CN102441396B - The application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method - Google Patents
The application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method Download PDFInfo
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Abstract
The invention discloses the application of a kind of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method, described oxygen carrier is the composite metal oxide with structure of double perovskite, and the general formula of composite metal oxide is A
2b ' B " O
6, A is rare earth lanthanum, and B ' is transiting metal nickel, B " and position is transition metal iron, the temperature that oxygen carrier burns in steam is 500 ~ 1000 DEG C, and the temperature of reducing in fuel after burning is 500 ~ 1000 DEG C, and reaction pressure is all normal pressure.Preparation process is: with ferric nitrate, nickel nitrate, lanthanum nitrate for presoma, take citric acid as 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, then dry, roasting, and the sample after roasting is perovskite structure composite metal oxide.High, active high, the good stability of the oxygen carrier rate of oxygen carrier of the present invention.
Description
Technical field
The present invention relates to the application of a kind of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain and preparation method, belong to the catalyst technology in hydrogen production of chemical chain field.
Background technology
In the direct combustion process of traditional fossil fuel, due to N
2dilution, CO in the flue gas of generation
2only account for 10% ~ 14%, CO
2separating energy consumption higher.By novel energy transfer principle and CO
2enrichment process has combination, solves beyond doubt fossil energy and to utilize and of implementation environment protection is rich in change sexual development direction.Based on burning chemistry chains (chemicalloopingcombustion, CLC) technology, there is low energy consumption CO
2enrichment, high-energy conversion efficiency, low Conventional pollution (NO
xand SO
xdeng) characteristic such as discharge, become main research direction.Chemical chain burning technology take metal oxide as oxygen carrier, and oxygen carrier carries out oxidation reaction in atmosphere at a certain temperature, in conjunction with oxygen; Then reduction reaction is carried out with fuel gas, release oxygen.Gas-phase reaction product only has CO
2and H
2o (gas), condensation water outlet, obtains high-purity CO
2.CO in burning chemistry chains process
2by the nitrogen dilution in air, therefore can not can realize CO under the precondition not having energy loss
2be separated.The complete description of relevant chemical circulating combustion method is found in french patent application 02-14, and 071 and 04-08,549.
Oxygen carrier, as medium, circulates between two reactors, and ceaselessly the heat that the oxygen in air 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.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 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(CHOPetc.Fuel, 2004,83 (9)), Fe
2o
3/ Al
2o
3(MATTISSONTetc.Fuel, 2001,80 (13)) and CoO-NiO/YSZ (JINHGetc.EnergyFuels, 1998,12 (6)) etc. combination property is better, but has that reaction bed pressure drop is large, oxygen carrier aperture is little, oxygen carrier rate is limited, circular response is lower, cannot bear the not high deficiency of higher reaction temperature, metal oxide decentralization in oxygen carrier.
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, replace air to introduce as oxidant the regeneration that air reactor completes oxygen carrier using steam, steam is also reduced generation hydrogen simultaneously.Current, in the world a lot of seminar 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
3fanL-S for oxygen carrier, the U.S. teaches seminar to the Fe taking coal as fuel
2o
3for the CLC hydrogen production process of oxygen carrier etc. is studied.
Summary of the invention
For the deficiencies in the prior art, the invention provides oxygen carrier for hydrogen production of chemical chain technology of high, active high, the good stability of a kind of oxygen carrier rate and its preparation method and application.
The oxygen carrier of hydrogen production of chemical chain technology of the present invention is the composite metal oxide with structure of double perovskite, and general formula is A
2b ' B " O
6, A is rare earth lanthanum, and B ' is transiting metal nickel, B " and be transition metal iron.
The application of composite metal oxide in hydrogen production of chemical chain of the above-mentioned structure of double perovskite of the present invention, the temperature that wherein composite metal oxide burns in steam is 500 ~ 1000 DEG C, the temperature of reducing in fuel after burning is 500 ~ 1000 DEG C, and reaction pressure is all normal pressure.
Above-mentioned composite metal oxide oxygen carrier can be the suitable shape such as spherical, bar shaped, microballoon, and particle size is generally 10 μm-2000 μm, and preferred particle size is 50 μm-500 μm.Other suitable inorganic refractory component can be added 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 citric acid complex method preparation.Detailed process is as follows: with ferric nitrate, nickel nitrate, lanthanum 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, then dry, roasting, and the sample after roasting is perovskite structure composite metal oxide.
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 ~ 5: 1, is preferably 1: 1 ~ 3: 1.Preparation and agitating solution, at 30 ~ 90 DEG C, carry out at being preferably 50 ~ 80 DEG C.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 DEG C, is preferably 80 ~ 150 DEG C.Drying time is 1 ~ 36 hour, is preferably 8 ~ 24 hours.Sintering temperature is 600 ~ 1200 DEG C, and roasting time is 2-15 hour, preferably roasting 3 ~ 8 hours at 800 ~ 1000 DEG C.
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 and have difference again, similarity is that they all at high temperature just may form material, there is stable skeleton structure, cation in skeleton structure has necessarily can substituted, Lacking oxygen or transition metal oxide variation of valence can be produced and form defect, oxygen desorption desorption character can be changed thus, improve catalytic performance.Difference is in double-perovskite type composite oxides structure, and the octahedral structure of B position ion is by B ' O
6and B " O
6be alternately arranged, each B ' and B " ion separated by oxonium ion form B '-O-B " structure.Usually in double-perovskite type composite oxides, due to B ' and B " ion has different electron configurations; and the exchange interaction of different ionic radius and each other different ions kind and type; the combination therefore by changing them can realize regulate and control material property; so more abundant conversion combination and doping can be provided from double-perovskite type composite oxides viewed from structural chemistry angle to regulate and control space than single perovskite composite oxide, this point is the double-perovskite type catalyst place of fully developing talents in catalytic chemistry than single perovskite type catalyst just.
The oxygen carrier of hydrogen production of chemical chain of the present invention is the composite metal oxide of perovskite structure, and its general formula is A
2b ' B " O
6, A is rare earth lanthanum, and B ' is transiting metal nickel, B " and be transition metal iron, compared with prior art tool of the present invention has the following advantages:
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 carries out under 500 DEG C ~ 1000 DEG C high temperature, so the composite oxides with structure of double perovskite are more suitable for this reaction.
2, double-perovskite type composite oxides of the present invention can provide the conversion combination and doping regulation and control space more enriched viewed from structural chemistry angle than single perovskite composite oxide, abundanter fault of construction and Lacking oxygen can be formed, oxygen desorption desorption character can be changed, improve catalytic performance, so A
2b ' B " O
6the double-perovskite of structure is very applicable to oxidation-reduction process.
3, La of the present invention
2niFeO
6raw material is cheap and easy to get, and preparation method is simple.
Accompanying drawing explanation
Fig. 1 is the embodiment of the present invention 1, example 4, example 5 be respectively at the La with perovskite structure that 800 DEG C, 900 DEG C, 1000 DEG C roastings obtain
2niFeO
6x-ray diffractogram.
Fig. 2 is the embodiment of the present invention 1, example 4, example 5 be respectively at the La with perovskite structure that 800 DEG C, 900 DEG C, 1000 DEG C roastings obtain
2niFeO
6tPR figure.
Detailed description of the invention
Process and the effect of the inventive method is further illustrated below in conjunction with embodiment.
Embodiment 1
Get 16gFe (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, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Embodiment 2
Get 16gFe (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, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel nitrate, 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Embodiment 3
Get 16gFe (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, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Embodiment 4
Get 16gFe (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, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 900 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Embodiment 5
Get 16gFe (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, and then beaker is placed in the water-bath of 80 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 1000 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Embodiment 6
Get 16gFe (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, and then beaker is placed in the water-bath of 20 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Embodiment 7
Get 16gFe (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, and then beaker is placed in the water-bath of 50 DEG C, mixing speed is 400rpm, is stirred to whole dissolving.Get 34.3gLa (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 mixed solution of ferric nitrate and nickel 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 mixed solution 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 drying box of 110 DEG C, dried overnight.Then take out dried perovskite predecessor, be placed in Muffle furnace, rise to 400 DEG C with the heating rate of 3 DEG C/min from room temperature, constant temperature calcining 2 hours, rise to 800 DEG C with the heating rate of 10 DEG C/min again, constant temperature calcining 3 hours, obtain double-perovskite type composite metal oxide oxygen carrier.
Comparative example
Identical method is adopted to prepare single Ca-Ti ore type LaFeO
3oxide, sintering temperature is with embodiment 1.
Embodiment 8
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 catalyst 5ml, to mix at 1: 1 by volume with same order number quartz sand.Fuel gas is synthesis gas (30vol%H
2, 60vol%CO, 10vol%N
2), flow is 120ml/min, and reaction temperature is 750 DEG C, and reaction pressure is normal pressure.After reduction terminates, switch to nitrogen, simultaneous temperature is down to 600 DEG C, keeps 20 minutes.Then inject water with syringe pump, flow is 0.5ml/min, and water is first vaporized, and then enters preheater, and the temperature of preheater remains on 500 DEG C, then enters reactor.React after 10 minutes, then switch to nitrogen, simultaneous temperature rises to 750 DEG C.Pass into 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 PorapakQ post, TCD detects.Evaluation results is in table 1.
The reactivity worth of table 1 catalyst
*the productive rate of hydrogen carries out calculating (water is excessive) based on Fe, and namely every gram of Fe3+ reduction steam can generate the volume of hydrogen.
Claims (5)
1. the application of double perovskite type oxide oxygen carrier in hydrogen production of chemical chain, is characterized in that: described oxygen carrier is the composite metal oxide A with structure of double perovskite
2b ' B " O
6, A is rare earth lanthanum, and B ' is transiting metal nickel; B " for transition metal iron, the temperature that structure of double perovskite composite metal oxide oxygen carrier burns in steam is 500 ~ 1000 DEG C, and the temperature of reducing in fuel after burning is 500 ~ 1000 DEG C, and reaction pressure is normal pressure.
2. according to application according to claim 1, it is characterized in that: structure of double perovskite composite metal oxide oxygen carrier is spherical, bar shaped, particle size is 10 μm-2000 μm.
3. according to application according to claim 1, it is characterized in that: the preparation process with structure of double perovskite composite metal oxide oxygen carrier is: with ferric nitrate, nickel nitrate, lanthanum nitrate for presoma, take citric acid as 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, then dry, roasting, and the sample after roasting is structure of double perovskite composite metal oxide.
4. according to application according to claim 3, it is characterized in that: complexing agent and metal ion mol ratio are 1: 1 ~ 5: 1, the temperature of preparation and agitating solution is 30 ~ 90 DEG C, mixing time is 3 ~ 8 hours, baking temperature is 60 ~ 200 DEG C, drying time is 1 ~ 36 hour, and sintering temperature is 600 ~ 1200 DEG C, and roasting time is 2-15 hour.
5. according to application according to claim 3, 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 DEG C, mixing time is 4 ~ 6 hours, baking temperature is 80 ~ 150 DEG C, drying time is 8 ~ 24 hours, and sintering temperature is at 800 ~ 1200 DEG C, and roasting time is 3 ~ 8 hours.
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| CN109250763B (en) * | 2017-07-14 | 2020-11-10 | 中国石油化工股份有限公司 | Method for preparing hydrogen by reforming hydrogen sulfide and methane |
| CN108152337B (en) * | 2017-12-19 | 2020-06-02 | 太原理工大学 | LaFeO with high gas-sensitive performance3Ethanol-based gas sensor and preparation method thereof |
| CN108313978A (en) * | 2018-02-06 | 2018-07-24 | 中国科学院上海高等研究院 | A kind of Double Perovskite type hydrogen-storing material and its preparation method and application |
| CN109092313A (en) * | 2018-07-27 | 2018-12-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of perovskite catalyst and products thereof and application |
| CN109539284B (en) * | 2018-11-27 | 2020-06-16 | 中国科学院大连化学物理研究所 | Oxygen carrier for purifying inert gas and preparation and application thereof |
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| CN110970148B (en) * | 2019-12-24 | 2021-03-02 | 东北大学 | Composite oxide proton conductor material and preparation method thereof |
| CN111087026B (en) * | 2019-12-31 | 2022-06-28 | 天津大学 | Chemical chain methane partial oxidation oxygen carrier and preparation method and application thereof |
| CN110980644B (en) * | 2019-12-31 | 2021-10-22 | 中国科学院工程热物理研究所 | Water-based chemical chain circulation hydrogen production system and method |
| CN111266113A (en) * | 2020-02-27 | 2020-06-12 | 西北大学 | Oxygen carrier for chemical chain combustion and cracking and preparation method and application thereof |
| CN111545212A (en) * | 2020-04-29 | 2020-08-18 | 南京中微纳米功能材料研究院有限公司 | Double perovskite La2NiFeO6Method for catalytic degradation of antibiotic wastewater |
| CN112811476B (en) * | 2020-12-31 | 2022-05-17 | 华中科技大学 | Nickel-doped brownmillerite type oxygen carrier and preparation method and application thereof |
| CN114405511B (en) * | 2022-01-24 | 2023-06-23 | 西北大学 | Oxygen carrier for preparing synthesis gas and combining CO and hydrogen as well as preparation method and application thereof |
| CN114570379B (en) * | 2022-03-17 | 2024-01-16 | 厦门大学 | Catalyst for preparing hydrogen by reforming high-carbon hydrocarbon liquid fuel and preparation method and application thereof |
| CN115784318A (en) | 2022-10-08 | 2023-03-14 | 天津大学 | Medium-entropy perovskite oxygen carrier and preparation method and application thereof |
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| 稀土双钙钛矿型催化剂La2NiBO6（B=Mn、Fe、V）的制备及性能研究;马岚;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20100415(第04期);第10页第2.2.2节以及第15页第3.3.1节 * |
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