CN101306330B - Production method of mixed conductor oxygen permeable membrane and oxygen/carbon monoxide mixed gas - Google Patents
Production method of mixed conductor oxygen permeable membrane and oxygen/carbon monoxide mixed gas Download PDFInfo
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- CN101306330B CN101306330B CN2008100205595A CN200810020559A CN101306330B CN 101306330 B CN101306330 B CN 101306330B CN 2008100205595 A CN2008100205595 A CN 2008100205595A CN 200810020559 A CN200810020559 A CN 200810020559A CN 101306330 B CN101306330 B CN 101306330B
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Abstract
The invention discloses a mixed conducting oxygen-permeable membrane and a method for the production of O2/CO2 mixed gas, which is characterized in that the B-site of the ABO3 perovskite structure is doped with high valence or high electronegativity ions and the chemical formula is XxYyZzO3-Delta, wherein, X is one or more of lanthanides, alkaline earth metal or alkali metal elements; Y is selected from Cr, Mn, Fe, Co, Ni, Cu and/or Zn; Z is selected from Ti, Zr, Ge, Sn, Mo, W, V, Nb, Ta, Ce, Al, and or Ga, x, y and z are mole fractions, x is not less than 0.9 and not more than 1.0, z is more than 0 and not more than 0.4, and y plus z is equal to 1.0. The mixed conducting oxygen-permeable membrane has corrosion resistant ability of CO2 with high concentration, and high oxygen permeable ability, thereby being used for producing the O2/CO2 mixed gas, reducing energy consumption, simplifying the operation, continuously supplying high-purity oxygen and overcoming the shortcomings of great energy consumption and complex operation of the prior art.
Description
Technical field
The invention belongs to the ceramic oxygen-permeable membrane technical field, particularly Ca-Ti ore type composite conductor oxygen-permeating film material and producing O
2/ CO
2The application of gaseous mixture aspect.
Background technology
A large amount of CO are discharged in mankind's activity
2The caused greenhouse effects of gas have caused catastrophic destruction to earth environment, wherein cause CO in the atmosphere owing to fossil fuel especially a large amount of uses of the fuel of high carbon content (such as coal) has become
2How the main cause that content raises reduces CO among the human production activity
2Discharging become the focus of global scientist research.U.S.'s " year looks back " (Annual Reviews, 1996,21:145) introduced minimizing CO
2The whole bag of tricks of discharging, one of them is exactly to collect the CO that combustion of fossil fuel generates
2, be stored in it underground then or the ocean in.Yet the CO in the combustion of fossil fuel discharging tail gas
2Concentration is no more than 15%, separate, collect CO from the gas of low concentration like this
2, difficulty is big, cost is high.This magazine (Annual Reviews, 1996,21:145) introduced, handled CO from large-scale energy resource system recovery
2Various possibility methods, O wherein
2/ CO
2Combustion technology is a kind of feasible method.U.S.'s " air and waste management association proceedings " (Journal of the Air and Waste Management Association, 1991,41:449) to O
2/ CO
2Combustion technology (also claiming air separation/flue gas recirculating technique) is introduced, and thinks that this technology is to be hopeful to be applied to the large-scale thermal power station most to realize CO
2The advanced combustion technology of zero-emission.The gaseous mixture that this technology adopts the boiler exhaust of the oxygen that obtains from air separation and part circulation to constitute replaces the act as a fuel oxidant of burning of air, and the combustion product of gained is the CO of high concentration
2Gas is convenient to CO
2Separation, collection and storage, thereby realize CO
2Zero-emission.Though this method can realize CO
2Recovery fully, but want the energy of additive decrementation 30% to be used for and compress CO from the air oxygen separation
2, this will make the cost of generating increase about 80%.Therefore, the energy consumption and the cost of reduction air separation can promote O
2/ CO
2The popularization of combustion technology and enforcement, thus realize large-scale CO
2Reduce discharging.
At present from air the method for oxygen separation based on cryogenic rectification method.Chinese patent 200510054064.0 has been introduced the general technology flow process of cryogenic rectification system oxygen: air after filtration, enter molecular sieve adsorber to remove CO after the compression, precooling
2And H
2O enters high-pressure rectification tower initial gross separation oxygen again after cooling and nitrogen obtains thick oxygen, and thick then oxygen enters the further removing foreign matter nitrogen of low-pressure distillation tower, finally obtains highly purified oxygen.This technical matters flow process complexity, equipment needed thereby is various, investment is big, therefore only is applicable to large-scale production; In addition, this Technology Need just can carry out oxygen production with air pressurized at least 6 atmospheric pressures, and Compressed Gas will consume big energy, so this technology energy consumption is bigger.
The employing ceramic oxygen-permeable membrane of mentioning in the Chinese patent application 200710191177.4 is produced O
2/ CO
2The method of gaseous mixture is used oxygen ion conductor and the compound composite conductor oxygen-permeating film material preparation of electronic conductor two-phase hollow fiber film tube, feeds normal pressure or is higher than the oxygen gas mixture that contains of normal pressure in film pipe one side, feeds CO at opposite side
2, film pipe tail end can obtain O under 850～1150 ℃ of temperature conditions
2/ CO
2Gaseous mixture.This method is with air-separating oxygen-making and O
2, CO
2Mix two steps and be combined into a step, and making oxygen is simple, energy consumption is little, overcome the shortcoming that the cryogenic rectification technology exists.But this specification requirement oxygen permeable film material must the ability high concentration CO
2The corrosion of gas simultaneously can be at high concentration CO
2Keep sufficiently high oxygen flow ability in the atmosphere, though the compound composite conductor oxygen-permeating film material of its two-phase that adopts has anti-preferably CO
2Corrosive power, but its oxygen flow ability is also undesirable, the highlyest can only reach 10
-7Mol/cm
2The s magnitude.In addition, the biphase mixed conducting oxygen-permeable membrane material is to synthesize ion conductor respectively mutually both to be mixed and make at high temperature sintering after mutually with electronic conductor, two-phase tends to the phase counterdiffusion at high temperature, thereby reaction causes oxygen permeability to descend, U.S.'s " electrochemistry meeting will " (Journalof The Electrochemical Society, 2005,152:A1347) just introduced La
0.8Sr
0.2MnO
3With the stable ZrO of yttrium
2Two kinds of examples that material reacts at high temperature.
One-component ceramic oxygen permeable film material with perovskite structure has higher oxygen flow ability.Japan's " chemical communication " (Chemistry Letters, 1985,173:1743) the La that reports at first with perovskite structure
1-xSr
xCo
1-yFe
yO
3-δSrCo in the system
0.8Fe
0.2O
3-δOxygen permeable film material has high oxygen transmission rate, and its oxygen permeability can reach 10 at 850 ℃
-6Mol/cm
2The s magnitude; Holland " membrane science magazine " (Journal of Membrane Science, 2000,172:177) Bao Dao Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3-δOxygen permeable film material also has high oxygen flow ability.But this class material can not be at CO
2Use in the atmosphere, because its anti-CO
2The corrosive power extreme difference.Holland's " membrane science magazine " (Journal of Membrane Science, 2007,293:44) report Ba
0.5Sr
0.5Co
0.8Fe
0.2O
3-δOxygen permeable film material and CO
2Reaction is violent, at CO
2Almost lose the oxygen flow ability in the atmosphere.According to another Holland's " solid-state ionics " (Solid State Ionics, 2001,139:219) report, Sr
xCa
1-xCo
0.5Fe
0.5O
3-δSeries oxygen permeable film material meeting and CO
2Vigorous reaction takes place, even can be used as CO
2Absorbing material.
Summary of the invention:
The present invention proposes a kind of resisting high-concentration CO that has
2Corrosive power and have the composite conductor oxygen-permeating film of high oxygen flow ability and use it for and produce O
2/ CO
2The method of gaseous mixture is to overcome that existing oxygen permeation membrane exists and CO
2The shortcoming that reaction is violent, the oxygen flow ability is lower.
Composite conductor oxygen-permeating film of the present invention is characterised in that it is for having ABO
3Perovskite structure also mixes the single-phase or biphase mixed conducting oxygen-permeable membrane of high valence state or high electronegativity ion in the B position, its composition can be A with chemical formulation
xB
yB '
zO
3-δ, wherein A is one or more in lanthanide series, alkali earth metal or the alkali metal; B is selected from Cr, Mn, Fe, Co, Ni, Cu and/or Zn; B ' ion has high valence state or high electronegativity, and B ' is selected from Ti, Zr, Ge, Sn, Mo, W, V, Nb, Ta, Al and/or Ga; Subscript x, y, z are molar fraction, wherein 0.9≤x≤1.0,0＜z≤0.4 and y+z=1.0; δ is non-metering oxygen, 0＜δ＜1.
Adopt above-mentioned composite conductor oxygen-permeating film of the present invention to be used to produce O
2/ CO
2The method of gaseous mixture, be characterised in that its flow process is: with main component is CO
2Combustion tail gas 4, obtaining drying and burning tail gas 5 through purifying processor 10 after dewatering, account for volume fraction in the drying and burning tail gas 5 and be 10～50% part and enter CO
2Collector unit 11, remaining accounts for volume fraction is that the compressed air 1 that 50～90% part and the pressure after the preheating are 1～5 atmospheric pressure enters composite conductor oxygen-permeating film assembly 7 simultaneously, at 800～1100 ℃, oxygen in the compressed air 1 is penetrated into the combustion tail gas 5 of opposite side drying the O that produces from a side of composite conductor oxygen-permeating film 8
2/ CO
2Gaseous mixture 6 enters combustion chamber 9 oxidation fossil fuels 3; The low oxygen content compressed air 2 that comes out from composite conductor oxygen-permeating film assembly 7 emptying or do other uses after reclaiming heat.
Described composite conductor oxygen-permeating film assembly 7 can be to place cavity to constitute one or one group ceramic membrane that uses composite conductor oxygen-permeating film material of the present invention to make, the ceramic membrane both sides that link to each other with pipeline respectively can feed gas with various respectively, described ceramic membrane profile can be flat board, also can be the hollow polyhedron of hollow circular tube, spherical shell or the hemispherical Shell of an end or both ends open, a face or several openings.
Compared with prior art, the present invention has following characteristics and advantage:
1, composite conductor oxygen-permeating film of the present invention has resisting high-concentration CO preferably
2Corrosive power is at CO
2Stability in the atmosphere significantly improves, and has overcome the one-component ceramic oxygen permeation membrane and the CO of existing perovskite structure
2Thereby react the violent shortcoming that the oxygen flow ability declines to a great extent that makes.
2, composite conductor oxygen-permeating film of the present invention is at CO
2Have high oxygen flow ability in the atmosphere.The thickness that uses composite conductor oxygen-permeating film material preparation of the present invention is the oxygen flow diaphragm of the 1mm CO at 900 ℃
2Oxygen transmission rate in the atmosphere can reach 10
-6Mol/cm
2The s order of magnitude, this oxygen transmission rate can satisfy the needs of commercial Application.
3, composite conductor oxygen-permeating film material of the present invention is to rise to react back and making of high temperature after various raw materials are mixed, and the amount of substance of the B ' element in raw material surpasses it at ABO
3Just have second phase AB ' O during solid solubility in the perovskite structure
3Generate, but since in the principal phase material solid solution enough B ' ions reached the chemically stable state, so do not have principal phase and second AB ' O mutually
3Between situation about reacting to each other, overcome the shortcoming that reacts to each other between existing oxygen ion conductor and the compound composite conductor oxygen-permeating film material of the electronic conductor two-phase two-phase.
4, O of the present invention
2/ CO
2The production method of gaseous mixture only needs CO
2Gas purging is crossed the oxygen permeation membrane assembly and can be realized oxygen separation from air and make O
2/ CO
2Gaseous mixture, production procedure is simple; Overcome prior art adopt cryogenic rectification method system oxygen then with CO
2The mixed O that gets
2/ CO
2The shortcoming of gaseous mixture flow process complexity, complex operation.
5, O of the present invention
2/ CO
2The production method of gaseous mixture only needs air pressurized to 1～5 atmospheric pressure just can be produced O
2Volume content is not less than 20% O
2/ CO
2Gaseous mixture, and existing cryogenic rectification oxygenerating technology need just can be produced O more than the atmospheric pressure with air pressurized to 6
2Thereby produce O
2/ CO
2Gaseous mixture.The inventive method can cut down the consumption of energy and cost of investment greatly owing to can adopt lower compressed air pressure.
Description of drawings
Fig. 1 is that the present invention adopts the ceramic oxygen-permeable membrane assembly to produce O
2/ CO
2The basic procedure schematic diagram of gaseous mixture.
Fig. 2 is Sr (Co
0.8Fe
0.2)
1-zZr
zO
3-δ(z=0,0.10) material is different CO in the time of 900 ℃
2Relative oxygen transmission rate in the content atmosphere.
Fig. 3 is Sr (Co
0.8Fe
0.2)
1-zZr
zO
3-δ(z=0,0.10) material is at 900 ℃ of different CO
2Sample section microscopic appearance after oxygen transmission rate is measured in the content atmosphere.A is the z=0 material, and b is the z=0.10 material.
Fig. 4 is Sr (Co
0.8Fe
0.2)
0.9Zr
0.1O
3-δThe film pipe is at 900 ℃ of O that produce
2/ CO
2O in the gaseous mixture
2Content and film pipe oxygen transmission rate.
Fig. 5 is Sr (Co
0.8Fe
0.2)
1-zTi
zO
3-δ(z=0,0.10) material is different CO in the time of 950 ℃
2Relative oxygen transmission rate in the content atmosphere.
Fig. 6 is Sr (Co
0.8Fe
0.2)
1-zTi
zO
3-δ(z=0,0.10) material in the time of 950 ℃ at CO
2Weight change in the atmosphere.
Fig. 7 is Sr (Co
0.8Fe
0.2)
0.9Ti
0.1O
3-δThe film pipe is at 950 ℃ of O that produce
2/ CO
2O in the gaseous mixture
2Content and film pipe oxygen transmission rate.
Fig. 8 is SrCo
0.8Fe
0.2O
3-δAnd SrCo
0.6Nb
0.4O
3-δMaterial in the time of 900 ℃ at CO
2Weight change in the atmosphere
The specific embodiment
Below in conjunction with description of drawings the specific embodiment of the present invention.
Embodiment 1:Sr (Co
0.8Fe
0.2)
1-zZr
zO
3-δ(z=0,0.10) ceramic oxygen-permeable membrane material and O
2/ CO
2Gaseous mixture is produced
For proving that composite conductor oxygen-permeating film material of the present invention has anti-preferably CO
2Corrosive power is with unadulterated SrCo
0.8Fe
0.2O
3-δ(being z=0) material is as with reference to comparing, from material at CO
2The variation of aspects such as the oxygen flow ability in the atmosphere, microscopic appearance illustrates that composite conductor oxygen-permeating film material of the present invention has stronger anti-CO
2Corrosive power.
Adopt synthesis by solid state reaction to prepare SrCo earlier
0.8Fe
0.2O
3-δCompact ceramic oxygen permeable membrane sheet: accurately take by weighing 23.0677 gram SrCO
3, 10.3668 the gram Co
2O
3With 2.4953 gram Fe
2O
3,, carry out twice pre-burning at 950～1050 ℃ then and promptly obtain SrCo the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing
0.8Fe
0.2O
3-δPowder; Adopt the single shaft dry pressing that pressed by powder is become disk shape ceramic body, in cold isostatic press, be forced into 300MPa then; 1～the 2mm that suppresses is thick, the base substrate of diameter 15mm is warming up to 1150 ℃ and carried out sintering in 10～15 hours in the insulation of this temperature, reduces to room temperature then, promptly obtains the compact ceramic oxygen permeable membrane sheet; XRD determining shows that sample is the cubic perovskite structure of pure phase.
Adopt synthesis by solid state reaction to prepare Sr (Co then
0.8Fe
0.2)
0.9Zr
0.1O
3-δ(being z=0.10) dense ceramic membrane: accurately take by weighing 22.6828 gram SrCO
3, 9.1745 the gram Co
2O
3, 2.2083 the gram Fe
2O
3With 1.8932 gram ZrO
2, with the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing, to carry out twice pre-burning at 950～1050 ℃ again and promptly obtain preparing the ceramic diaphragm powder, each pre-burning was maximum temperature insulation 10 hours; Adopt the single shaft dry pressing that pressed by powder is become disk shape ceramic body, in cold isostatic press, be forced into 300MPa then; 1～the 2mm that suppresses is thick, the base substrate of diameter 15mm is warming up to 1250 ℃ and carried out sintering in 10～15 hours in the insulation of this temperature, reduces to room temperature then, promptly obtains the compact ceramic oxygen permeable membrane sheet; XRD determining shows that sample is the two-phase composite, and principal phase is a cubic perovskite structure, and second is SrZrO mutually
3
Described material is at CO
2The measuring method of the oxygen flow ability in the atmosphere is as follows: the compact ceramic oxygen permeable membrane sheet is bonded on the alundum tube of hollow with the sealing-in agent and is placed in the heating furnace, and a side surface air purge on the diaphragm, the opposite side surface is with He or CO
2Or the gaseous mixture of the two purging, the gas behind the purging enters wherein O of gas chromatographic detection
2Content, concrete measurement mechanism and method can be referring to " solid-state ionics " (Solid State Ionics, 1999, the 133:23) introductions in.
The relative oxygen transmission rate of definition material is that material is at finite concentration CO
2Oxygen transmission rate in the atmosphere and this material purge the percent value of the oxygen transmission rate under the atmosphere at He.Two kinds of materials are at 900 ℃ of different CO
2Relative oxygen transmission rate in the content atmosphere is seen accompanying drawing 2.Being in following among Fig. 2 is that the relative oxygen transmission rate of z=0 material is with CO in the atmosphere by the punctuate curve a that is linked to be of open circles
2The variation of content, the relative oxygen transmission rate that the top curve b that is linked to be by the filled box point is the z=0.10 material is with CO in the atmosphere
2The variation of content.The relative oxygen transmission rate of two kinds of materials is all along with CO in the sweep gas
2The increase of content and reducing shows CO
2The corrosion that the high more material of content is subjected to is serious more, thereby causes the oxygen flow ability constantly to descend.CO at variable concentrations
2In the atmosphere, the relative oxygen transmission rate of z=0.10 material is big than z=0 material all the time, CO
2Less to z=0.10 material oxygen flow ability influence, the anti-CO of z=0.10 material is described
2The ability of corrosion is more intense.
Adopt the micro-instrument of electron scanning that the section of two kinds of materials after oxygen transmission rate is measured observed, wherein CO
2The microscopic appearance that purges side is seen accompanying drawing 3.Left hand view (a) shows the surface of z=0 material loose, the porous that becomes, and generated the porous layer that a layer thickness is about 15 μ m, shows that this surface is subjected to CO
2Corrosion and cause pattern to change; Right part of flg (b) demonstration z=0.10 material surface then almost be can't see porous layer, and CO is described
2Corrosion to material is slight.This shows the anti-CO of z=0.10 material
2Corrosive power is stronger than z=0 material.
Above result shows z=0 material and CO
2Reaction is serious, causes the oxygen flow ability to decline to a great extent, and it is loose porous that the surface of sample also becomes; And composite conductor oxygen-permeating film material of the present invention---z=0.10 material and CO
2Reaction is slight, and oxygen flow ability institute is influenced less, has stronger anti-CO
2Corrosive power.
The oxygen permeable film material composition is adjusted into La
0.1Sr
0.9(Co
0.8Fe
0.2)
1-zZr
zO
3-δ, Ca
0.5Sr
0.5(Co
0.8Fe
0.2)
1-zZr
zO
3-δ, Ba
0.1Sr
0.9(Co
0.5Fe
0.5)
1-zZr
zO
3-δ, Sm
0.1Sr
0.9Co
1-zZr
zO
3-δ, Sr
0.9(Co
0.8Fe
0.2)
1-zZr
zO
3-δ, Sr (Co
0.8Cu
0.2)
1-zZr
zO
3-δ, Sr
0.9(Co
0.8Zn
0.2)
1-zZr
zO
3-δ, 0＜z≤0.4 wherein, other conditions are constant, also can make to have resisting high-concentration CO
2Corrosive power and have the composite conductor oxygen-permeating film of high oxygen flow ability.
Fig. 1 has provided the present invention and has adopted the composite conductor oxygen-permeating film assembly to produce O
2/ CO
2The basic procedure schematic diagram of gaseous mixture.With main component is CO
2Combustion tail gas 4, obtaining drying and burning tail gas 5 through purifying processor 10 after dewatering, account for volume fraction in the drying and burning tail gas 5 and be 10～50% part and enter CO
2Collector unit 11, remaining accounts for volume fraction is that the compressed air 1 that 50～90% part and the pressure after the preheating are 1～5 atmospheric pressure enters composite conductor oxygen-permeating film assembly 7 simultaneously, at 800～1100 ℃, oxygen in the compressed air 1 is penetrated into the combustion tail gas 5 of opposite side drying the O that produces from a side of composite conductor oxygen-permeating film 8
2/ CO
2Gaseous mixture 6 enters combustion chamber 9 oxidation fossil fuels 3; The low oxygen content compressed air 2 that comes out from composite conductor oxygen-permeating film assembly 7 emptying or do other uses after reclaiming heat.
Introduce below and adopt Sr (Co
0.8Fe
0.2)
0.9Zr
0.1O
3-δOxygen permeation membrane pipe assembling composite conductor oxygen-permeating film assembly is also produced O
2/ CO
2The idiographic flow step of gaseous mixture.Adopt the synthetic Sr (Co of solid reaction process earlier
0.8Fe
0.2)
0.9Zr
0.1O
3-δPowder: accurately take by weighing 22.6828 gram SrCO
3, 9.1745 the gram Co
2O
3, 2.2083 the gram Fe
2O
3With 1.8932 gram ZrO
2, with the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing, to carry out twice pre-burning at 950～1050 ℃ then and promptly obtain preparing the effective powder of oxygen permeation membrane, each pre-burning was maximum temperature insulation 10 hours.Powder filled in special mould with what synthesize, in cold isostatic press, be forced into 300MPa, the demoulding obtains the film pipe body of an end closure, this base substrate is warming up to 1250 ℃ and remained on this temperature sintering 10～15 hours in air atmosphere, reduces to room temperature then, promptly obtain the compact oxygen permeable film pipe of an end closure of the similar test tube of profile, the film external diameter of pipe is 1.10cm, thickness is 0.18cm, and effective length is 1.32cm, and effectively the oxygen flow area is 3.5cm
2The effective sealing-in agent of film is bonded on the alundum tube of hollow and places heating furnace, so just be assembled into composite conductor oxygen-permeating film assembly 7.Adopt the steel cylinder air to simulate following in working order required compressed air 1, the steel cylinder CO of composite conductor oxygen-permeating film
2The dry combustion tail gas 5 of gas simulation.Purging pressure in the film pipe outside is 4.5 atmospheric compressed air, and film pipe inside is 1 atmospheric CO with pressure then
2Air-blowing is swept, by regulating CO
2The flow velocity of sweep gas is controlled the O of production
2/ CO
2O in the gaseous mixture
2Content.Accompanying drawing 7 is depicted as the O that this film pipe is produced in the time of 900 ℃
2/ CO
2O in the gaseous mixture
2Content and oxygen transmission rate be relation curve over time.The curve c that is got by the filled box point among Fig. 4 is the O that produces
2/ CO
2O in the gaseous mixture
2Content, be film pipe oxygen transmission rate by the open circles curve d that gets that punctuates.Work as O
2Content is about at 16% o'clock, and oxygen transmission rate is at 1.1mL/cm
2About min, promptly 8 * 10
-7Mol/cm
2About s; When regulating CO
2The sweep gas flow makes O
2Content reaches at 30% o'clock, and oxygen transmission rate is at 0.9mL/cm
2About min, promptly 7 * 10
-7Mol/cm
2About s.The film pipe is worked under this situation and still can be kept the stable of oxygen flow ability, the O that produces in 100 hours
2/ CO
2O in the gaseous mixture
2Volume content stable remain on about 30% the O that so makes
2/ CO
2Gaseous mixture can replace air to be used as the combustion adjuvant of various fuel combustions.
Described composite conductor oxygen-permeating film assembly 7 also can place cavity to constitute one or one group ceramic membrane that uses composite conductor oxygen-permeating film material of the present invention to make, the ceramic membrane both sides that link to each other with pipeline respectively can feed gas with various respectively, described ceramic membrane profile can be flat board, also can be the hollow polyhedron of hollow circular tube, spherical shell or the hemispherical Shell of an end or both ends open, a face or several openings.
Described composite conductor oxygen-permeating film assembly 7 can be used to produce O 800～1100 ℃ of work in said process
2/ CO
2Gaseous mixture replaces compressed air still can produce O with normal air
2/ CO
2Gaseous mixture.
Theoretical calculating shows, when using O
2Volume content is 20% O
2/ CO
2Gaseous mixture need be that 90% drying and burning tail gas feeding oxygen permeation membrane assembly 7 is used to purge composite conductor oxygen-permeating film production O with volume fraction as combustion adjuvant, when natural gas is fuel
2/ CO
2Gaseous mixture; When using O
2Volume content is 50% O
2/ CO
2Gaseous mixture need be that 50% drying and burning tail gas feeding oxygen permeation membrane assembly is used to purge composite conductor oxygen-permeating film production O with volume fraction as combustion adjuvant, when coal is fuel
2/ CO
2Gaseous mixture.
Embodiment 2:Sr (Co
0.8Fe
0.2)
1-zTi
zO
3-δ(z=0,0.10) ceramic oxygen-permeable membrane material
For proving that composite conductor oxygen-permeating film material of the present invention has anti-preferably CO
2Corrosive power is with unadulterated SrCo
0.8Fe
0.2O
3-δ(being z=0) material is as with reference to comparing, from material at CO
2The variation of aspects such as the oxygen flow ability in the atmosphere, weight illustrates that composite conductor oxygen-permeating film material of the present invention has stronger anti-CO
2The ability of corrosion.
Adopt synthesis by solid state reaction to prepare SrCo earlier
0.8Fe
0.2O
3-δCompact ceramic oxygen permeable membrane sheet: accurately take by weighing 23.0677 gram SrCO
3, 10.3668 the gram Co
2O
3With 2.4953 gram Fe
2O
3, with the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing, carry out twice pre-burning at 950-1050 ℃ again, promptly obtain SrCo
0.8Fe
0.2O
3-δPowder; Adopt the single shaft dry pressing with pressed by powder slabbing ceramic body, in cold isostatic press, be forced into 300MPa then; Base substrate 1～the 2mm that suppresses is thick, diameter 15mm is warming up to 1150 ℃ and carried out sintering in 10～15 hours in the insulation of this temperature, reduces to room temperature then, promptly obtains the compact ceramic oxygen permeable membrane sheet; XRD determining shows that sample is the cubic perovskite structure of pure phase.
Adopt synthesis by solid state reaction to prepare Sr (Co then
0.8Fe
0.2)
0.9Ti
0.1O
3-δ(being z=0.10) compact ceramic oxygen permeable membrane sheet: accurately take by weighing 23.1922 gram SrCO
3, 9.3805 the gram Co
2O
3, 2.2578 the gram Fe
2O
3With 1.2552 gram TiO
2, the raw material that taken by weighing ball milling in the alcohol medium is mixed flash baking after 24 hours, carry out twice pre-burning at 950～1050 ℃ again and promptly obtain preparing the ceramic diaphragm powder, be incubated 10 hours after burning maximum temperature in advance at every turn; Adopt the single shaft dry pressing with pressed by powder slabbing ceramic body, in cold isostatic press, be forced into 300MPa then; Base substrate 1～the 2mm that suppresses is thick, diameter 15mm is warming up to 1250 ℃ and carried out sintering in 10～15 hours in the insulation of this temperature, reduces to room temperature then, promptly obtains the compact ceramic oxygen permeable membrane sheet; XRD determining shows that this sample is the cubic perovskite structure of pure phase.
The relative oxygen transmission rate of definition material is that material is at finite concentration CO
2Oxygen transmission rate in the atmosphere and material purge the percent value of the oxygen transmission rate under the atmosphere at He.Accompanying drawing 5 has provided Sr (Co
0.8Fe
0.2)
1-xTi
xO
3-δ(z=0,0.10) series material is at 950 ℃ of different CO
2Relative oxygen transmission rate in the content.Be that the relative oxygen transmission rate of z=0 material is with CO in the atmosphere by the punctuate curve e that is linked to be of open circles among the figure
2The variation of content, the curve f that is linked to be by the filled box point is that the relative oxygen transmission rate of z=0.10 material is with CO in the atmosphere
2The variation of content.The relative oxygen transmission rate of two kinds of materials is all along with CO in the sweep gas
2The increase of content and reducing shows CO
2The corrosion that the high more material of content is subjected to is serious more, thereby causes the oxygen flow ability constantly to descend.CO at variable concentrations
2In the atmosphere, the relative oxygen transmission rate of z=0 material is littler than z=0.10 all the time, especially at CO
2Content is higher than at 40% o'clock, and the relative oxygen transmission rate of z=0 material is more much smaller than z=0.10---such as working as CO
2Content is 80% o'clock, and the relative oxygen transmission rate of z=0 material is 51%, z=0.10 then up to 89%; This shows that the z=0.10 material is at CO
2Stability is than z=0 material height in the atmosphere.
Two kinds of materials are at 950 ℃ CO
2Weight change in the atmosphere is seen accompanying drawing 6.The curve g that is linked to be by hollow triangulation point among the figure is that z=0 material powder is at CO
2Weight change in the atmosphere, the curve h that is linked to be by the filled box point is that z=0.10 material powder is at CO
2Weight change in the atmosphere.Two kinds of materials are at CO
2Weight in the atmosphere all increases along with the increase of time, shows material and CO
2Thereby reaction makes weight increase.The weight of process two kinds of materials after about 40 hours remains unchanged substantially, illustrates and CO
2Reaction reach balance substantially.At this moment, it is about 19% that the z=0 material weight increases, and the increase of z=0.10 material weight only is 8%.Calculate under this temperature the z=0 material all and CO according to reaction equation
2Reaction, and the z=0.10 material only has an appointment 47% and CO
2Reaction.The anti-CO of this explanation z=0.10 material
2Corrosive power improves a lot than z=0 material.
Above result shows z=0 material and CO
2Reaction is serious, causes the oxygen flow ability to decline to a great extent, at CO
2Weight in the atmosphere also increases greatly; And composite conductor oxygen-permeating film material of the present invention---z=0.10 material and CO
2Reaction is slight, and oxygen flow ability institute is influenced less, has stronger anti-CO
2Corrosive power.
The oxygen permeable film material composition is adjusted into La
0.1Sr
0.9(Co
0.8Fe
0.2)
1-zTi
zO
3-δ, Pr
0.1Sr
0.9(Co
0.8Fe
0.2)
1-zTi
zO
3-δ, La
0.5K
0.5(Co
0.8Fe
0.2)
1-zTi
zO
3-δ, Sr
0.95Co
1-zTi
zO
3-δ, Sr
0.5(Co
0.8Mn
0.2)
1-zTi
zO
3-δ, Sr (Co
0.9Cr
0.1)
1-zTi
zO
3-δ, Sr (Co
0.9Ni
0.1)
1-zTi
zO
3-δ, 0＜z≤0.4 wherein, other conditions are constant, also can make to have resisting high-concentration CO
2Corrosive power and have the composite conductor oxygen-permeating film of high oxygen flow ability.
Adopt Sr (Co
0.8Fe
0.2)
0.9Ti
0.1O
3-δOxygen permeation membrane pipe assembling composite conductor oxygen-permeating film assembly is also produced O
2/ CO
2Gaseous mixture.Adopt the synthetic Sr (Co of solid reaction process earlier
0.8Fe
0.2)
0.9Ti
0.1O
3-δPowder: accurately take by weighing 23.1922 gram SrCO
3, 9.3805 the gram Co
2O
3, 2.2578 the gram Fe
2O
3With 1.2552 gram TiO
2, with the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing, to carry out twice pre-burning at 950～1050 ℃ then and promptly obtain preparing the effective powder of oxygen permeation membrane, each pre-burning was maximum temperature insulation 10 hours.Powder filled in special mould with what synthesize, in cold isostatic press, be forced into 300MPa, the demoulding obtains the film pipe body of an end closure, this base substrate is warming up to 1250 ℃ and remained on this temperature sintering 10～15 hours in air atmosphere, reduce to room temperature then, promptly obtain the compact oxygen permeable film pipe of an end closure of the similar test tube of profile.Made film external diameter of pipe is 1.23cm, and thickness is 0.13cm, and effective length is 3.28cm, and effectively the oxygen flow area is 11.3cm
2The effective sealing-in agent of film is bonded on the alundum tube of hollow and places heating furnace, so just be assembled into composite conductor oxygen-permeating film assembly 7.Adopt the steel cylinder air to simulate following in working order required compressed air 1, the steel cylinder CO of composite conductor oxygen-permeating film
2The dry combustion tail gas 5 of gas simulation.Purging pressure in the film pipe outside is 4.5 atmospheric compressed air, and film pipe inside is 1 atmospheric CO with pressure then
2Purge, by regulating CO
2The flow velocity of sweep gas is controlled the O of production
2/ CO
2O in the gaseous mixture
2Content.Accompanying drawing 7 is depicted as the O that this film pipe is produced in the time of 950 ℃
2/ CO
2O in the gaseous mixture
2Content and oxygen transmission rate be relation curve over time.The curve i that is got by the filled box point among the figure is the O that produces
2/ CO
2O in the gaseous mixture
2Content, be film pipe oxygen transmission rate by the open circles curve j that gets that punctuates.The oxygen transmission rate of composite conductor oxygen-permeating film pipe remains on 1.4～1.7mL/cm in the whole service process
2Min, the O of production
2/ CO
2O in the gaseous mixture
2Content remains on 30-36%, the O that so makes
2/ CO
2Gaseous mixture can replace air to be used as the combustion adjuvant of various fuel combustions.
In the said process, the oxygen permeation membrane pipe can be used to produce O 800～1100 ℃ of work
2/ CO
2Gaseous mixture replaces compressed air still can produce O with normal air
2/ CO
2Gaseous mixture.
Embodiment 3:SrCo
0.6Nb
0.4O
3-δCeramic oxygen-permeable membrane material
For proof composite conductor oxygen-permeating film material of the present invention has anti-preferably CO
2Corrosive power is with unadulterated SrCo
0.8Fe
0.2O
3-δMaterial is as with reference to comparing, from material at CO
2Weight change in the atmosphere illustrates that ceramic oxygen-permeable membrane material used in the present invention has stronger anti-CO
2The ability of corrosion.
Adopt the synthetic SrCo of solid reaction process earlier
0.8Fe
0.2O
3-δCeramic powder: accurately take by weighing 23.0677 gram SrCO
3, 10.3668 the gram Co
2O
3With 2.4953 gram Fe
2O
3,, carry out twice pre-burning at 950～1050 ℃ again and promptly obtain SrCo the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing
0.8Fe
0.2O
3-δPowder; XRD determining shows that prepared sample is the cubic perovskite structure of pure phase.
Adopt solid reaction process to synthesize SrCo then
0.6Nb
0.4O
3-δCeramic powder: accurately take by weighing 21.4932 gram SrCO
3, 7.2444 the gram Co
2O
3With 7.7398 gram Nb
2O
5,, carry out twice pre-burning at 1100-1200 ℃ again and promptly obtain required ceramic powder the raw material ball milling mixing flash baking after 24 hours in the alcohol medium that is taken by weighing; XRD determining shows that prepared sample is the cubic perovskite structure of pure phase.
Two kinds of materials are at 900 ℃ CO
2Weight change in the atmosphere is seen accompanying drawing 8.The curve k that is formed by hollow triangulation point among the figure is SrCo
0.8Fe
0.2O
3-δThe material powder is at CO
2Weight change in the atmosphere, the curve 1 that is formed by filled box point is SrCo
0.6Nb
0.4O
3-δThe material powder is at CO
2Weight change in the atmosphere.Two kinds of materials are at CO
2Weight in the atmosphere all increases along with the increase of time, shows material and CO
2Thereby reaction makes weight increase.SrCo
0.8Fe
0.2O
3-δContinuous and the CO of material
2Reaction, increase through weight after 20 hours about 8%, and SrCo
0.6Nb
0.4O
3-δMaterial weight under the same conditions increases less than 1%.And curve e still has in time and to continue the trend that increases, and SrCo is described
0.8Fe
0.2O
3-δMaterial and CO
2Reaction also do not reach balance, reaction will be proceeded down, this moment, curve f then kept level substantially, and SrCo is described
0.6Nb
0.4O
3-δMaterial and CO
2Reaction reached balance, can not continue and CO
2Reaction.This illustrates SrCo of the present invention
0.6Nb
0.4O
3-δThe anti-CO of composite conductor oxygen-permeating film material
2Corrosive power compares SrCo
0.8Fe
0.2O
3-δMaterial improves a lot.
The oxygen permeable film material composition is adjusted into SrCo
0.8Fe
0.1Ge
0.1O
3-δ, SrCo
0.8Fe
0.1W
0.1O
3-δ, SrCo
0.8Fe
0.1Mo
0.1O
3-δ, SrCo
0.8Fe
0.1Ce
0.1O
3-δ, Sr (Co
0.8Fe
0.2)
0.9Al
0.1O
3-δ, SrCo
0.8Fe
0.1Sn
0.1O
3-δ, SrCo
0.8Fe
0.1V
0.1O
3-δ, other conditions are constant, also can make to have resisting high-concentration CO
2Corrosive power and have the composite conductor oxygen-permeating film of high oxygen flow ability.
Claims (3)
1. a composite conductor oxygen-permeating film is characterised in that it is for having ABO
3Perovskite structure also mixes the single-phase or biphase mixed conducting oxygen-permeable membrane of high valence state or high electronegativity ion in the B position, its composition can be A with chemical formulation
xB
yB '
zO
3-δ, wherein A is one or more in lanthanide series, alkali earth metal or the alkali metal; B is selected from Cr, Mn, Fe, Co, Ni, Cu and/or Zn; B ' ion has high valence state or high electronegativity, and B ' is selected from Ti, Zr, Ge, Sn, Mo, W, V, Nb, Ta, Al and/or Ga; Subscript x, y, z are molar fraction, wherein 0.9≤x≤1.0,0＜z≤0.4 and y+z=1.0; δ is non-metering oxygen, 0＜δ＜1.
2. one kind is adopted the described composite conductor oxygen-permeating film of claim 1 to produce O
2/ CO
2The method of gaseous mixture, be characterised in that its flow process is: with main component is CO
2Combustion tail gas (4), obtaining drying and burning tail gas (5) through purifying processor (10) after dewatering, account for volume fraction in the drying and burning tail gas (5) and be 10～50% part and enter CO
2Collector unit (11), remaining accounts for volume fraction is that the compressed air (1) that 50～90% part and the pressure after the preheating are 1～5 atmospheric pressure enters composite conductor oxygen-permeating film assembly (7) simultaneously, at 800～1100 ℃, oxygen in the compressed air (1) is penetrated into the combustion tail gas (5) of opposite side drying the O that produces from a side of composite conductor oxygen-permeating film (8)
2/ CO
2Gaseous mixture (6) enters combustion chamber (9) oxygenated fuel (3); The low oxygen content compressed air (2) that comes out from composite conductor oxygen-permeating film assembly (7) emptying or do other uses after reclaiming heat.
3. produce O as employing composite conductor oxygen-permeating film as described in the claim 2
2/ CO
2The method of gaseous mixture, be characterised in that described composite conductor oxygen-permeating film assembly is to place cavity to constitute the ceramic membrane that or a group use the composite conductor oxygen-permeating film material to make, the ceramic membrane both sides that link to each other with pipeline respectively feed gas with various, and described ceramic membrane profile is the hollow polyhedron of dull and stereotyped or hollow circular tube, spherical shell or the hemispherical Shell of an end or both ends open, a face or several openings.
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| CN102489175A (en) * | 2011-12-20 | 2012-06-13 | 天津工业大学 | Preparation method of ceramic/molten salt double-phase composite gas separating film |
| CN103638825A (en) * | 2013-12-10 | 2014-03-19 | 天津工业大学 | Preparation method and application of integrated three-layer structural inorganic oxygen permeating membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258557A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院大连化学物理研究所 | Preparation and application of perovskite Bi-containing mixed oxygen-penetrating conductor film |
| CN1795972A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | Mixed conductorial oxygen penetrated membrane in perovskite type in cerium series, prepartion and application |
| CN1864830A (en) * | 2005-05-16 | 2006-11-22 | 中国科学技术大学 | A biphase mixed conducting oxygen-permeable membrane and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258557A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院大连化学物理研究所 | Preparation and application of perovskite Bi-containing mixed oxygen-penetrating conductor film |
| CN1795972A (en) * | 2004-12-23 | 2006-07-05 | 中国科学院大连化学物理研究所 | Mixed conductorial oxygen penetrated membrane in perovskite type in cerium series, prepartion and application |
| CN1864830A (en) * | 2005-05-16 | 2006-11-22 | 中国科学技术大学 | A biphase mixed conducting oxygen-permeable membrane and preparation method thereof |
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