow is 50ml/h, and water is first vaporized, and then enters preheater, and the temperature of preheater remains on 300 ℃, then enters reactor.React after 10 minutes, switch to air and continue oxidation 3min, then switch to nitrogen, simultaneous 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 is in Table 1.
The reactivity worth of table 1 catalyst.
| Catalyst | CO conversion ratio (%) | H 2Output ※, (ml/g Co) |
| Embodiment 1 | 99 | 368 |
| Embodiment 2 | 99 | 337 |
| Embodiment 3 | 96 | 312 |
| Embodiment 4 | 96 | 339 |
| Embodiment 5 | 97 | 342 |
| Embodiment 6 | 100 | 389 |
| Embodiment 7 | 97 | 361 |
| Comparative example | 84 | 268 |
The productive rate of ※ hydrogen be take Co and as basis, is calculated (water is excessive), i.e. every gram of Co reductive water steam
Can generate the volume of hydrogen.CO conversion ratio and hydrogen output are the circulation mean value of 30 times.
Claims (2)
1. the application of perovskite structure composite oxide in recycle chemistry chain hydrogen production, is characterized in that: perovskite structure composite oxide is to have perovskite ABO
3the composite metal oxide of structure, A position is rare earth lanthanum, and B position is transition metals cobalt, and composite metal oxide oxygen carrier is spherical, bar shaped or abnormity, and particle size is 10 μ m-2000 μ m, perovskite ABO
3the reaction temperature of structure composite metal oxide oxygen carrier in fuel is 600 ~ 1200 ℃, and the reaction temperature of oxygen carrier in steam is 600 ~ 1200 ℃, perovskite ABO
3the preparation process of structure composite metal oxide is: take cobalt nitrate, lanthanum nitrate is presoma, take citric acid as complexing agent, wiring solution-forming mixing and stirring; Then carry out moisture evaporation, solution is transformed into the gel of thickness by transparent colloidal sol, then dry, last roasting, the sample after roasting is perovskite structure composite metal oxide, wherein complexing agent and metal ion mol ratio are 1:1～5:1, the temperature of preparation and agitating solution is 30～90 ℃, and mixing time is 3～8 hours, and baking temperature is 60～200 ℃, be 1～36 hour drying time, and roasting is roasting 2-15 hour at 400～1000 ℃.
2. according to application claimed in claim 1, it is characterized in that: complexing agent and metal ion mol ratio are 1:1～3:1, the temperature of preparation and agitating solution is 50～80 ℃, mixing time is 4～6 hours, baking temperature is 80～150 ℃, be 8～24 hours drying time, roasting roasting 3～8 hours at 600～900 ℃.
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| CN114684860A (en) * | 2022-03-31 | 2022-07-01 | 华中科技大学 | BaMnO suitable for direct chemical looping hydrogen production of coal3Preparation and application of perovskite oxygen carrier |
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