CN102441396A - Application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method - Google Patents
Application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method Download PDFInfo
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- CN102441396A CN102441396A CN2010105108989A CN201010510898A CN102441396A CN 102441396 A CN102441396 A CN 102441396A CN 2010105108989 A CN2010105108989 A CN 2010105108989A CN 201010510898 A CN201010510898 A CN 201010510898A CN 102441396 A CN102441396 A CN 102441396A
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 52
- 239000001301 oxygen Substances 0.000 title claims abstract description 52
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000126 substance Substances 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 24
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000446 fuel Substances 0.000 claims abstract description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 3
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 16
- 238000001354 calcination Methods 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 8
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002737 fuel gas Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 229910000943 NiAl Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000036301 sexual development Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
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Abstract
The invention discloses application of a double perovskite type oxide oxygen carrier in the hydrogen production of a chemical chain and a preparation method. The oxygen carrier is a composite metal oxide with a double perovskite structure; the general formula of the composite metal oxide is A2B'B''O6, wherein A is rare earth metal lanthanum, B' is transition metal nickel, and B'' is transition metal iron; the combustion temperature of the oxygen carrier in water vapor is 500-1,000 DEG C; the reduction temperature of the oxygen carrier in fuel after the oxygen carrier is combusted is 500-1,000 DEG C; and the reaction pressure is the normal pressure. The preparation method comprises the following steps of: taking iron nitrate, nickel nitrate and lanthanum nitrate as precursors, taking citric acid as a complexing agent, preparing a solution from the precursors and the complexing agent, and evenly mixing and stirring; and then, carrying out water evaporation while the solution changes into viscous gel from transparent colloidal sol, then, drying, and roasting, wherein the roasted sample is the composite metal oxide with the double perovskite structure. The oxygen carrier prepared by the preparation method has high oxygen-carrying rate, high activity and good stability.
Description
Technical field
The present invention relates to application and the preparation method of a kind of double-perovskite type oxide oxygen carrier in chemical chain hydrogen manufacturing, belong to the catalyst technology of chemical chain hydrogen preparation field.
Background technology
In the direct combustion process of traditional fossil fuel, because N
2Dilution, CO in the flue gas of generation
2Only account for 10%～14%, CO
2Separating energy consumption higher.With novel energy transfer principle and CO
2Enrichment process has combination, and one that solves fossil energy utilization and enforcement environmental protection beyond doubt is rich in change sexual development direction.(chemical looping combustion, CLC) technology has low energy consumption CO based on burning chemistry chains
2Enrichment, high-energy conversion efficiency, low conventional pollutant (NO
xAnd SO
xDeng) characteristic such as discharging, become main research direction.Chemical chain burning technology is oxygen carrier with the metal oxide, and oxygen carrier carries out oxidation 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 energy 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 reactors 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. combination property is better, and the reaction bed pressure drop is big, the oxygen carrier aperture is little, the oxygen carrier rate is limited, circular response property is lower, can't bear the not high deficiency of higher reaction temperature, metal oxide decentralization in oxygen carrier but exist.
Hydrogen has received close concern as pollution-free, the eco-friendly economy energy, and purposes is widely arranged.CO in view of the burning chemistry chains method
2Interior separation characteristic, the hydrogen manufacturing of applied chemistry chain firing method also become a current research focus.Similar with the CLC process, replace air to introduce the regeneration that air reactor is accomplished oxygen carrier with steam as oxidant, steam also is reduced generation hydrogen simultaneously.Current, the Hatano that a lot of in the world seminar comprise Japan is to being fuel NiO and Fe with solid waste such as polyethylene
2O
3Deng being people such as oxygen carrier, Korea S Son to CH
4Be fuel NiO and Fe
2O
3For the Fan L-S of oxygen carrier, U.S. professor seminar to being the Fe of fuel with the coal
2O
3For the CLC hydrogen production process of oxygen carrier etc. is studied.
Summary of the invention
To the deficiency of prior art, the invention provides the oxygen carrier that is used for chemical chain hydrogen producing technology of high, the active height of a kind of oxygen carrier rate, good stability.
The oxygen carrier of the present invention's chemistry chain hydrogen producing technology is the composite metal oxide with structure of double perovskite, and general formula is A
2B ' B " O
6, A is a rare earth lanthanum, B ' is a transiting metal nickel, B " and be transition metal iron.
The application of the composite metal oxide of the above-mentioned structure of double perovskite of the present invention in chemical chain hydrogen manufacturing; Wherein the composite metal oxide temperature of in steam, burning is 500～1000 ℃; The temperature that reduce in fuel the burning back is 500～1000 ℃, and reaction pressure all is a normal pressure.
Above-mentioned composite metal oxide oxygen carrier can be suitable shape such as sphere, bar shaped, microballoon, 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 citric acid complex method preparation.Detailed process is following: with ferric nitrate, nickel nitrate, lanthanum nitrate is presoma, and citric acid or ethylene glycol are complexing agent, wiring solution-forming and mixing and stirring.Carry out water evaporates then, solution is transformed into the gel of thickness by transparent colloidal sol, dry then, 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.Sintering temperature is 600～1200 ℃, and roasting time is 2-15 hour, preferably 800～1000 ℃ of following roastings 3～8 hours.
Perovskite composite oxides has good high high-temp stability and catalytic, and the character of its redox catalysis is paid close attention to widely.Structurally double-perovskite and individual layer perovskite composite oxide ABO
3Compare existing similarity difference is arranged again; Similarity is that they all at high temperature just possibly form material; Stable skeleton structure is all arranged, and the cation in the skeleton structure has certain instead property, can produce oxygen room or transition metal oxide variation of valence and forms defective; Can change oxygen adsorption/desorption character thus, improve catalytic performance.Difference is in the double-perovskite type composite oxides structure, and the octahedral structure of B position ion is by B ' O
6And B " O
6Alternately arrange and form each B ' and B " ion separated by oxonium ion form B '-O-B " structure.Usually in the double-perovskite type composite oxides; Because B ' and B " ion has different electron configurations; the different ionic radius and the exchange interaction of different ions kind and type each other; therefore can realize material property regulate and control; so see that from the structural chemistry angle double-perovskite type composite oxides can provide abundant more conversion compound mode to regulate and control the space with doping than single perovskite composite oxide, this point is the double-perovskite type catalyst place of in catalytic chemistry, fully developing talents than single perovskite type catalyst just through the combination that changes them.
The oxygen carrier of the present invention's chemistry chain hydrogen manufacturing is the composite metal oxide of perovskite structure, and its general formula is A
2B ' B " O
6, A is a rare earth lanthanum, B ' is a transiting metal nickel, B " be transition metal iron, compared with prior art the present invention has following advantage:
1, double-perovskite type composite oxides of the present invention are better than the high high-temp stability of oxide alone, and activity is higher, because reaction is under 500 ℃～1000 ℃ high temperature, to carry out, are more suitable for this reaction so have the composite oxides of structure of double perovskite.
2, double-perovskite type composite oxides of the present invention are seen than single perovskite composite oxide from the structural chemistry angle can provide abundant more conversion compound mode and the regulation and control space of mixing; Can form more abundant structures defective and oxygen room; Can change oxygen adsorption/desorption character; Improve catalytic performance, so A
2B ' B " O
6The double-perovskite of structure is to be fit to very much the OR process.
3, La of the present invention
2NiFeO
6Raw material is cheap and easy to get, and the preparation method is simple.
Description of drawings
Fig. 1 is the La with perovskite structure that the embodiment of the invention 1, example 4, routine 5 make 800 ℃, 900 ℃, 1000 ℃ roastings respectively
2NiFeO
6X-ray diffractogram.
Fig. 2 is the La with perovskite structure that the embodiment of the invention 1, example 4, routine 5 make 800 ℃, 900 ℃, 1000 ℃ roastings respectively
2NiFeO
6TPR figure.
The specific embodiment
Further specify the process and the effect of the inventive method below in conjunction with embodiment.
Embodiment 1
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 80 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Embodiment 2
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 80 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir while dripping.Get the 67g 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Embodiment 3
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 80 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Embodiment 4
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 80 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 900 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Embodiment 5
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 80 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 1000 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Embodiment 6
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 20 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Embodiment 7
Get 16g Fe (NO
3)
39H
2O, 11.5gNi (NO
3)
26H
2O puts into the beaker of 500mL, and wherein the mol ratio of Fe and Ni is 1/1, adds the distilled water of 100mL, places beaker 50 ℃ water-bath then, and mixing speed is 400rpm, is stirred to whole dissolvings.Get 34.3g La (NO
3)
36H
2O puts into the beaker of 100mL distilled water, is stirred to whole dissolvings.Be added drop-wise to lanthanum nitrate hexahydrate in the mixed solution of ferric nitrate and nickel nitrate then, stir 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, treat that above-mentioned mixed solution stirred after 30 minutes, add citric acid solution slowly, stir while dripping.Stir after 5 hours, brown solution has dewatered and has become thick gel, gel is taken out in the drying box of putting into 110 ℃ dried overnight.Take out dried perovskite predecessor then, place Muffle furnace, rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min; Constant temperature calcining 2 hours; Heating rate with 10 ℃/min rises to 800 ℃ again, and constant temperature calcining 3 hours obtains double-perovskite type composite metal oxide oxygen carrier.
Comparative example
Adopt identical method to prepare single Ca-Ti ore type LaFeO
3Oxide, sintering temperature is with embodiment 1.
Catalyst performance evaluation prepared in the foregoing description and the comparative example is carried out as follows.Evaluating catalyst test is carried out in continuous fixed bed reactor, gets catalyst 5ml, and counts quartz sand with order and mixes in 1: 1 by volume.Fuel gas is synthesis gas (30vol%H
2, 60vol%CO, 10vol%N
2), flow is 120ml/min, and reaction temperature is 750 ℃, and reaction pressure is a normal pressure.Reduction switches to nitrogen after finishing, and simultaneous temperature is reduced to 600 ℃, keeps 20 minutes.Inject water with syringe pump then, flow is 0.5ml/min, and water is gasified earlier, gets into preheater then, and the temperature of preheater remains on 500 ℃, gets into reactor again.React after 10 minutes, switch to nitrogen again, simultaneous temperature rises to 750 ℃.Feed fuel gas again, reaction condition 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.Performance evaluation result sees table 1.
The reactivity worth of table 1 catalyst
*The productive rate of hydrogen is that (water is excessive) calculated on the basis with Fe, and promptly every gram iron reductive water steam can generate the volume of hydrogen.
Claims (6)
1. the application of double-perovskite type oxide oxygen carrier in chemical chain hydrogen manufacturing, described oxygen carrier is the composite metal oxide A with structure of double perovskite
2B ' B " O
6, A is a rare earth lanthanum, B ' is a transiting metal nickel, B " and be transition metal iron.
2. according to the described application of claim 1, it is characterized in that: perovskite structure composite metal oxide oxygen carrier is sphere, bar shaped, microballoon, and particle size is 10 μ m-2000 μ m.
3. according to the described application of claim 1; It is characterized in that: the temperature that structure of double perovskite composite metal oxide oxygen carrier burns in steam is 500～1000 ℃; The temperature that reduce in fuel the burning back is 500～1000 ℃, and reaction pressure is normal pressure.
4. the preparation method in the said application of claim 1 to 3 with structure of double perovskite composite metal oxide oxygen carrier; The preparation process is: with ferric nitrate, nickel nitrate, lanthanum nitrate is presoma; With the citric acid is complexing agent, wiring solution-forming and mixing and stirring; Carry out water evaporates then, solution is transformed into the gel of thickness by transparent colloidal sol, dry then, roasting, and the sample after the roasting is the perovskite structure composite metal oxide.
5. according to the described method of claim 4; It is characterized in that: complexing agent and metal ion mol ratio are 1: 1～5: 1, and the temperature of preparation and agitating solution is 30～90 ℃, and mixing time is 3～8 hours; Baking temperature is 60～200 ℃; Be 1～36 hour drying time, and sintering temperature is 600～1200 ℃, and roasting time is 2-15 hour.
6. according to the described method of claim 4; It is characterized in that: complexing agent and metal ion mol ratio are 1: 1～3: 1, and the temperature of preparation and agitating solution is 50～80 ℃, and mixing time is 4～6 hours; Baking temperature is 80～150 ℃; Be 8～24 hours drying time, and sintering temperature is under 800～1200 ℃, and roasting time is 3～8 hours.
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