CN102862956B - The application of a kind of oxygen carrier with perovskite structure in hydrogen production of chemical chain and preparation - Google Patents
The application of a kind of oxygen carrier with perovskite structure in hydrogen production of chemical chain and preparation Download PDFInfo
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- CN102862956B CN102862956B CN201110188426.0A CN201110188426A CN102862956B CN 102862956 B CN102862956 B CN 102862956B CN 201110188426 A CN201110188426 A CN 201110188426A CN 102862956 B CN102862956 B CN 102862956B
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Abstract
The invention discloses the application of a kind of perovskite structure composite oxide in recycle chemistry chain hydrogen production and preparation, there is the complex metal oxides AB ' of perovskite structure
xb
1-xo
3, wherein A is rare earth lanthanum, B, B ' and be respectively transition metals cobalt and copper, 0<x<1.The application of oxygen carrier in recycle chemistry chain hydrogen production, the temperature of combustion wherein in water vapour reactor is 500 ~ 800 DEG C, and the reduction temperature in fuel reactor is 500 ~ 800 DEG C.Oxygen carrier preparation method is for presoma with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, lanthanum nitrate, with citric acid or ethylene glycol for complexing agent, wiring solution-forming mixing and stirring, then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, the sample after roasting is the complex metal oxides with perovskite structure.Oxygen carrier of the present invention has the advantages such as oxygen carrier rate is high, activity is high, good stability.
Description
Technical field
The present invention relates to the application of a kind of perovskite structure composite oxide in recycle chemistry chain hydrogen production technology and preparation method, belong to hydrogen production of chemical chain field.
Background technology
Nineteen eighty-three, Germany scientist Richter and Knoche proposes the concept of burning chemistry chains (chemical looping combustion, CLC) first.This combustion technology and the maximum difference of common combustion technology are the oxygen molecules directly do not used in air, but use the Sauerstoffatom in oxygen carrier to complete the combustion processes of fuel, products of combustion (mainly CO
2and water vapour) can not by the nitrogen dilution in air very high concentrations, almost pure CO can be obtained by simple condensation
2, achieve CO to simple and less energy-consumption
2separation and trapping; In addition, because the operating temperature of fuel reactor and air reactor is relatively low, almost generate without thermal NO x and Quick-type NOx in air reactor, and in fuel reactor, owing to not contacting with oxygen, do not have fuel type NOx to generate.
Hydrogen receives close concern as pollution-free, the eco-friendly economy energy, has purposes widely.In view of the CO 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, complete the regeneration of oxygen carrier using water vapour replacement air as oxygenant introducing air reactor, water vapour is also reduced generation hydrogen simultaneously.Current, in the world a lot of study group Hatano of comprising Japan to solid waste such as polyethylene for fuel NiO and Fe
2o
3deng for the people such as oxygen carrier, Korea S Son are to CH
4for fuel NiO and Fe
2o
3fan L-S for oxygen carrier, the U.S. teaches study group to the Fe taking coal as fuel
2o
3for the CLC hydrogen production process of oxygen carrier etc. is studied.
Oxygen carrier is as medium, circulate between two reactors, ceaselessly the heat that the oxygen in air (water vapour) reactor and reaction generate is delivered to fuel reactor and carries out reduction reaction, therefore the character of oxygen carrier directly affects the operation of whole burning chemistry chains/hydrogen manufacturing.Therefore, high-performance oxygen carrier realizes 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, and comprise Fe, Ni, Co, Cu, Mn, Cd etc., 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. over-all properties is better, but has that oxygen carrier rate is limited, circulating reaction is lower, cannot bear the not high deficiency of higher temperature of reaction, metal oxide dispersity in oxygen carrier.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of by complex metal oxides oxygen carrier being used for recycle chemistry chain hydrogen production of perovskite structure and preparation method thereof, the oxygen carrier rate of this oxygen carrier is high, oxygen cycle ability is strong, good stability.
The complex metal oxides oxygen carrier of recycle chemistry chain hydrogen production of the present invention is the complex metal oxides with perovskite structure, and general formula is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, and B is transition metals cobalt, 0<x<1.
In the present invention's application, with uhligite AB '
xb
1-xo
3the complex metal oxides of structure is oxygen carrier, and the temperature of reaction of oxygen carrier in fuel is 500 ~ 800 DEG C, and the temperature of reaction of oxygen carrier in water vapour is 500 ~ 800 DEG C, and the fuel of use can be solid fuel also can be gaseous fuel, preferred the latter.
Above-mentioned complex metal oxides oxygen carrier can be spherical, bar shaped, the suitable shape such as microballoon or abnormity, and particle size is generally 10 μm ~ 500 μm, and preferred particle size is 50 μm ~ 200 μm.Other suitable inorganic refractory component can be added during use, as aluminum oxide, titanium oxide, magnesium oxide, silicon oxide etc. one or more.
The complex metal oxides of perovskite structure of the present invention adopts citric acid complex method preparation.Detailed process is as follows: with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate, cupric nitrate for presoma, and citric acid or ethylene glycol are complexing agent, wiring solution-forming mixing and stirring; Then carry out moisture evaporation, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, and the sample obtained is for having perovskite structure complex metal oxides.
In 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 ~ 8:1, is preferably 1:1 ~ 4:1.Preparation and stirred solution, at 20 ~ 90 DEG C, carry out at being preferably 50 ~ 70 DEG C.Stir speed (S.S.) is 200 ~ 500rpm, is preferably 300 ~ 400rpm.Churning time is 3 ~ 8 hours, is preferably 4 ~ 6 hours.Drying temperature is 60 ~ 200 DEG C, is preferably 80 ~ 150 DEG C.Time of drying is 1 ~ 36 hour, is preferably 8 ~ 24 hours.Maturing temperature is 400 ~ 1000 DEG C, and roasting time is roasting 2 ~ 15 hours, is preferably roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
Compared with prior art, recycle chemistry chain hydrogen production composite metal oxide oxygen carrier of the present invention and its preparation method and application tool has the following advantages:
1, the present invention prepares a kind of complex metal oxides general formula with perovskite structure is AB '
xb
1-xo
3, wherein A is rare earth lanthanum, and B ' is transition metal copper, and B is transition metals cobalt, 0<x<1.
2, the present invention has the application of complex metal oxides in hydrogen production of chemical chain technology of perovskite structure, rare earth lanthanum on A position can improve structural stability and the thermostability of uhligite, improve oxygen carrier persistent loop ability and work-ing life, the upper two kinds of different transition metal in B position adulterate mutually, make its metal ion electric charge, radius changes, lattice parameter changes, forming more Lacking oxygen for hydrogen production of chemical chain provides enough lattice oxygen, improve the oxygen carrier rate of oxygen carrier, promote that oxygen carrier carries out efficient oxidation-reduction process, accelerate the cycle efficiency of oxygen carrier in air reactor and combustion reactor.
3, the present invention has that the complex metal oxides oxygen carrier preparation method of perovskite structure is simple, cost is low, is suitable for industrial application.
Accompanying drawing explanation
The X-ray diffractogram with the complex metal oxides oxygen carrier of perovskite structure of Fig. 1 prepared by the embodiment of the present invention 1.
Embodiment
Process and the effect of the inventive method is further illustrated below in conjunction with embodiment.
Embodiment 1
Get 20.7gCo (NO
3)
26H
2o and 1.9gCu (NO
3)
23H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Cu be 0.9/0.1, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, stirring velocity is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
36H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, now after above-mentioned mixing solutions stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the loft drier of 110 DEG C, dried overnight.Then take out dried uhligite precursor, be placed in retort furnace, rise to 400 DEG C with the temperature rise rate of 3 DEG C/min from room temperature, constant temperature calcining 3 hours, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min again, constant temperature calcining 4 hours, obtain complex metal oxides oxygen carrier.
Embodiment 2
Get 16.1gCo (NO
3)
26H
2o and 5.7gCu (NO
3)
23H
2o puts into the beaker of 500mL, and the mol ratio making Co and Cu is 0.7/0.3, is stirred to whole dissolving.Add the distilled water of 100mL, then beaker is placed in the water-bath of 80 DEG C, stirring velocity is 400rpm.Get 34.3g La (NO
3)
36H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and copper nitrate solution, dropping limit, limit is stirred.Get 67g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixing solutions stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the loft drier of 110 DEG C, dried overnight.Then take out dried uhligite precursor, be placed in retort furnace, rise to 400 DEG C with the temperature rise rate of 3 DEG C/min from room temperature, constant temperature calcining 3 hours, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min again, constant temperature calcining 4 hours, obtain complex metal oxides oxygen carrier.
Embodiment 3
Get 11.5g Co (NO
3)
26H
2o, 9.5gCu (NO
3)
23H
2o puts into the beaker of 500mL, and the mol ratio making Co and Cu is 0.5/0.5, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, stirring velocity is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
36H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixing solutions stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the loft drier of 110 DEG C, dried overnight.Then take out dried uhligite precursor, be placed in retort furnace, rise to 400 DEG C with the temperature rise rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain complex metal oxides oxygen carrier.
Embodiment 4
Get 4.6g Co (NO
3)
26H
2o and 15.2gCu (NO
3)
23H
2o puts into the beaker of 500mL, makes the mol ratio of Co and Cu be put into the beaker of 500mL, makes the mol ratio of Co and Cu be 0.2/0.8, add the distilled water of 100mL, then beaker is placed in the water-bath of 80 DEG C, stirring velocity is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
36H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, dropping limit, limit is stirred.Get 40g citric acid, citric acid and metal ion total amount mol ratio are 1.2:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixing solutions stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the loft drier of 110 DEG C, dried overnight.Then take out dried uhligite precursor, be placed in retort furnace, rise to 400 DEG C with the temperature rise rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain complex metal oxides oxygen carrier.
Embodiment 5
Get 20.7gCo (NO
3)
26H
2o and 1.9gCu (NO
3)
23H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Cu be 0.9/0.1, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, stirring velocity is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
36H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, dropping limit, limit is stirred.Get 67g citric acid, citric acid and metal ion total amount mol ratio are 2:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixing solutions stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the loft drier of 110 DEG C, dried overnight.Then take out dried uhligite precursor, be placed in retort furnace, rise to 400 DEG C with the temperature rise rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain complex metal oxides oxygen carrier.
Embodiment 6
Get 20.7gCo (NO
3)
26H
2o and 1.9gCu (NO
3)
23H
2o puts into the beaker of 500mL, makes the mol ratio of its Co and Cu be 0.9/0.1, adds the distilled water of 100mL, and then beaker is placed in the water-bath of 80 DEG C, stirring velocity is 400rpm, is stirred to whole dissolving.Get 34.3g La (NO
3)
36H
2o, is placed with in the beaker of 100mL distilled water, is stirred to whole dissolving.Then lanthanum nitrate hexahydrate is added drop-wise in the mixing solutions of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and cupric nitrate, dropping limit, limit is stirred.Get 100g citric acid, citric acid and metal ion total amount mol ratio are 3:1, are placed with in the beaker of 100mL and are stirred to whole dissolving, after above-mentioned mixing solutions stirs 30 minutes, add citric acid solution slowly, and dropping limit, limit is stirred.Stir after 5 hours, brown solution has dewatered and has become thick gel, is taken out by gel and puts in the loft drier of 110 DEG C, dried overnight.Then take out dried uhligite precursor, be placed in retort furnace, rise to 400 DEG C with the temperature rise rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the temperature rise rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain complex metal oxides oxygen carrier.
Comparative example 1
Adopt conventional sol-gel method to prepare cobalt oxide particle (load is on silicon oxide), maturing temperature is with embodiment 1.
Comparative example 2
A position undopes potassium metal, adopts same method preparation to have the LaCoO of perovskite structure
3complex metal oxides.
Catalyst performance evaluation prepared in above-described embodiment and comparative example is carried out as follows.Catalyst Evaluation Test carries out in continuous fixed bed reactor, gets catalyzer 5ml, with same order number quartz sand by volume 1:1 mix.Fuel gas is synthetic gas (30vol%H
2, 60vol%CO, 10 vol%N
2), flow is 120ml/min, and temperature of reaction is 700 DEG C, and reaction pressure is normal pressure.After reduction in 3 minutes terminates, switch to nitrogen, simultaneous temperature is down to 600 DEG C, keeps 30 minutes.Then pass into water vapour, flow is 30ml/min, and temperature remains on 600 DEG C.React after 10 minutes, then switch to nitrogen, simultaneous temperature rises to 700 DEG C.Pass into fuel gas again, reaction conditions is consistent with above-mentioned reduction reaction conditions.Adopt the on-line analysis of SP-3820 type gas-chromatography, 5A molecular sieve column and Porapak Q post, TCD detects.Evaluation results is in table 1.
The reactivity worth of table 1 catalyzer.
| Catalyzer | Circulate 50 times, CO transformation efficiency % | Circulate 100 times, CO transformation efficiency % | H 2Output *,（ml/g Co） | Coke content, wt% |
| Embodiment 1 | 98 | 98 | 347 | 0.54 |
| Embodiment 2 | 98 | 98 | 355 | 0.37 |
| Embodiment 3 | 98 | 98 | 351 | 0.48 |
| Embodiment 4 | 99 | 97 | 329 | 0.29 |
| Embodiment 5 | 98 | 98 | 335 | 0.43 |
| Embodiment 6 | 98 | 98 | 324 | 0.46 |
| Comparative example 1 | 87 | 85 | 220 | 5.35 |
| Comparative example 2 | 97 | 95 | 259 | 1.42 |
*the productive rate of hydrogen carries out calculating (water is excessive) based on Co, i.e. every gram of Co reductive water steam
The volume of hydrogen can be generated.
Claims (3)
1. the application of oxygen carrier in hydrogen production of chemical chain, is characterized in that: this oxygen carrier is the complex metal oxides with perovskite structure, and general formula is AB '
xb
1-xo
3wherein A is rare earth lanthanum, B ' is transition metal copper, B is transition metals cobalt, 0<x<1, and the temperature of combustion of oxygen carrier in water vapour reactor is 500 ~ 800 DEG C, reduction temperature in fuel reactor is 500 ~ 800 DEG C, the preparation process of oxygen carrier is as follows: with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, lanthanum nitrate, cupric nitrate for presoma, and citric acid or ethylene glycol are complexing agent, wiring solution-forming mixing and stirring; Then moisture evaporation is carried out, the colloidal sol of solution went from clear is transformed into the gel of thickness, final drying, roasting, the sample obtained is for having perovskite structure complex metal oxides, and its complexing agent and metal ion mol ratio are 1:1 ~ 8:1, preparation and stirred solution carry out at 20 ~ 90 DEG C, churning time is 3 ~ 8 hours, and stirring velocity is 200 ~ 500rpm, and drying temperature is 60 ~ 200 DEG C, time of drying is 1 ~ 36 hour, and roasting is roasting 2-15 hour at 400 ~ 1000 DEG C.
2. according to application according to claim 1, it is characterized in that: described complex metal oxides oxygen carrier is spherical, bar shaped or abnormity, and particle size is 10 μm ~ 500 μm.
3. according to application according to claim 1, it is characterized in that: complexing agent and metal ion mol ratio are 1:1 ~ 4:1, preparation and stirred solution carry out at 50 ~ 70 DEG C, churning time is 4 ~ 6 hours, stir speed (S.S.) is 300 ~ 400rpm, drying temperature is 80 ~ 150 DEG C, and time of drying is 8 ~ 24 hours, roasting roasting 3 ~ 8 hours at 700 ~ 900 DEG C.
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