CN109589910B - Preparation method and application of barium-cobalt-based perovskite composite metal oxide oxygen carrier - Google Patents
Preparation method and application of barium-cobalt-based perovskite composite metal oxide oxygen carrier Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a barium-cobalt-based perovskite composite metal oxide oxygen carrier, wherein the method comprises the steps of firstly weighing barium nitrate and cobalt nitrate, mixing to prepare a nitrate solution, and then sequentially adding citric acid or urea and EDTA into the nitrate solution; mixing uniformly; adding MO again2Heating and stirring in a water bath at the temperature of 70-85 ℃ until the sol is formed, and collecting the sol; and finally, drying and sectionally burning the sol to obtain the barium-cobalt-based perovskite composite metal oxide oxygen carrier. The composite oxygen carrier has more excellent oxygen desorption performance and reaction activity, and the preparation process is simple and efficient, and is convenient for industrial production. The oxygen carriers produced by the process of the invention are expected to be a very promising new type of chained oxygen production application for oxycombustion applications.
Description
Technical Field
The invention relates to a composite perovskite metal oxygen carrier used in the field of oxygen-enriched combustion, in particular to a preparation method and application of a barium cobalt-based perovskite composite metal oxide oxygen carrier.
Background
CO, a major greenhouse gas, is increasing in global warming and climate change2Emissions issues are increasingly attracting global attention.
The oxygen-enriched combustion technology is a large-scale reduction of CO in coal2The technology of emission, one of the key problems of the technology is to reduce the cost of oxygen production and improve the economy. The cryogenic process is the only commercial operation large-scale oxygen generation method at presentThe method has the disadvantages of complex device, large investment and high energy consumption. Compared with the cryogenic process, the chain oxygen generation technology based on perovskite oxide has better economical efficiency, and researches indicate that the energy consumption of the new oxygen generation technology is about 70 percent of that of the traditional cryogenic process, the investment cost is about 50 percent of that of the cryogenic process, and the oxygen generation cost can be effectively reduced. This is to recycle CO in the flue gas2Preparation of O by reaction with perovskite at high temperature for desorption of gas2/CO2The method for directly supplying the mixed gas to the oxygen-enriched combustion successfully avoids a series of problems of thermal stability, chemical stability and the like of the perovskite membrane material in a high-temperature reducing atmosphere. The novel oxygen production method becomes a potential oxygen production method which can be applied to oxygen-enriched combustion and can continuously and directly supply O required by combustion2/CO2The method of (1).
In this process, the study of oxygen carriers is a key issue; although some research has been carried out on the production of O based on perovskites as high temperature sorbents2/CO2Mixed gas[1-5]. However, the perovskite materials mentioned above all have the disadvantage of low desorption rate. Therefore, it is necessary to find a perovskite-type oxygen carrier having good desorption properties.
[1]Yang,Z.H.,Lin,Y.S.,High-temperature oxygen sorption in a fixed bed packed with perovskite-type ceramic sorbents.Ind.Eng.Chem.Res.,2003,42:4376-4381.
[2]Yang,Z.H.,Lin,Y.S.,Synergetic thermal effects for oxygen sorption and order-disorder transition on perovskite-type oxides.Solid State Ionics,2005,176:89-96.
[3]Yin,Q.H.，Lin,Y.S.,Effect of doping addition on oxygen sorption properties of La-Sr-Co-Fe-O perovskite-type oxide.Adsorption,2006,12(5-6):329-338.
[4]Yin,Q.H.,Lin,Y.S.,The beneficial effect of order-disorder phase transition on oxygen sorption properties of perovskite-type oxides.Solid State Ionics,2007,178(1-2):83-89.
[5]Guntuka,S.,Banerjee,S.,Farooq,S.,Srinivasan,M.P.,A-and B-Site substituted lanthanum cobaltite perovskite as high temperature oxygen sorbent.Ind.Eng.Chem.Res.,2008,47:154-162.
Therefore, the development of a perovskite oxygen carrier with simple preparation process, good activity and strong oxygen desorption performance is urgently needed.
Disclosure of Invention
The invention provides a preparation method and application of a barium-cobalt-based perovskite composite metal oxide oxygen carrier, aiming at the problems that the conventional perovskite oxygen carrier cannot meet the requirement of the amount of oxygen required by oxygen-enriched combustion, and has low reaction activity, oxygen release amount and the like; the method adopts oxide MO with large specific surface area and fluorite structure with oxygen ion diffusion conduction mechanism2The oxygen carrier is cooperated with perovskite to be used as a composite metal compound oxygen carrier, so that the oxygen carrier with high activity and high performance is used for oxygen-enriched combustion chain type oxygen generation.
In order to achieve the aim, the invention designs a preparation method of a barium-cobalt-based perovskite composite metal oxide oxygen carrier, which comprises the following steps:
1) weighing barium nitrate and cobalt nitrate according to the molar ratio of barium ions to cobalt ions of 1: 1, and mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing citric acid or urea, the total mole number of metal ions and EDTA according to the mole ratio of the citric acid or the urea of 1: 1-1.5;
3) sequentially adding citric acid or urea and EDTA into the nitrate solution; mixing uniformly;
4) by barium or cobalt ions with MO2The mol ratio of MO to the mixed solution is 1: 0.3-1.52Heating and stirring in a water bath at the temperature of 70-85 ℃ until the sol is formed, and collecting the sol; wherein M is Ce or Zr;
5) drying the sol in a vacuum drying oven at the temperature of 105-110 ℃, then carrying out staged combustion, firstly calcining at the temperature of 350-450 ℃ for 0.2-1 h, then calcining at the temperature of 850-1000 ℃ for 8-12 h, cooling at room temperature, and grinding to obtain a final powder product, namely the barium-cobalt-base perovskite composite metal oxide oxygen carrier BaCoO3-δ/MO2Wherein M ═ Ce or Zr.
Further, in the step 1), the molar ratio of barium ions to cobalt ions is 1: 1.
Still further, in the step 2), EDTA: total molar number of metal ions: the molar ratio of citric acid or urea is 1: 1.
Still further, in the step 4), MO and barium ions or cobalt ions are reacted2The molar ratio of (A) to (B) is 1: 0.4.
And furthermore, in the step 5), in the staged combustion process, firstly calcining at 350-450 ℃ for 0.5h, and then calcining at 850-1000 ℃ for 10 h.
The invention also provides a method for preparing pure oxygen or oxygen-enriched air or O at high temperature by using the barium-cobalt-based perovskite composite metal oxide oxygen carrier prepared by the method2/CO2Mixed gases, and direct oxygen supply to oxycombustion.
The invention has the beneficial effects that:
the composite oxygen carrier has more excellent oxygen desorption performance, and adopts oxide MO with large specific surface area and fluorite structure with oxygen ion diffusion conduction mechanism2The composite oxygen carrier has higher oxygen desorption amount and reactivity, and the preparation process is simple and efficient, thereby being convenient for industrial production. The oxygen carriers produced by the process of the invention are expected to be a very promising new type of chained oxygen production application for oxycombustion applications.
Drawings
FIG. 1 is a graph showing oxygen desorption of a barium cobalt based perovskite composite metal oxide oxygen carrier prepared in example 1;
Detailed Description
The present invention is described in further detail below with reference to specific examples so as to be understood by those skilled in the art.
Example 1
The preparation method of the barium-cobalt-based perovskite composite metal oxide oxygen carrier comprises the following steps:
1) analytically pure Ba (NO) is weighed according to the molar ratio of barium ions to cobalt ions of 1: 13)2、Co(NO3)2·6H2O, mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: EDTA, the total mole number of metal ions and citric acid are weighed according to the mole ratio of 1: 1 of citric acid;
3) sequentially adding citric acid and EDTA to the nitrate solution; mixing uniformly;
4) by reacting barium ions or cobalt ions with CeO2In a molar ratio of 1: 0.4, CeO is added2Heating and stirring in a water bath at the temperature of 75 ℃ until the sol is formed, and collecting the sol;
5) drying the sol in a vacuum drying oven at 105 ℃, then carrying out staged combustion, firstly calcining at 350 ℃ for 0.5h, then calcining at 850 ℃ for 8h, cooling at room temperature, and grinding to obtain a final powder product, namely the barium-cobalt-based perovskite composite metal oxide oxygen carrier BaCoO3-δ/CeO2。
Example 2
The preparation method of the barium-cobalt-based perovskite composite metal oxide oxygen carrier comprises the following steps:
1) analytically pure Ba (NO) is weighed according to the molar ratio of barium ions to cobalt ions of 1: 13)2、Co(NO3)2·6H2O, mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing EDTA, the total mole number of metal ions and citric acid according to the mole ratio of 1: 1.2 of the citric acid;
3) sequentially adding citric acid and EDTA to the nitrate solution; mixing uniformly;
4) by reacting barium ions or cobalt ions with CeO2In a molar ratio of 1: 1, CeO is added2Heating and stirring in a water bath at the temperature of 75 ℃ until the sol is formed, and collecting the sol;
5) vacuum drying the sol at 110 deg.CDrying, performing staged combustion, calcining at 400 deg.C for 0.5 hr, calcining at 850 deg.C for 8 hr, cooling at room temperature, and grinding to obtain final powder product, i.e. barium-cobalt-base perovskite composite metal oxide oxygen carrier BaCoO3-δ/CeO2。
Example 3
The preparation method of the barium-cobalt-based perovskite composite metal oxide oxygen carrier comprises the following steps:
1) analytically pure Ba (NO) is weighed according to the molar ratio of barium ions to cobalt ions of 1: 13)2、Co(NO3)2·6H2O, mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing EDTA, the total mole number of metal ions and citric acid according to the mole ratio of 1: 1.5 of citric acid;
3) sequentially adding citric acid and EDTA to the nitrate solution; mixing uniformly;
4) by reacting barium ions or cobalt ions with CeO2In a molar ratio of 1: 1.2, CeO is added2Heating and stirring in a water bath at the temperature of 75 ℃ until the sol is formed, and collecting the sol;
5) drying the sol in a vacuum drying oven at 110 ℃, then carrying out staged combustion, firstly calcining at 400 ℃ for 0.5h, then calcining at 850 ℃ for 10h, cooling at room temperature, and grinding to obtain a final powder product, namely the barium-cobalt-based perovskite composite metal oxide oxygen carrier BaCoO3-δ/CeO2。
Example 4
The preparation method of the barium-cobalt-based perovskite composite metal oxide oxygen carrier comprises the following steps:
1) analytically pure Ba (NO) is weighed according to the molar ratio of barium ions to cobalt ions of 1: 13)2、Co(NO3)2·6H2O, mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing EDTA, the total mole number of metal ions and citric acid according to the mole ratio of 1: 1.5 of citric acid;
3) sequentially adding citric acid and EDTA to the nitrate solution; mixing uniformly;
4) by reacting barium ions or cobalt ions with CeO2In a molar ratio of 1: 1.5, CeO is added2Heating and stirring in a water bath at the temperature of 75 ℃ until the sol is formed, and collecting the sol;
5) drying the sol in a vacuum drying oven at 110 ℃, then carrying out staged combustion, firstly calcining at 400 ℃ for 0.5h, then calcining at 850 ℃ for 8h, cooling at room temperature, and grinding to obtain a final powder product, namely the barium-cobalt-based perovskite composite metal oxide oxygen carrier BaCoO3-δ/CeO2。
Example 5
The preparation method of the barium-cobalt-based perovskite composite metal oxide oxygen carrier comprises the following steps:
1) analytically pure Ba (NO) is weighed according to the molar ratio of barium ions to cobalt ions of 1: 13)2、Co(NO3)2·6H2O, mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing EDTA, the total mole number of metal ions and citric acid according to the mole ratio of 1: 1.5 of citric acid;
3) sequentially adding citric acid and EDTA to the nitrate solution; mixing uniformly;
4) according to the formula of barium ion or cobalt ion and ZrO2ZrO was added in a molar ratio of 1: 0.42Heating and stirring in a water bath at the temperature of 5 ℃ until the sol is formed, and collecting the sol;
5) drying the sol in a vacuum drying oven at 110 ℃, then carrying out staged combustion, firstly calcining at 400 ℃ for 1h, then calcining at 850 ℃ for 8h, cooling at room temperature, and grinding to obtain a final powder product, namely the barium-cobalt-based perovskite composite metal oxide oxygen carrier BaCoO3-δ/ZrO2。
Example 6
The preparation method of the barium-cobalt-based perovskite composite metal oxide oxygen carrier comprises the following steps:
1) analytically pure Ba (NO) is weighed according to the molar ratio of barium ions to cobalt ions of 1: 13)2、Co(NO3)2·6H2O, mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing EDTA, the total mole number of metal ions and citric acid according to the mole ratio of 1: 1.2 of the citric acid;
3) sequentially adding citric acid and EDTA to the nitrate solution; mixing uniformly;
4) according to the formula of barium ion or cobalt ion and ZrO2ZrO was added in a molar ratio of 1: 12Heating and stirring in a water bath at the temperature of 70 ℃ until the sol is formed, and collecting the sol; wherein M is Ce or Zr;
5) drying the sol in a vacuum drying oven at the temperature of 110 ℃, then carrying out sectional combustion, firstly calcining for 0.5h at the temperature of 400 ℃, then calcining for 12h at the temperature of 900 ℃, cooling at room temperature and then grinding to obtain a final powder product, namely the barium-cobalt-based perovskite composite metal oxide oxygen carrier BaCoO3-δ/ZrO2。
Placing the composite metal oxide oxygen carrier prepared in the embodiment 1 in an oxygen generation workbench in an adsorption stage, and introducing air at the temperature of 700-900 ℃ to enable the perovskite oxygen carrier to adsorb oxygen in the air;
in the desorption stage, with CO2As a purge gas, oxygen is desorbed from the perovskite oxygen carrier and oxygen-enriched CO is formed2A gas stream;
as shown in FIG. 1, CO was added at a reaction temperature of 850 deg.C2When used for desorbing gas, the composite oxygen carrier BaCoO of the invention3-δ/CeO2The oxygen desorption performance is more excellent compared with that of a single perovskite oxygen carrier (the molar ratio is 1: 0.4), and the oxygen desorption amount is 1.2 times that of the single perovskite oxygen carrier.
Other parts not described in detail are prior art. Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (1)
1. Preparation of O from barium-cobalt-based perovskite composite metal oxide oxygen carrier at high temperature2/CO2The application in mixed gas is that the barium-cobalt-based perovskite composite metal oxide oxygen carrier is prepared by the following steps:
1) weighing barium nitrate and cobalt nitrate according to the molar ratio of barium ions to cobalt ions of 1: 1, and mixing to prepare a nitrate solution for later use;
2) according to the weight ratio of EDTA: total molar number of metal ions: weighing citric acid or urea, the total mole number of metal ions and EDTA according to the mole ratio of the citric acid or the urea of 1: 1;
3) sequentially adding citric acid or urea and EDTA into the nitrate solution; mixing uniformly;
4) according to the formula of barium ion or cobalt ion and ZrO2ZrO was added in a molar ratio of 1: 0.42Heating and stirring in a water bath at the temperature of 70-85 ℃ until the sol is formed, and collecting the sol;
5) drying the sol in a vacuum drying oven at the temperature of 105-110 ℃, then carrying out staged combustion, firstly calcining for 0.5h at the temperature of 350-450 ℃, then calcining for 10h at the temperature of 850-1000 ℃, cooling at room temperature, and grinding to obtain a final powder product, namely the barium-cobalt-based perovskite composite metal oxide oxygen carrier BaCoO3-δ/ZrO2。
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