CN114988875B - Copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and preparation method thereof - Google Patents

Copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and preparation method thereof Download PDF

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CN114988875B
CN114988875B CN202210679646.1A CN202210679646A CN114988875B CN 114988875 B CN114988875 B CN 114988875B CN 202210679646 A CN202210679646 A CN 202210679646A CN 114988875 B CN114988875 B CN 114988875B
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oxygen
copper
permeable membrane
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membrane material
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罗惠霞
张超
王晓鹏
黄彦昊
曾令勇
何溢懿
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Sun Yat Sen University
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Abstract

The invention belongs to the technical field of inorganic functional ceramic manufacturing, and discloses a copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and a preparation method thereof. The copper-containing two-phase mixed conductor oxygen permeable membrane material with high oxygen flux comprises the following components: ce 0.85 Nd 0.1 Cu 0.05 O 2‑δ ‑Nd x Sr 1‑x Fe 1‑y Cu y O 3‑δ Wherein x =0.4 or 0.6; y =0.05 or 0.1. The copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux is prepared by adding a complexing agent and a dispersing agent, preparing powder by a sol-gel one-pot method, calcining the powder to obtain precursor powder, and tabletting and sintering the precursor powder to obtain the finally required mixed conductor oxygen-permeable membrane. The material is doped with copper element, so that on one hand, the sintering temperature is effectively reduced, the manufacturing cost is reduced, and on the other hand, the electron conductivity and the number of oxygen vacancies of the system are remarkably improved due to the low valence (+ 2) of the Cu element and the improvement of the electron conductivity after doping, thereby enhancing the oxygen permeability of the system.

Description

Copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and preparation method thereof
Technical Field
The invention relates to the technical field of inorganic functional ceramic manufacturing, in particular to a copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and a preparation method thereof.
Background
Mixed conductor (MIEC) oxygen permeable membranes (OTMs) are an inorganic ceramic-like material with both electronic and oxygen ion conductivity. Under different oxygen partial pressure gradients, oxygen on the high oxygen partial pressure side of the membrane body can spontaneously permeate to the low oxygen partial pressure side, so that the separation of the oxygen is realized. At high temperatures, the permeability behavior of oxygen permeable membranes to oxygen is enhanced, with a theoretical permselectivity to oxygen of 100%. Therefore, the oxygen permeable membrane has wide application prospect in high-temperature oxygen demand industries such as oxygen-enriched combustion, pure oxygen preparation, solid fuel cells and the like, and the oxygen flux and the stability of the oxygen permeable membrane under the high-temperature condition are two important indexes for measuring the performance of the oxygen permeable membrane.
In recent years, single phase perovskite structure ABO 3 Oxygen permeable membrane materials of mixed conducting type are of particular interest, typical of these being, for example, ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3-δ 、SrCo 0.8 Fe 0.2 O 3-δ 、La 0.6 Ca 0.4 Co 1–x Fe x O 3-δ 、BaBi 0.05 Co 0.8 Ta 0.15 O 3-δ And the like have been widely studied. Due to the characteristics of the perovskite structure, the doping of positive ions with different valence states can cause the distortion of the structure, and mixed valence states are generated at the same crystal lattice position, and the deviation of the positive ions/negative ions from the stoichiometry results in the change of the concentration of oxygen ion vacancies, so that the perovskite material becomes an adjustable ionic conductor. The increase of oxygen vacancy is beneficial to the rapid and sustainable transportation of oxygen ions under certain conditions, and good oxygen ion conductivity is shown, so that the single-phase perovskite type mixed conductor oxygen permeable membrane has high oxygen permeability. However, single phase mixed conductor oxygen permeable membranes in CO 2 、H 2 S、SO 2 And the mechanical strength is deteriorated due to insufficient chemical stability and structural stability in corrosive atmosphere, which is not suitable for large-scale industrial application. In addition, the traditional high oxygen permeability single-phase perovskite structure mixed conductor oxygen permeable membrane generally takes Co element as B site element, and the perovskite material containing the Co element generally has larger thermal expansion coefficient, thereby leading to poor stability under high temperature working condition. To this end, researchers have utilized elements of higher valence (e.g., zr) 4+ 、Ti 4+ 、Nb 5+ 、Ta 5+ 、Cr 6+ 、Mo 6+ 、W 6+ ) Replacement of B-site transition metal elements (e.g. Co) in perovskite phases 3+ ) Using lanthanides (e.g. La) 3+ 、Pr 3+ ) Substitute of calcium and titaniumAlkaline earth element at A site in mineral structure (such as Sr) 2+ 、Ba 2+ ) To improve the structural and chemical stability of the material, but the doping of ions in higher valence states leads to a decrease in the concentration of oxygen vacancies, which is detrimental to the penetration of oxygen ions.
In order to balance the oxygen permeability and stability of mixed conductor oxygen permeable membrane materials, researchers have proposed two-phase mixed conductor oxygen permeable membrane materials. Generally, a fluorite phase structure is used as an oxygen ion transporter, a perovskite phase structure is used as an oxygen ion and electron mixed transporter, and the two phase structures are uniformly mixed to form a compact oxygen permeation network, so that the permeation and the transportation of oxygen ions and electrons are facilitated. Compared with a single-phase mixed conductor oxygen permeable membrane material, the fluorite phase can reduce the system conductivity when being used as a pure oxygen ion conductor, the dual-phase membrane has better stability, but the oxygen flux is lower. However, the two-phase composition and proportion of the two-phase mixed oxygen-permeable conductor membrane can be adjusted according to actual conditions, and the performance of the two-phase mixed oxygen-permeable conductor membrane can be adjusted and controlled to a greater extent so as to balance the contradiction between the oxygen permeability and the stability of the material, so that the two-phase mixed oxygen-permeable conductor membrane is expected to replace a single-phase mixed oxygen-permeable conductor membrane.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a copper-containing two-phase mixed conductor oxygen-permeable membrane material with high oxygen flux and a preparation method thereof. The material is doped with copper element, so that on one hand, the sintering temperature is effectively reduced, the manufacturing cost is reduced, and on the other hand, the electron conductivity and the number of oxygen vacancies of the system are remarkably improved due to the low valence (+ 2) of the Cu element and the improvement of the electron conductivity after doping, thereby enhancing the oxygen permeability of the system.
In order to achieve the aim of the invention, the copper-containing two-phase mixed conductor oxygen permeable membrane material with high oxygen flux comprises the following components: ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ Wherein x =0.4 or 0.6; y =0.05 or 0.1.
Further, the invention also provides a preparation method of the copper-containing two-phase mixed conductor oxygen permeable membrane material with high oxygen flux, which comprises the following steps:
(1) Ce is weighed in turn according to the stoichiometric ratio 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ Dissolving the corresponding nitrate in water, fully stirring the mixture until the nitrate is dissolved, and adding a complexing agent and a dispersing agent to obtain a mixed solution;
(2) Stirring the solution obtained in the step (1) until the solution becomes clear and transparent, then stirring and heating until the solution is converted into gel, drying the gel to obtain dry gel, fully grinding, preserving heat and calcining to remove organic matters to obtain powder;
(3) Calcining the powder obtained in the step (2) at 950-1000 ℃ to obtain Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1- y Cu y O 3-δ The powder of (4);
(4) And (4) tabletting the powder obtained in the step (3) to obtain a cake-shaped sheet body, heating the sheet body to 1210-1235 ℃, calcining, slowly cooling, sintering to obtain a compact two-phase mixed conductor oxygen permeable membrane, and polishing to obtain the copper-containing two-phase mixed conductor oxygen permeable membrane material with the required thickness and high oxygen flux.
Further, in some embodiments of the present invention, the complexing agent may be a polybasic organic acid such as EDTA (ethylenediaminetetraacetic acid), CA (citric acid), or HEDTA (hydroxyethylethylenediaminetriacetic acid). Among them, EDTA (ethylenediaminetetraacetic acid) or/and citric acid is preferable; more preferably citric acid, such as citric acid monohydrate.
The complexing agent plays a role in complexing metal ions to form a complex with uniformly dispersed metal ions, and is beneficial to the formation of sol and gel. EDTA has stronger complexing effect, but only complexes with metal ions, and citric acid is also a polybasic acid and simultaneously contains hydroxyl and carboxyl, and the complexing effect is also realized simultaneouslyCan be esterified to form a reticular polyester macromolecule, thereby enhancing the uniformity of ion dispersion. In addition, the complexing effect of EDTA is greatly influenced by the pH value, ammonia water and the like are needed to adjust the pH value, and Fe ions are easy to form Fe (OH) under weak alkalinity 3 Precipitation, citric acid has better complexing effect in a wider range of pH 4-8, is suitable for all ions in a sample, has a price of only about one tenth of that of EDTA, and is low in cost.
Further, in some embodiments of the present invention, the dispersant may be a polyhydric alcohol such as ethylene glycol, glycerin, polyvinyl alcohol, etc., and functions to enhance esterification efficiency and a degree of crosslinking, and ultimately, to increase uniformity of metal ion dispersion. Wherein, the glycol is miscible with water, and compared with the glycerol, the glycol is dihydric alcohol, has higher activity, is easy to generate esterification reaction, has weaker hydroscopicity and viscosity, and is easy to store and use.
Further, in some embodiments of the invention, the ratio of the amounts of the metal ions, complexing agent and dispersant in the solution is 1:1.5-2.5:1.5-2.5. Theoretically, citric acid and metal ions are complexed according to the proportion of 1, but the complexing agent citric acid is weak acid, and under the condition of not adjusting pH, the excessive citric acid is beneficial to complexing, and meanwhile, the excessive citric acid is more beneficial to dispersing the metal ions, so that the particle size of the calcined product is reduced. The dispersant is used for forming polyester and has the same amount as citric acid, but the complexing agent and the dispersant are organic matters, and are not easy to be completely removed in the later calcining process after being excessively added.
Further, in some embodiments of the present invention, the drying in step (2) is drying the gel at 140-200 ℃ to obtain a xerogel. The drying step is to dry the gel to obtain dry gel which is convenient to grind, and simultaneously, nitrate impurities in reactants are thoroughly removed, the temperature can be raised to accelerate the drying speed under the safe condition at the normal temperature of 140 ℃.
Further, in some embodiments of the present invention, the heat-preservation calcination in the step (2) is a heat-preservation calcination at 600 to 750 ℃. The calcination step is to calcine the ground powder to remove organic impurities in the powder, theoretically, the polymer starts to be oxidized and decomposed when the powder is heated to a temperature of more than 400 ℃, and can be completely removed at a temperature of 600 ℃.
Further, in some embodiments of the present invention, the temperature increase in the step (4) is a temperature increase at a rate of 2.5 ℃/min or less.
Further, in some embodiments of the present invention, the temperature reduction in the step (4) is performed at a rate of 2.5 ℃/min or less.
The sample in the step (4) is a cake-shaped sheet obtained by pressing, and simultaneously contains a two-phase structure, the thermal expansion under heating condition is possibly inconsistent, so that the film body is curled or cracked, the temperature rising/reducing rate is optimal at 1 ℃ per minute, and the temperature rising/reducing rate is not higher than 2.5 ℃ per minute, so that the film body can be prevented from curling or cracking.
Compared with the prior art, the invention has the following advantages:
(1) The copper-containing two-phase mixed conductor oxygen permeable membrane material prepared by the invention has compact surface, no obvious cracks, defects and through holes, excellent mechanical property and capability of being applied to He/CO 2 And the like, and stably works for 100 hours in low-oxygen and corrosive atmosphere.
(2) The copper-containing two-phase mixed conductor oxygen permeable membrane material prepared by the invention has excellent oxygen permeability. For example, 0.6mm mixed conductor oxygen permeable membrane material 60wt.% Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -40wt.％Nd 0.4 Sr 0.6 Fe 0.9 Cu 0.1 O 3-δ (the mass fraction of two phases is determined by calculation of the weighing of the raw material nitrate hydrate, and if 3g of two-phase powder is synthesized, the amount of the two-phase substance is calculated from the mass of 1.8g to 1.2g, and the amount and mass of the substance corresponding to each nitrate hydrate are further calculated, and the weighing is performed), 3.17mL of cm can be obtained under the working condition of 1000 ℃ with helium as a purge gas - 2 min -1 Oxygen flux of 1.90mL cm was obtained even when carbon dioxide was used as a purge gas -2 min -1 The oxygen flux of the composite oxygen-permeable membrane is superior to that of the reported two-phase mixed conductor oxygen-permeable membrane material.
(3) The invention obtains a series of copper-containing two-phase mixed conductor oxygen-permeable membrane materials with high oxygen flux by regulating and controlling the proportion of Nd element to Cu element,and can be used in inert gas and CO-containing 2 The catalyst can stably work for a long time under the atmosphere, and can be used as a novel gas separation material and a carbon capture material to be applied to the oxygen industry of high-temperature complex atmosphere, such as the fields of oxygen-enriched combustion, water decomposition, methane partial oxidation and the like.
Drawings
FIG. 1 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) room temperature XRD pattern of copper-containing two-phase mixed conductor oxygen permeable membrane powder.
FIG. 2 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) XRD refinement results of copper-containing two-phase mixed conductor oxygen permeable membrane powder.
FIG. 3 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ SEM and BSEM photographs of (x =0.4,0.6.
FIG. 4 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) oxygen permeability of copper-containing two-phase mixed conductor oxygen permeable membrane material changes with temperature when He is used as purge gas.
FIG. 5 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) copper-containing two-phase mixed conductor oxygen-permeable membrane material as CO 2 Oxygen permeability as a sweep gas varies with temperature.
FIG. 6 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) XRD result after calcination of copper-containing two-phase mixed conducting oxygen permeable membrane powder in Ar atmosphere at 800 ℃ for 24 h.
FIG. 7 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) XRD result after calcination of copper-containing two-phase mixed oxygen-permeable conductor membrane powder in Ar atmosphere at 900 ℃ for 24 h.
FIG. 8 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) XRD result after calcination of copper-containing two-phase mixed conducting oxygen permeable membrane powder in Ar atmosphere at 1000 ℃ for 24 h.
FIG. 9 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05, 0.1) copper-containing two-phase mixed conductor oxygen-permeable membrane powder at 800 ℃ in CO 2 XRD results after calcination in atmosphere for 24 hours.
FIG. 10 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) copper-containing two-phase mixed conductor oxygen-permeable membrane powder in CO at 900 deg.C 2 XRD results after calcination in atmosphere for 24 h.
FIG. 11 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05, 0.1) copper-containing two-phase mixed conductor oxygen-permeable membrane powder at 1000 ℃ in CO 2 XRD results after calcination in atmosphere for 24 h.
FIG. 12 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) EDS picture of copper-containing two-phase mixed conductor oxygen permeable membrane material.
FIG. 13 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05, 0.1) oxygen permeability curve over time for a copper-containing two-phase mixed conductor oxygen permeable membrane under helium purge at 1000 ℃.
FIG. 14 shows Ce prepared by the method of the present invention 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ (x =0.4,0.6, y =0.05,0.1) oxygen permeability curve over time of copper-containing two-phase mixed conductor oxygen permeable membrane under carbon dioxide purge at 1000 ℃.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 8230comprises" excludes any non-specified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230title" appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates only the singular.
Furthermore, the description below of the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Example 1
3.9401g of Ce (NO) was accurately weighed 3 ) 3 ·6H 2 O，1.4633g Nd(NO 3 ) 3 ·6H 2 O，2.1474g Fe(NO 3 ) 3 ·9H 2 O,0.7139g Sr(NO 3 ) 2 ，0.1985g Cu(NO 3 ) 2 ·3H 2 O,8.7669g of citric acid monohydrate and 2.7217g of ethylene glycol are dissolved in water, the solution is stirred until the solution becomes clear and transparent, a beaker is placed on a magnetic stirrer, the heating and the evaporation are continuously carried out until the solution becomes gel, then the gel is placed in an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, the fluffy dry gel is fully ground and then is placed in a crucible, and the crucible is kept at 600 ℃ for 8 hours to be calcined to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 12 hours at 950 ℃ to obtain Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd 0.4 Sr 0.6 Fe 0.95 Cu 0.05 O 3-δ Pressing the powder under 10MPa to obtain a cake-shaped sheet body, slowly heating the sheet body to 1225 ℃ at the speed of 1 ℃/min, calcining for 5 hours, then slowly cooling at the speed of 1 ℃/min, sintering to obtain a compact two-phase mixed conductor oxygen-permeable membrane material, and polishing by using abrasive paper to obtain the copper-containing two-phase mixed conductor oxygen-permeable membrane with high oxygen flux.
Example 2
3.9401g of Ce (NO) was accurately weighed 3 ) 3 ·6H 2 O，1.4615g Nd(NO 3 ) 3 ·6H 2 O，2.0307g Fe(NO 3 ) 3 ·9H 2 O,0.7127g Sr(NO 3 ) 2 ，0.2665g Cu(NO 3 ) 2 ·3H 2 O,9.1876g citric acid monohydrate and 2.7192g ethylene glycol are dissolved in water, the solution is stirred until the solution becomes clear and transparent, a beaker is placed on a magnetic stirrer, the solution is continuously heated and evaporated until the solution becomes gel, then the gel is placed in an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, the fluffy dry gel is fully ground and then is placed in a crucible and is insulated at 600 ℃ for 8 hours to remove organic matters by calcination. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 12 hours at 950 ℃ to obtain Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd 0.4 Sr 0.6 Fe 0.9 Cu 0.1 O 3-δ Pressing the powder under 10MPa to obtain a cake-shaped sheet body, slowly heating the sheet body to 1225 ℃ at the speed of 1 ℃/min, calcining for 5 hours, then slowly cooling at the speed of 1 ℃/min, sintering to obtain a compact two-phase mixed conductor oxygen-permeable membrane material, and polishing by using abrasive paper to obtain the copper-containing two-phase mixed conductor oxygen-permeable membrane with high oxygen flux.
Example 3
3.9401g of Ce (NO) was accurately weighed 3 ) 3 ·6H 2 O，1.8842g Nd(NO 3 ) 3 ·6H 2 O，2.0397g Fe(NO 3 ) 3 ·9H 2 O,0.4521g Sr(NO 3 ) 2 ，0.1950g Cu(NO 3 ) 2 ·3H 2 O,8.9600g of citric acid monohydrate and 2.6519g of ethylene glycol are dissolved in water, the solution is stirred until the solution becomes clear and transparent, a beaker is placed on a magnetic stirrer, the heating and the evaporation are continuously carried out until the solution becomes gel, then the gel is placed in an oven at the temperature of 140 ℃ for drying for 24 hours to obtain fluffy xerogel, and the fluffy xerogel is fully ground and then is placed in a crucible for heat preservation at the temperature of 600 ℃ for 8 hours to remove organic matters by calcination. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 12 hours at 950 ℃ to obtain Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd 0.6 Sr 0.4 Fe 0.95 Cu 0.05 O 3-δ Pressing the powder into a cake-shaped sheet body under the pressure of 10MPa, slowly heating the sheet body to 1225 ℃ at the speed of 1 ℃/min, calcining for 5 hours,then slowly cooling at 1 ℃/min, sintering to obtain a compact two-phase mixed conductor oxygen permeable membrane material, and grinding with abrasive paper to obtain the copper-containing two-phase mixed conductor oxygen permeable membrane with high oxygen flux.
Example 4
3.9401g of Ce (NO) was accurately weighed 3 ) 3 ·6H 2 O，1.8818g Nd(NO 3 ) 3 ·6H 2 O，1.9290g Fe(NO 3 ) 3 ·9H 2 O,0.4513g Sr(NO 3 ) 2 ，0.2597g Cu(NO 3 ) 2 ·3H 2 O,8.9524g of citric acid monohydrate and 2.6496g of ethylene glycol are dissolved in water, the solution is stirred until the solution becomes clear and transparent, a beaker is placed on a magnetic stirrer, the solution is continuously heated and evaporated until the solution becomes gel, then the gel is placed in an oven at 140 ℃ for drying for 24 hours to obtain fluffy dry gel, the fluffy dry gel is fully ground and then is placed in a crucible, and the crucible is kept at 600 ℃ for 8 hours to be calcined to remove organic matters. Fully grinding the calcined powder, putting the powder into a crucible, and calcining the powder for 12 hours at 950 ℃ to obtain Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd 0.6 Sr 0.4 Fe 0.9 Cu 0.1 O 3-δ Pressing the powder at 10MPa to obtain a cake-shaped sheet body, slowly heating the sheet body to 1225 ℃ at the speed of 1 ℃/min, calcining for 5 hours, then slowly cooling at the speed of 1 ℃/min, sintering to obtain a compact two-phase mixed conductor oxygen-permeable membrane material, and grinding with abrasive paper to obtain the copper-containing two-phase mixed conductor oxygen-permeable membrane with high oxygen flux.
Effects of the embodiment
When the air flow is 150mL min -1 Purge gas 49mL min -1 He+1mL min -1 Ne，60wt.％Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ --40wt.％Nd 0.4 Sr 0.6 Fe 0.9 Cu 0.1 O 3-δ Example 2 3.17mL cm was obtained at 1000 deg.C -2 min -1 The above oxygen fluxes can be repeated with the worst performance of 60wt.% Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ --40wt.％Nd 0.6 Sr 0.4 Fe 0.9 Cu 0.1 O 3-δ (examples of the invention)4) Also exhibited 2.0mL cm -2 min -1 The above oxygen flux. All systems can be in the presence of CO 2 Working for more than 100 hours in the working environment atmosphere, and when the air flow is 150mL min -1 Purge gas 49mL min - 1 CO 2 +1mL min -1 Ne，60wt.％Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ --40wt.％Nd 0.4 Sr 0.6 Fe 0.9 Cu 0.1 O 3-δ Example 2 at 1000 ℃ 1.90mL cm can be obtained -2 min -1 The above oxygen flux.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (13)

1. A copper-containing two-phase mixed oxygen-permeable conductor membrane material with high oxygen flux is characterized in that the composition of the copper-containing two-phase mixed oxygen-permeable conductor membrane material with high oxygen flux is as follows: ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ Wherein x =0.4 or 0.6; y =0.05 or 0.1.
2. The preparation method of the high-oxygen-flux copper-containing two-phase mixed conductor oxygen-permeable membrane material of claim 1, which is characterized by comprising the following steps:
(1) Ce is weighed in turn according to the stoichiometric ratio 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ Dissolving the corresponding nitrate in water, fully stirring the mixture until the nitrate is dissolved, and adding a complexing agent and a dispersing agent to obtain a mixed solution;
(2) Stirring the solution obtained in the step (1) until the solution becomes clear and transparent, then stirring and heating until the solution is converted into gel, drying the gel to obtain dry gel, fully grinding, preserving heat and calcining to remove organic matters to obtain powder;
(3) Calcining the powder obtained in the step (2) at 950-1000 ℃ to obtain Ce 0.85 Nd 0.1 Cu 0.05 O 2-δ -Nd x Sr 1-x Fe 1-y Cu y O 3-δ The powder of (4);
(4) And (4) tabletting the powder obtained in the step (3) to obtain a cake-shaped sheet body, heating the sheet body to 1210-1235 ℃, calcining, slowly cooling, sintering to obtain a compact two-phase mixed conductor oxygen permeable membrane, and polishing to obtain the copper-containing two-phase mixed conductor oxygen permeable membrane material with the required thickness and high oxygen flux.
3. The preparation method of the high oxygen flux copper-containing two-phase mixed conductor oxygen permeable membrane material according to claim 2, wherein the complexing agent is one or more of EDTA, citric acid or HEDTA.
4. The preparation method of the copper-containing two-phase mixed conductor oxygen permeable membrane material with high oxygen flux according to claim 2, wherein the complexing agent is EDTA or/and citric acid.
5. The preparation method of the high-oxygen-flux copper-containing two-phase mixed conductor oxygen-permeable membrane material according to claim 2, wherein the complexing agent is citric acid.
6. The preparation method of the high-oxygen-flux copper-containing two-phase mixed conductor oxygen-permeable membrane material according to claim 2, characterized in that the dispersant is one or more of ethylene glycol, glycerol or polyvinyl alcohol.
7. The preparation method of the high oxygen flux copper-containing two-phase mixed conductor oxygen permeable membrane material according to claim 2, wherein the dispersant is ethylene glycol.
8. The preparation method of the copper-containing two-phase mixed conductor oxygen permeable membrane material with high oxygen flux according to claim 2, characterized in that the ratio of the amounts of the metal ions, the complexing agent and the dispersing agent in the solution in the step (1) is 1:1.5-2.5:1.5-2.5.
9. The preparation method of the copper-containing two-phase mixed oxygen permeable membrane material with high oxygen flux according to claim 2, wherein the drying in the step (2) is drying the gel at 140-200 ℃ to obtain xerogel.
10. The preparation method of the copper-containing two-phase mixed oxygen permeable membrane material with high oxygen flux according to claim 2, wherein the heat-preservation calcination in the step (2) is heat-preservation calcination at 600-750 ℃.
11. The preparation method of the high-oxygen-flux copper-containing two-phase mixed conductor oxygen-permeable membrane material according to claim 2, wherein the temperature rise in the step (4) is at a rate of 2.5 ℃/min or less.
12. The preparation method of the copper-containing two-phase mixed conductor oxygen permeable membrane material with high oxygen flux according to claim 2, wherein the temperature reduction in the step (4) is carried out at a rate of less than 2.5 ℃/min.
13. The use of the high oxygen flux copper containing two-phase mixed conducting oxygen permeable membrane material of claim 1 for performance analysis of oxygen separation and its stability.
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