CN102463039A - CO2, SO2 resistant composite oxygen permeable ceramic membrane, preparation and application thereof - Google Patents

CO2, SO2 resistant composite oxygen permeable ceramic membrane, preparation and application thereof Download PDF

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CN102463039A
CN102463039A CN2010106005778A CN201010600577A CN102463039A CN 102463039 A CN102463039 A CN 102463039A CN 2010106005778 A CN2010106005778 A CN 2010106005778A CN 201010600577 A CN201010600577 A CN 201010600577A CN 102463039 A CN102463039 A CN 102463039A
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朱雪峰
刘焕英
丛铀
杨维慎
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses a novel CO2, SO2 resistant composite oxygen permeable ceramic membrane, which is formed by oxygen ion conductive oxides and electron-oxygen ion mixing conductive oxides, wherein the oxygen ion conductor is the oxide with a fluorite structure; the mixing conductor is the oxide with a perovskite structure; the mass ratio of the oxygen ion conductive oxide to the mixing conductive oxide is 9:1-1:4; the chemical formula is (100-x)wt%Cel-yLnyO2-y/2-xwt%Ln1-zCazM11-wM2wO3; in the formula, x is not less than 10 and not greater than 80; y is not less than 0.05 and not greater than 0.5; z is not less than 0 and not greater than 0.8; w is not less than 0 and not greater than 1; Ln is any one or both of lanthanide and Y; and M1 and M2 are two different elements in the Mn, Fe, Co and Ni. The composite oxides are prepared by a solid-phase synthesis method for mixing all metal oxides powder directly. The composite oxides are used for separating the air comprising CO2 and SO2 at a high temperature and an air separating process which adopts flue gas as sweep gas.

Description

A kind of anti-CO 2, SO 2Composite oxygen penetrating ceramics membrane and preparation thereof and application
Technical field
The present invention relates to novel anti-CO 2And SO 2The design of composite oxygen penetrating ceramics membrane, preparation, structure, and be used for high temperature and separate and to contain CO 2And SO 2Air separation and be the air separation process of sweep gas with flue gas.
Background technology
[0002] composite conductor oxygen-permeating film refer to one have oxygen conduction and electron conduction roughly the same the time the new ceramics film.This material at high temperature (is worked as temperature greater than 700 especially oDuring C), when there was oxygen concentration gradient in the film both sides, oxygen can be conducted to the hypoxemia nip by the hyperoxia nip through body with the form of oxonium ion, and electronics can conduct in the opposite direction simultaneously, thereby makes material keep electroneutral.This material does not resemble needs external circuits to come conduction electron the SOFC.And because oxygen is to conduct with the form of oxonium ion, the permselective property of oxygen is 100% in theory.
Thermal power generation is discharging CO 2Maximum industry, 40% CO in the world has an appointment 2Discharging comes from the power plant of combustion of fossil fuels.Therefore, discharging CO 2Maximum coal-burning power plants becomes tool potentiality and implements CO 2The industry that captures.At present, the generally acknowledged reduction CO in the whole world 2Discharging one of effective method is that technology (CCS-Carbon Capture and Storage) is caught and sealed up for safekeeping to carbon, promptly separates from the emission source of the industry or the relevant energy, be transported to one and seal the place up for safekeeping, and a process of long-term and atmospheric isolation.CCS comprises and catching, and transports and store three links, is wherein catching this step up to the energy consumption more than 75%, and therefore how research reduces CO 2Catching cost is the most important thing of development CCS technology.To can be used for catching with the fossil fuel be main and CO that in power generation process, produce numerous 2New method in, the Oxyfuel power generation process is the most noticeable, this process is used oxygen (>95%) replaces air to carry out fuel, produce with steam and CO as primary combustion 2Be main flue gas and a spot of SO 2, its CO 2Concentration is up to more than 80%.Remove steam through air-flow is cooled off and compresses then, can obtain the high concentration CO that can be used to seal up for safekeeping 2Yet the high-concentration oxygen cost that obtains based on conventional art is higher, makes that catching cost based on the carbon of Oxyfuel process significantly increases.
Under the high temperature, in film separation system, being unstripped gas with compressed air, is CO with the main component 2Power plant tail gas be sweep gas, can realize air separation.The separating obtained gaseous mixture that is rich in oxygen generates electricity with combustion of fossil fuel again, a part of CO of generation 2Return film separation system, another part is then through heat exchange, be used to bury after compressing and liquefying.Can find out that oxygen permeation membrane technology is with after oxygen fuel generation technology combines, the heat energy that impermeable gas keeps in the air separation process can effectively be become electric energy by steam turbine with the compression ability.With the cryogenic air separation compared with techniques, the development of oxygen permeation membrane technology will reduce the equipment investment and the operating cost of air-seperation system.Therefore, just have more competitiveness, realize that more effectively low cost catches CO based on the oxygen fuel power generation process of oxygen permeation membrane 2Though the research about oxygen permeable ceramic film has continued to surpass 30 years, the research at aspects such as air separation and conversion of natural gas also makes significant progress, and applies it to the Oxyfuel generating and is faced with great challenge.Existing composite conductor oxygen-permeating film material based on perovskite structure is difficult in and contains CO 2, SO 2, H 2Stable existence in the power plant tail gas of O is easy to and the above-mentioned gas reaction generates carbonate, sulfate etc. as the alkali earth metal of this type oxygen permeable film material important composition, thereby makes the oxygen permeable film material structural deterioration, and oxygen permeating amount sharply descends.And the oxygen permeating amount of the perovskite oxygen permeable film material of alkali-free earth metal element is often very low, is difficult to reach industrial application requirements.A pair of like this contradiction is difficult to unified in perovskite, therefore, develops novel high stability, and the oxygen permeable film material of high osmosis is imperative, and this also is the key point of improved Oxyfuel generation technology.Membrane material layout strategy in the past can not satisfy the requirement of Oxyfuel process to membrane material; But the design of two-phase oxygen permeable film material then can break through the stability and the conflicting restriction of permeability of perovskite material; The electronic conduction that the researcher can require to design respectively membrane material according to reality mutually with ionic conduction mutually, thereby obtain high stability and infiltrative membrane material more easily.
Summary of the invention
The object of the present invention is to provide a kind of anti-CO 2, SO 2Composite oxygen penetrating ceramics membrane makes it can satisfy the requirement of Oxyfuel power generation process to membrane material stability.
For realizing above-mentioned purpose, anti-CO provided by the invention 2And SO 2Composite oxygen penetrating ceramics membrane; It is characterized in that: said composite oxygen penetrating ceramics membrane is made up of oxide ion conduction oxide and electronics-oxonium ion hybrid conductive oxide; Wherein oxygen ion conductor is the oxide with fluorite structure; Mixed conductor is the oxide with perovskite structure, and the mass ratio of oxide ion conduction oxide and hybrid conductive oxide is: 9: 1 ~ 1: 4; Chemical formula is:
（100-x）wt%?Ce 1-yLnyO 2-y/2?–?xwt%?Ln 1-zCa zM1 1-wM2 wO 3;
10≤x in the formula≤80,0.05≤y≤0.5,0≤z≤0.8,0≤w≤1;
Be preferably: 10≤x≤70,0.05≤y≤0.3,0≤z≤0.8,0≤w≤1.
Wherein Ln is selected from+among 3 valency lanthanide series and the Y one or more;
M1 and M2 are selected from one or more among Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, the Zn.
Anti-CO provided by the invention 2And SO 2Composite oxygen penetrating ceramics membrane is characterized in that: expression formula Ce 1-yLnyO 2-y/2In Ln be preferably among La, Sm, Gd, Dy, Yb, the Y one or more; The best is a kind of among La, Sm, the Gd.Expression formula Ln 1-zCa zM1 1-wM2 wO 3In Ln be preferably among La, Sm, Gd, Dy, Yb, the Y one or more; The best is one or both the mixing among Mn, the Co.
Ce in the expression formula 1-yLnyO 2-y/2Ln and expression formula Ln 1-zCa zM1 1-wM2 wO 3In Ln identical.
Anti-CO provided by the invention 2And SO 2Composite oxygen penetrating ceramics membrane is characterized in that: expression formula Ln 1-zCa zM1 1-wM2 wO 3In M1 and M2 be preferably among Mn, Fe, Co, Ni, the Cu one or more, the best is one or both the mixing among Mn, the Co.
Anti-CO provided by the invention 2And SO 2Composite oxygen penetrating ceramics membrane is the solid phase synthesis process preparation through all metal oxide powder of direct mixing; Concrete preparation method is: directly mix the synthetic composite membrane of all metal oxides; According to the relative mass ratio of desired two kinds of oxides, the corresponding oxide of getting chemical dose is in agate jar, to wherein adding an amount of absolute ethyl alcohol; Behind the high speed ball milling 2 hours, 1200 oC roasting 10 hours.The gained powder is continued ball milling, roasting, thresh three times, finally obtain anti-CO 2And SO 2Composite oxide powder.With this powder in 400 MPa lower sheeting moulding.With the raw cook that presses 1360 ~ 1400 oPromptly get behind C sintering 3 h.
Anti-CO provided by the invention 2And SO 2Composite oxygen penetrating ceramics membrane is characterized in that: can be applied to the high temperature separation and contain CO 2And SO 2Air separation and be the air separation process of sweep gas with flue gas.
Description of drawings
Fig. 1 is typical anti-CO 2And SO 2The XRD figure of composite oxygen penetrating ceramics membrane;
Fig. 2 is typical anti-CO 2And SO 2Composite oxygen penetrating ceramics membrane Electronic Speculum figure;
Fig. 3 is the long-term oxygen osmotic stability figure of 75wt%SDC-25wt%SMC;
Fig. 4 is the long-term oxygen osmotic stability figure of 75wt%SDC-25wt%SCMC.
 
The specific embodiment
Embodiment 1
Directly mix synthetic (100-x) wt% Ce of all metal oxides 0.95Gd 0.05O 1.975-x wt% Gd 0.2Ca 0.8MnO 3Composite membrane, wherein x=10.According to the relative mass ratio of desired two kinds of oxides, the corresponding oxide of getting chemical dose is in agate jar, and to wherein adding an amount of absolute ethyl alcohol, the high speed ball milling is after 2 hours, 1200 oC roasting 10 hours.The gained powder is continued ball milling, roasting, thresh three times, finally obtain anti-CO 2And SO 2Composite oxide powder.With this powder in 400 MPa lower sheeting moulding.With the raw cook that presses 1400 oPromptly get desired composite membrane behind C sintering 3 h.With this anti-CO 2And SO 2Composite membrane is labeled as GDC-GSM.Its XRD figure and electromicroscopic photograph are as depicted in figs. 1 and 2.
 
Embodiment 2
Directly mix synthetic (100-x) wt% Ce of all metal oxides 0.8Gd 0.2O 1.9-x wt% Gd 0.9Ca 0.1CoO 3Composite membrane, wherein x=30.According to the relative mass ratio of desired two kinds of oxides, the corresponding oxide of getting chemical dose is in agate jar, and to wherein adding an amount of absolute ethyl alcohol, the high speed ball milling is after 2 hours, 1200 oC roasting 10 hours.The gained powder is continued ball milling, roasting, thresh three times, finally obtain anti-CO 2And SO 2Composite oxide powder.With this powder in 400 MPa lower sheeting moulding.With the raw cook that presses 1360 oPromptly get desired composite membrane behind C sintering 3 h.With this anti-CO 2And SO 2Composite membrane is labeled as GDC-GCC.Its XRD figure and electromicroscopic photograph are as depicted in figs. 1 and 2.
 
Embodiment 3
Directly mix synthetic (100-x) wt% Ce of all metal oxides 0.75Sm 0.25O 1.875-x wt% SmMn 0.5Co 0.5O 3Composite membrane, wherein x=80.According to the relative mass ratio of desired two kinds of oxides, the corresponding oxide of getting chemical dose is in agate jar, and to wherein adding an amount of absolute ethyl alcohol, the high speed ball milling is after 2 hours, 1200 oC roasting 10 hours.The gained powder is continued ball milling, roasting, thresh three times, finally obtain anti-CO 2And SO 2Composite oxide powder.With this powder in 400 MPa lower sheeting moulding.With the raw cook that presses 1360 oPromptly get desired composite membrane behind C sintering 3 h.With this anti-CO 2And SO 2Composite membrane is labeled as SDC-SMC.Its XRD figure and electromicroscopic photograph are as depicted in figs. 1 and 2.
 
Embodiment 4
Directly mix the synthetic 90wt% Ce of all metal oxides 0.85Sm 0.15O 1.925-10wt% Sm 0.8Ca 0.2CoO 3Composite membrane and 40wt% Ce 0.85Sm 0.15O 1.925-60 wt% Sm 0.8Ca 0.2CoO 3According to the relative mass ratio of desired two kinds of oxides, the corresponding oxide of getting chemical dose is in agate jar, and to wherein adding an amount of absolute ethyl alcohol, the high speed ball milling is after 2 hours, 1200 oC roasting 10 hours.The gained powder is continued ball milling, roasting, thresh three times, finally obtain anti-CO 2And SO 2Composite oxide powder.With this powder in 400 MPa lower sheeting moulding.With the raw cook that presses 1360 oPromptly get desired composite membrane behind C sintering 3 h.Its oxygen permeating amount is 900 oC can reach 0.4 and 0.2 ml cm respectively -2.min -1About.
 
Embodiment 5
Adopt above-mentioned (with embodiment 1) method to synthesize 75wt% Ce 0.85Sm 0.15O 1.925-25 wt% SmMn 0.5Co 0.5O 3Composite membrane is measured its long-time oxygen flow stability.Adopt chromatography, He is sweep gas and chromatogram carrier gas, with 13X molecular sieve separating nitrogen oxygen, is the infiltration source of the gas with the air.Oxygen standard gas with 3.4% carries out chromatogram to be demarcated, and adopts high temperature straight pipe type osmotic cell, and diaphragm thickness is 0.50 mm, and gold ring is adopted in the sealing-in of diaphragm and osmotic cell, and measuring temperature is 940 oC, oxygen flow can find out that stable back oxygen permeating amount can reach 0.21 ml.cm -2.min -1About, as shown in Figure 3.
 
Embodiment 6
Adopt above-mentioned (with embodiment 1) method to synthesize 75wt% Ce 0.85Sm 0.15O 1.925-25 wt% Sm 0.8Ca 0.2Mn 0.5Co 0.5O 3, measure it with CO 2Long-time oxygen flow stability for sweep gas.Adopt chromatography, He is sweep gas and chromatogram carrier gas, with 13X molecular sieve separating nitrogen oxygen, is the infiltration source of the gas with the air.Oxygen standard gas with 3.4% carries out chromatogram to be demarcated, and adopts high temperature straight pipe type osmotic cell, and diaphragm thickness is 0.50 mm, and the silver circle is adopted in the sealing-in of diaphragm and osmotic cell, and the oxygen flow data are as shown in Figure 4.
 
Embodiment 7
Adopt above-mentioned (with embodiment 1) method to synthesize 80wt% Ce 0.8Sm 0.2O 1.9-20 wt% SmMn 0.5Co 0.5O 3, measure it to contain SO 2The CO of (1000 ppm) 2For the long-time oxygen flow of sweep gas steady.The employing said method is synthetic.Adopt chromatography, He is sweep gas and chromatogram carrier gas, with 13X molecular sieve separating nitrogen oxygen, is the infiltration source of the gas with the air.Oxygen standard gas with 3.4% carries out chromatogram to be demarcated, and adopts high temperature straight pipe type osmotic cell, and diaphragm thickness is 0.40 mm, and the silver circle is adopted in the sealing-in of diaphragm and osmotic cell, and measuring temperature is 850 oC, stable back oxygen permeating amount can reach 0.3 ml.cm -2.min -1About.
 
Embodiment 8
Adopt above-mentioned (with embodiment 1) method to synthesize 80wt% Ce 0.85La 0.15O 1.925-20 wt% La 0.8Ca 0.2Mn 0.5Co 0.5O 3, measure it to contain SO 2The CO of (1000 ppm) 2For the long-time oxygen flow of sweep gas steady.Adopt chromatography, He is sweep gas and chromatogram carrier gas, with 13X molecular sieve separating nitrogen oxygen, is the infiltration source of the gas with the air.Oxygen standard gas with 3.4% carries out chromatogram to be demarcated, and adopts high temperature straight pipe type osmotic cell, and diaphragm thickness is 0.50 mm, and the silver circle is adopted in the sealing-in of diaphragm and osmotic cell, and measuring temperature is 850 oC, stable back oxygen permeating amount can reach 0.2 ml.cm -2.min -1About.

Claims (8)

1. anti-CO 2, SO 2Composite oxygen penetrating ceramics membrane is characterized in that:
Said composite oxygen penetrating ceramics membrane is made up of oxide ion conduction oxide and electronics-oxonium ion hybrid conductive oxide; Wherein oxygen ion conductor is the oxide with fluorite structure; Mixed conductor is the oxide with perovskite structure, and the mass ratio of oxide ion conduction oxide and hybrid conductive oxide is: 9: 1 ~ 1: 4; Chemical formula is:
（100-x）wt%?Ce 1-yLnyO 2-y/2?–?xwt%?Ln 1-zCa zM1 1-wM2 wO 3；
10≤x in the formula≤80,0.05≤y≤0.5,0≤z≤0.8,0≤w≤1;
Ln is selected from+among 3 valency lanthanide series and the Y one or more;
M1 and M2 are selected from one or more among Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, the Zn.
2. according to the described anti-CO of claim 1 2, SO 2Composite oxygen penetrating ceramics membrane is characterized in that, in the said chemical expression:
10?≤?x?≤?70,?0.05?≤?y?≤?0.3,?0?≤?z?≤?0.8,?0?≤?w?≤?1。
3. according to the described anti-CO of claim 1 2, SO 2Composite oxygen penetrating ceramics membrane is characterized in that, said expression formula Ce 1-yLnyO 2-y/2In Ln be among La, Sm, Gd, Dy, Yb, the Y one or more; Expression formula Ln 1-zCa zM1 1-wM2 wO 3In Ln be among La, Sm, Gd, Dy, Yb, the Y one or more; And Ce in the expression formula 1-yLnyO 2-y/2Ln and expression formula Ln 1-zCa zM1 1-wM2 wO 3In Ln identical.
4. according to the described anti-CO of claim 1 2, SO 2Composite oxygen penetrating ceramics membrane is characterized in that expression formula Ln 1-zCa zM1 1-wM2 wO 3In M1 and M2 be among Mn, Fe, Co, Ni, the Cu one or more.
5. according to the described anti-CO of claim 3 2, SO 2Composite oxygen penetrating ceramics membrane is characterized in that expression formula Ce 1-yLnyO 2-y/2In Ln be a kind of among La, Sm, the Gd.
6. according to the described anti-CO of claim 4 2, SO 2Composite oxygen penetrating ceramics membrane is characterized in that expression formula Ln 1-zCa zM1 1-wM2 wO 3In M1 and M2 be one or both the mixing among Mn, the Co.
7. described anti-CO of claim 1-6 2, SO 2The preparation method of composite oxygen penetrating ceramics membrane is characterized in that concrete preparation method is:
According to the relative mass ratio of desired two kinds of oxides, the corresponding oxide of getting chemical dose is in agate jar, and to wherein adding absolute ethyl alcohol, the high speed ball milling is after 2 hours, 1200 oC roasting 10 hours; The gained powder is continued ball milling, roasting, thresh three times, finally obtain anti-CO 2And SO 2Composite oxide powder; With this powder in 400 MPa lower sheeting moulding, with the raw cook that presses 1360 ~ 1400 oPromptly get behind C sintering 3 h.
8. according to the described anti-CO of claim 1-6 2, SO 2Composite oxygen penetrating ceramics membrane is used for the high temperature separation and contains CO 2And SO 2Air separation and be the air separation process of sweep gas with flue gas.
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Publication number Priority date Publication date Assignee Title
CN103071397A (en) * 2013-01-17 2013-05-01 南京工业大学 Method for preparing high temperature CO2 separation membrane
CN108117388A (en) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 Ti base two-phase oxygen permeable ceramic film materials
CN108117389A (en) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 Fe base two-phase oxygen permeable ceramic film materials
CN108117044A (en) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 A kind of method for preparing high-purity hydrogen

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103071397A (en) * 2013-01-17 2013-05-01 南京工业大学 Method for preparing high temperature CO2 separation membrane
CN108117388A (en) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 Ti base two-phase oxygen permeable ceramic film materials
CN108117389A (en) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 Fe base two-phase oxygen permeable ceramic film materials
CN108117044A (en) * 2016-11-26 2018-06-05 中国科学院大连化学物理研究所 A kind of method for preparing high-purity hydrogen

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