CN1314620C - Oxygen permeable film material of densified ceramics enhanced by perovskite typed oxide and oxygen spearator - Google Patents

Oxygen permeable film material of densified ceramics enhanced by perovskite typed oxide and oxygen spearator Download PDF

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CN1314620C
CN1314620C CNB031133223A CN03113322A CN1314620C CN 1314620 C CN1314620 C CN 1314620C CN B031133223 A CNB031133223 A CN B031133223A CN 03113322 A CN03113322 A CN 03113322A CN 1314620 C CN1314620 C CN 1314620C
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oxygen
oxygen permeable
ceramic
permeable film
powder
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CN1539791A (en
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陈初升
樊传刚
邓增强
刘卫
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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Abstract

The present invention relates to oxygen permeable film materials of densified ceramics enhanced by perovskite typed oxide, and an oxygen separator, which is characterized in that after a proper quantity of compatible structural perovskite phase materials are introduced in the existing mixed oxygen permeable film materials with high oxygen permeable rate and poor stability to enhance second phases, the oxygen permeable film materials whose chemical formula is (M<1-y>M<y>'Co<1-x>Fe<x>O<3-delta>)z(NBO<3>)<1-z> are obtained; by adding the second phases, the oxygen permeable structure of an original oxygen permeable system develops completely, and the oxygen permeable property is improved; powder can be prepared by the traditional solid-phase reaction or a wet chemical synthetic method, the powder is prepared into compact tubular enhanced ceramic oxygen permeable films, and thus, a device which can separate oxygen from air is formed. The separator of the present invention can separate pure oxygen from raw air without influence on separating efficiency, and cost is reduced; the separator can satisfy oxygen supply requirements in a large scale, and can be made into a medium or miniature direct oxygen supply device which is convenient and agile and is easy to move; the separator has the advantages of simple and convenient operating technology, reliable operation, and long service life of the oxygen permeable film materials.

Description

Perofskite type oxide enhanced compact ceramic oxygen permeable membrane material and oxygen separator thereof
Technical field:
The invention belongs to compact ceramic oxygen permeable membrane material applied technical field, particularly relate to the oxygen separator of uhligite or perovskite-like type composite conductor oxygen-permeating film and formation thereof.
Background technology:
Oxygen is a kind of and the closely-related oxygenant of mankind's activity.Along with the quickening of human development paces, existing oxygen separation technology has been difficult to satisfy people in the flexible demands of different occasions to oxygen.Can only be fit to extensive oxygen separation as existing general alternating temperature oxygenerating technology, and gas products is difficult for the oxygen product that compressibility separate to obtain this method and is difficult for a large amount of storages and transportation, has restricted the pure oxygen of this method preparation or effective utilization of oxygen rich gas; Utilize the transformation molecular sieve adsorption rule can not continuous oxygen generation, it also equally with polymeric membrane can't prepare the higher oxygen of purity in addition.For example, the isolated oxygen concentration of describing in the invention of Application No. 323968 of hollow fiber membrane separator has only 30-40%.
Pure oxygen ion conductivity type solid electrolyte ceramic film can separate the acquisition pure oxygen for the oxygen separator on basis.A kind of yttrium-stabile zirconium dioxide (yttrium-stabilized zirconia) solid electrolyte oxygen permeable film and oxygen separator have based on this been introduced as U.S. Patent number 6475657.This oxygen separation membrane needs additional circuit, and in the time of 750 ℃, it needs the impressed current of/2 volts of 10 peaces just can isolate oxygen, and this makes complicated operationization.In order to improve oxygen permeability, this patent has plated porous mixed conductor material and noble metal electrode to reduce solid electrolyte surface resistance at the membrane structure surfaces externally and internally, but this oxygen permeable film must adopt very fine layered composite structure, makes the macro preparation of separatory membrane relatively more difficult like this; Because the material difference of each layer, the matching problem between the layer makes the bad stability of membrane structure; Also sintering phenomenon can take place when adopting noble metal electrode to work, make the highly porous dispersive electrode structure of beginning destroyed, be not suitable for long-time running under the service temperature more than 750 ℃.The problems referred to above have limited their application in oxygen separates.
The mixed conductive oxygen ion conductor also has the function of separated oxygen.The ceramic of compact separatory membrane of making by this material, hereinafter to be referred as " mixed type ceramic oxygen-permeable membrane ", under the situation that film both sides aerobic partial pressure difference exists, oxygen can transport to the low oxygen partial pressure end by intravital oxygen room from the high keto sectional pressure end of oxygen permeable film, and electronics (or electron hole) then oppositely moves to keep the electric neutrality of material.Because said process need not additional circuit, therefore at oxygen separator with relate in the application of oxygen membrane reactor and can simplify tripping device and the technology that simplifies the operation.Ceramic oxygen-permeable membrane material must be worked under middle pyritous strong reducing property condition in membrane reactor is used, and can be reduced out unstable because of transition metal ion in the mould material; The high oxygen gradient that while film two ends are applied can cause that thereby very big internal stress makes ceramic oxygen-permeable membrane easily cracked.In the application of oxygen separator, the working conditions of oxygen permeable film harshness is eased, and serviceability increases, and the oxygen permeable film life-span can prolong.Therefore the oxygen separator based on the mixed type oxygen permeable film can effectively satisfy family health care, hospital care and giving emergency treatment to a patient, metal cutting processing, the high altitude localities is oxygenation on the spot, the oxygen enrichment of aircraft fuel and pure oxygen burning, the oxygen supply of oxygenation cabin, and the aerobic requirement of the aspects such as pure oxygen cleanburning of fossil energy such as coal and hydrogen energy source.
Holland " solid state ionics " (Solid State Ionics, 2000,134, the oxygen separator of introducing 21-23) that utilizes the mixed type ceramic oxygen-permeable membrane to separate oxygen in the high-pressure air can satisfy above requirement, but need being compressed to air more than 200 pounds, it just can isolate oxygen with practical value, this just need be furnished with air compressor and high pressure resistant elevated temperature vessel, thus the cost increase that makes the cost of oxygen separator and isolate oxygen.
Seek the oxygen transmission rate height and have the mixed type ceramic oxygen-permeable membrane material chemical under bigger oxygen partial pressure gradient and middle hot conditions, that structural stability is good concurrently, and utilize them to prepare the work of oxygen separator with using value, just causing the interest that people are increasing.In numerous mixed type ceramic oxygen-permeable membrane material systems of present report, the oxygen flow ability is the highest remains Japan's " chemical communication " (Chem.Lett., 1985,1743-1746) La of report at first 1-xSr xCo 1-yFe yO 3-δSrCo in the system 0.8Fe 0.2O 3-δThe oxygen permeable film material that this name is formed, its oxygen permeability can reach 10 at 850 ℃ -6The mole centimetre -2Second -1Magnitude; But for this oxygen permeable film material, the oxygen flow ability and the stability of different research group report differ greatly, and minimum and the highlyest differ two orders of magnitude unexpectedly.For example, and " solid state ionics " (Solid State Ionics, 1993,63-65,816-822) oxygen permeability of 900 ℃ of this materials of report has only 10 -8The mole centimetre -2Second -1" solid state ionics " (Solid State Ionics, 1995,76,321-329) this material of report is separating artificial air (N 2/ O 2=4/1 distribution) time, oxygen permeability has only 1/5 of " chemical communication " report, and under middle pyritous oxygen partial pressure gradient condition, this material opposing Carbon Dioxide in Air destructive ability is relatively poor, and when separating actual air, oxygen permeability has reduced by 5 times again.The high mould material of some oxygen transmission rates of other report, the different transformation situation of degree also can appear in oxygen transmission rate behind experience oxygen permeability test.La for example 1-xBa xCo 1-yFe yO 3-δAnd La 1-xSr xCo 1-yFe yO 3-δThe sample surfaces of oxygen permeable film material system after the infiltration of the long-term oxygen of experience has and decomposes and precipitate produces, oxygen penetration number even change in quality to having only about half of starting value in the time of seriously.It is to be noted: the rate of permeation the when oxygen permeability that relates in this specification sheets is oxygen partial pressure 1 crust.Have the oxygen permeable film material that separates using value and not only will have high oxygen permeability, also will have very high chemical stability and structural stability simultaneously." solid state ionics " (Solid State Ionics, 2000,133,57-56), Switzerland's " materials chemistry physics " (Materials Chemistry ﹠amp; Physics, 1998,53,6-12), Holland " membrane science " (J.Mem.Sci., 1999,163,307-317), U.S.'s " investigation of materials circular " (Materials Research Bulletin, 1999, Vol 34 1921-1928) etc. reported a series of by ion (Cr, Ti, Fe, Mn, Cu, rare earth element etc.) doping enhanced uhligite phase mixed type ceramic oxygen-permeable membrane materials.Adopting ion (Cr, Ti, Fe, Mn, Cu, rare earth element etc.) doping enhanced shortcoming is when the oxygen permeable film material structure is enhanced, and the oxygen permeability regular meeting of material reduces significantly.Especially it is to be noted, report according to pertinent literature, the oxygen permeability sign of present existing most of mixed type oxygen permeable film all is to finish by the air and the helium that are more or less the same at oxygen permeable film both sides purging pressure, therefore can not determine whether these oxygen permeable films can bear the big pressure difference that need be applied to the ceramic membrane both sides in the actual oxygen separator, and this pressure difference is the motivating force of oxygen in the mixed type oxygen permeable film separation of air.
Technology contents:
The structure-type uhligite phase material that the present invention proposes to introduce in a kind of mixed type oxygen permeable film material of and less stable higher at existing oxygen transmission rate an amount of rerum natura coupling is as strengthening the second enhancement type compact ceramic oxygen permeable membrane material that obtain of back mutually, to improve the physical strength and the chemical stability of oxygen permeable film material; And be basic establishment can separate pure oxygen from air practical oxygen tripping device with this class enhancement type compact ceramic oxygen permeable membrane material, to overcome the shortcoming of existing oxygen permeability reduction when adopting ion (Cr, Ti, Fe, Mn, rare earth element etc.) to mix the mixed type oxygen permeable film material strengthened.
Perofskite type oxide enhanced compact ceramic oxygen permeable membrane material of the present invention is designated hereinafter simply as " enhancement type oxygen permeable film material ", it is characterized in that, it is by the second phase NBO 3(a kind of among N=Sr, Ba, Ca, the Mgo, among B=Sn, the Zr a kind of) enhanced M 1-yM y' Co 1-xFe xO 3-δ(at least a among M=Sr, Ba, Ca, the Mg, M '=rare earth element) basic two-phase composite ceramics oxygen permeable film material, its chemical constitution expression is: (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) z, wherein subscript x, y, z are molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50; Wherein base is M mutually 1-yM y' Co 1-xFe xO 3-δ, be the mixed type ceramic oxygen-permeable membrane material of perovskite structure.
Compact ceramic oxygen permeable membrane so that perofskite type oxide enhanced compact ceramic oxygen permeable membrane material of the present invention is made is designated hereinafter simply as " enhancement type oxygen permeable film ".
Enhancement type oxygen permeable film material powder of the present invention can adopt traditional solid state reaction synthetic method to prepare, and it is characterized in that, by above-mentioned chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zIn contained various cationic mol ratios calculate the amount of corresponding raw material, with its analytically pure carbonate, nitrate, oxalate or oxide compound batching, ball milling mixes in the alcohol medium, carry out 2～3 pre-burnings after the flash baking: 850～950 ℃ carry out the 1st time 10～20 hours pre-burning after, through dry ball milling, carry out 1 to 2 pre-burning in 10～20 hours at 1000～1100 ℃ again, again behind dry ball milling, the type that promptly is enhanced oxygen permeable film material powder.
Enhancement type oxygen permeable film material powder of the present invention can also adopt wet chemical synthesis to prepare, and it is characterized in that, by above-mentioned chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zIn contained various cationic mol ratios calculate raw materials used amount, get analytically pure carbonate, nitrate, oxalate or oxide compound respectively and prepare burden, be dissolved in nitric acid; With the compound nitrate solution that obtains, atomizing sprays into the moisture eliminator of 300～400 ℃ band powder collector, obtains compound nitrate dry powder, 900～1000 ℃ of pre-burnings 5～10 hours, and the type that promptly is enhanced oxygen permeable film material powder; Described dry powder also can adopt the atomizing of compound nitrate solution sprayed in the refrigerator below-10 ℃ and obtain agar earlier, and the moisture content volatilization with agar obtains then; Described dry powder also can adopt Pei Qini (Pechini) method of introducing in the U.S. Patent number 3330697 or adopt Britain's " Materials science communication " (J.Mater.Sci.Lett., 1996,13,891-892) the middle sol-gel method acquisition of introducing.
Be the sign evaluation of convenience, need to use flaky enhancement type oxygen permeable film sample the oxygen permeability of resulting oxygen permeable film material.
Sheet enhancement type oxygen permeable film of the present invention, can adopt traditional ceramic preparation to prepare, it is characterized in that, with above-mentioned enhancement type oxygen permeable film material powder is raw material, adopt the single shaft dry pressing, be pressed into the flaky pottery base substrate of 13 millimeters of thick 1～2 millimeters, diameter, be warming up to 1120 ℃～1300 ℃ insulations with 1.5 ℃ of per minutes and carried out sintering in 10～20 hours with 350～550 MPa pressure, and then reduce to room temperature for 1～2 ℃ with per minute, promptly obtain sheet enhancement type oxygen permeable film.
Being generally used for the oxygen permeable film of tube furnace heating atmospheric oxygen tripping device, is piped enhancement type oxygen permeable film.
Tubulose enhancement type oxygen permeable film of the present invention, can adopt the traditional ceramics preparation method to prepare, it is characterized in that, with above-mentioned enhancement type oxygen permeable film material powder is raw material, adopt isostatic pressing method to make the tubular ceramic base substrate, be warming up to 1120 ℃～1300 ℃ insulations with 1.5 ℃ of per minutes then and carried out sintering in 10～20 hours, reduce to room temperature for 1～2 ℃ with per minute again, promptly get tubulose enhancement type oxygen permeable film; Also can adopt extrusion molding or rolling process that ceramic material is made the tubular ceramic base substrate of 0.5～2.5 millimeter one end closure of thickness of pipe, the other end opening or both ends open, drying, plastic removal and row's carbon, at 1130～1300 ℃ of sintering, tubulose enhancement type oxygen permeable film.
The fibrous enhancement type oxygen permeable film of hollow ceramic of the present invention, can adopt " solid state ionics " (Solid StateIonics, 2000,135,637-632) spin processes of Jie Shaoing prepares, described spin processes is meant that the ceramic material that will possess the weaving ability is woven into the method for hollow ceramic fiber base substrate, it is characterized in that: with above-mentioned enhancement type oxygen permeable film material powder is raw material, adopt spin processes that its ceramic material is made 0.01 millimeter of thickness of pipe, internal diameter is less than 1 millimeter, the hollow ceramic fiber base substrate of one end closure, through super-dry, plastic removal and row's carbon sinter the fibrous enhancement type oxygen permeable film of hollow ceramic at 1130～1300 ℃ at last.
Described ceramic material, can adopt following scheme to prepare:
Scheme one: will account for the ceramic powder of system gross weight 30～60%, 1～5% plastic agent, 0.5～2% deaerating agent, 20～40% deionized water, be 10～20% cellulose aqueous solution with 30～40% concentration expressed in percentage by weight, join that ball milling becomes to stablize mud in the ball grinder that zirconia balls is housed, slurry vacuum is stirred the dehydration deaeration, make ceramic material through pugging again; Described cellulose aqueous solution can be made up of one or more mixing of methylcellulose gum, polyvinyl alcohol and/or starch;
Scheme two: will account for the ceramic powder, 1～5% plastic agent of system gross weight 70～85% and 0.5～5% powder surface modifier, 15～30% the ethyl cellulose concentration expressed in percentage by weight that contains is that 5～20% organic solution is mixed at 60～80 ℃ and stirred 2～4 hours, be cooled to room temperature then, promptly get ceramic material.
Tube furnace heating atmospheric oxygen tripping device based on tubulose enhancement type oxygen permeable film of the present invention, it is characterized in that: the opening end of the oxygen flow pipe 2 that the above-mentioned fine and close enhancement type oxygen permeable film material of end closure on or a group is formed, build by laying bricks or stones respectively on each the subchannel mouth on the corundum ceramic pedestal tube 4 with pyroceramic sealing-in agent 3, put into the burner hearth of tube furnace 1; Main channels and each subchannel in the vitrified pipe pedestal 4 communicate, and it is outer with after cool metal pipe 5 links to each other that tube furnace 1 is stretched out in the main channel outlet, receives oilless vacuum pump 8 through cushioning gas-holder 6; Be connected to vacuum meter 7 on the gas-holder 6; Described pyroceramic sealing-in agent 3 is for being in harmonious proportion pug or the thick mud that forms by glass powder, the second phase powder and the Terpineol 350 that contains ethyl cellulose; This second phase powder is the second phase NBO in the enhancement type oxygen permeable film material noted earlier 3(a kind of among N=Sr, Ba, Ca, the Mg, among B=Sn, the Zr a kind of).
During work, be heated to the sintering temperature of high intermediate temperature sealing agent 3 earlier with tube furnace 1, the sintering of high intermediate temperature sealing agent 3 is linked as oxygen flow pipe 2 and vitrified pipe pedestal 4 integral body, the air 9 in oxygen flow pipe 2 inner chambers and the burner hearth is separated; After this tube furnace 1 continuation heating is kept and is entered the interior air 9 of burner hearth at 800-1000 ℃; Utilize vacuum pump oxygen flow pipe 2 to be vacuumized thereby to form the inside and outside oxygen partial pressure of oxygen flow pipe 2 poor, can from oxygen flow pipe 2, extract isolated oxygen 10 from air 9 out thus; Usually the oxygen 10 that vacuum pump outlet can be extracted out 1.5 crust is directly for using; Also can connect an oilless air compressor 11 at the vacuum pump outlet again, with the exert pressure of oxygen 10 to 5 Palestine and Israels for use.
Heat exchanger heats atmospheric oxygen tripping device based on tubulose enhancement type oxygen permeable film of the present invention, it is characterized in that: with ceramic plate 13 for its bottom, in have in the metal vessel 12 of high-temperature-resistant layer, with vitrified pipe 19 vertical insert and add the crack with refractory inorganic adhesive be fixed in the ceramic plate 13 intermediary circular holes; Oxygen flow pipe 2, annulus sealing-in agent 21, ceramic of compact disk 22, corundum matter or zirconia ceramic ball 23 and the vitrified pipe 24 upwards piling up high-temperature stable alloy annulus sealing-in agent 20 from vitrified pipe 19 tops successively, form by the above-mentioned fine and close enhancement type oxygen permeable film material of both ends open, the circular hole that vitrified pipe 24 passes in the middle of the ceramic plate 14 and caliber is complementary, its gap is stifled real with high temperature resistant rock wool, and these ceramic plate 14 usefulness refractory inorganic adhesives are fixed on spacing in the metal vessel 12 and are divided into cold house, top 15 and bottom inlet plenum 16; Pile up normal temperature soft metal nahlock 25, hard metal nahlock 26 successively at vitrified pipe 24 tops of stretching out ceramic plate 14, by the screw mandrel 27 that holds out against that is positioned in the metal vessel 12 top screws above-mentioned parts integral body is held out against at last, and screw mandrel 27 and vitrified pipe 19,24 are kept with one heart; Vitrified pipe 19 stretches out part outside metal vessel 12 with after a branch road metal tube 5 links to each other, and links on the main gas circuit pipe 5 through vacuum valve 28, and main gas circuit pipe 5 is linked air compressor machine 11 through vacuum pump 8; Inlet plenum 16 is provided with inlet mouth 17 and air outlet 18, and this inlet mouth 17 is connected in heated air 9 outlets 31 of heat exchanger 30, and air outlet 18 is connected on the inlet mouth 32 of heat exchanger 30 heating with medium air 9.
Heat exchanger heats atmospheric oxygen tripping device based on tubulose enhancement type oxygen permeable film of the present invention also can be by being held out against permeation unit 29 that screw mandrel 27, hard metal nahlock 26, soft metal nahlock 25, vitrified pipe 24 and 19, ceramic spheres 23, ceramic of compact disk 22, annulus sealing-in agent 20 and 21, oxygen flow pipe 2, branch road metal tube 5 and vacuum valve 28 constitute and be connected in parallel on the main gas circuit pipe 5 and form by above-mentioned more than two groups.
During work, after 800～1000 ℃ of warm airs 9 that provided by heat exchanger 30 fed inlet plenum 16, heating oxygen flow pipe 2 was to working temperature; The pyroplastic deformation that utilizes high-temperature stable alloy annulus sealing-in agent 20 and 21 is 2 inside and outside separating of oxygen flow pipe, utilizes 8 pairs of oxygen flow pipes 2 of vacuum pump to vacuumize to obtain the inside and outside oxygen partial pressure difference of tubular film and extracts from air 9 isolated 1.5 crust oxygen 10 out for use; Also can with air compressor machine 11 oxygen 10 be pressurized in 5 Palestine and Israels for use again.
When the heat exchanger heats atmospheric oxygen tripping device based on tubulose enhancement type oxygen permeable film uses when not having the occasion of heat exchanger 30, can change inlet plenum 16 into tube furnace 1, so above two kinds of oxygen tripping devices are identical in form.
The present invention is at existing M 1-yM y' Co 1-xFe xO 3-δ(more than one among M=Sr, Ba, Ca, the Mg, M '=rare earth element) introducing strengthens with second phase material of the perovskite typed that basic rerum natura is mutually mated, fusing point is higher in the oxygen permeable film material, and resultant new oxygen permeable film material system possesses oxygen-permeable, mechanical stability, chemical stability and the thermal shock resistance that former system does not have; The described second phase enhanced effect is: the adding of this second phase makes the oxygen flow structural development of former oxygen flow system perfect, thereby has improved oxygen permeability; Second when basic phase camber disperses because of with basic structural similitude mutually, make basic phase structure pinned, thereby the structural stability of new oxygen permeable film material improved, thermal-shock resistance improves; The adding of second phase improves the sintering temperature of new system, and when using under the oxygen separation temperature condition than low 300～500 ℃ of sintering temperature, its chemical stability is improved; The present invention utilizes the oxygen separator prototype of above-mentioned enhancement type tubular film material design, and a considerable number of pure oxygen is isolated in preparation from air.
Compared with prior art, the invention has the advantages that:
1. oxygen permeable film material
(1) passes through at basic phase M 1-yM y' Co 1-xFe xO 3-δIntroduce the second phase NBO in (among M=Sr, Ba, Ca, the Mg at least a, M '=rare earth element) oxygen permeable film material 3(a kind of among N=Sr, Ba, Ca, the Mg, among B=Sn, the Zr a kind of) prepares the enhancement type oxygen permeable film material with high oxygen transmission rate; The highest oxygen transmission rate of sheet enhancement type oxygen permeable film system that thickness of the present invention is 1.2 millimeters in the time of 1000 ℃ above 3.1 milliliters centimetres -2Minute -1Some forms thick 1.2 millimeters samples still can isolate 0.07 milliliter centimetre at 560 ℃ -2Minute -1Oxygen, and enhanced base phase oxygen permeable film system has not had the oxygen flow ability when this temperature; The oxygen transmission rate of the tubulose enhancement type oxygen permeable film that wall thickness of the present invention is 1.35 millimeters 900 ℃ 0.21 the crust/0.12 the crust little oxygen partial pressure gradient under above 0.7 milliliter centimetre -2Minute -1, under the oxygen partial pressure gradient of 940 ℃ 0.21 crust/0.12 crust, can long-term stability isolate 1.5 milliliters centimetres -2Minute -1Oxygen, be higher than Holland's " Materials Science and Engineering " (Mater.Sci ﹠amp; Eng., 1992, B13, in 79-87) 1.0 milliliters centimetres of the oxygen transmission rates that proposes -2Minute -1Applicating limit; The oxygen permeability instability of the single basic phase material of reporting in the document in addition, more than the oxygen permeability drop by half, the oxygen permeable film oxygen permeability of different experimenter's preparations differs one to two order of magnitude behind the long-play.
(2) pass through at basic phase M 1-yM y' Co 1-xFe xO 3-δIntroduce an amount of another kind of perovskite-type material NBO in (more than one among M=Sr, Ba, Ca, the Mg, M '=rare earth element) oxygen permeable film material 3(a kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr) prepared enhancement type oxygen permeable film that goes out can surpass the vacuum tightness of-0.099 MPa in the long-time opposing of temperature more than 950 ℃; And existing document does not see that as yet corresponding data report, the oxygen permeation data of the single phase oxygen permeable film material that they provide are to produce by helium purge to obtain under the situation of oxygen partial pressure difference basically, promptly do not have the true pressure difference to exist in the film both sides.
(3) pass through at basic phase M 1-yM y' Co 1-xFe xO 3-δIntroduce an amount of another kind of perovskite-type material NBO in (more than one among M=Sr, Ba, Ca, the Mg, M '=rare earth element) oxygen permeable film material 3The enhancement type oxygen permeable film of (a kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr) has higher chemistry and mechanical stability and thermal shock resistance under middle pyritous working conditions; And single basic phase oxygen permeable film material sample surfaces under middle pyritous oxygen separation condition of existing reported in literature can decompose or segregation, and these samples do not see that the report that stands heat shock resistance aspect data is arranged yet.
(4) pass through at basic phase M 1-yM y' Co 1-xFe xO 3-δIntroduce an amount of another kind of perovskite-type material NBO in (among M=Sr, Ba, Ca, the Mg a kind of, M '=rare earth element) oxygen permeable film material 3(a kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr), prepare the enhancement type oxygen permeable film material with higher sintering temperature, be easy to get rid of the organic additive that the moulding of tubulose film body internal cause adds in sintering process, the sintering character of sample is better improved; And the sintering temperature of single phase oxygen permeable film material is lower, and the shaping assistant that adds in the ceramic course of processing is difficult the eliminating in sintering, thereby influences the oxygen permeability and the structure properties of ceramic membrane.
(5) pass through at basic phase M 1-yM y' Co 1-xFe xO 3-δIntroduce an amount of another kind of perovskite-type material NBO in (among M=Sr, Ba, Ca, the Mg a kind of, M '=rare earth element) oxygen permeable film material 3(a kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr) makes the high oxygen flow structure of the more difficult synthetic of some reported in literature mutually obtained, and the oxygen permeability of enhancement type oxygen permeable film can be improved more than 2.5 times with respect to single basic phase composite sample; And the order-disorder transition in single phase sample middle-temperature section oxygen room is inhibited in the enhancement type oxygen permeable film, makes the enhancement type oxygen permeable film still have the ability of substantial sepn oxygen 780 ℃ of following temperature.
2. oxygen tripping device:
(1) existing porous oxygen permeable film, polymeric membrane can only obtain the oxygen-rich air of oxygen concn 30%-40% usually for the oxygen separator on basis does not possess the ability of separating pure oxygen; And tripping device of the present invention can be directly from air high efficiency separation go out 100% pure oxygen.
(2) existing alternating temperature separated oxygen device technique complexity, required corollary apparatus is many, and is bulky, only should provide fairly large oxygen demand fixedly, be not suitable for providing portable oxygen supply, and isolated oxygen need rely on huge transport pipe network or liquid oxygen to transport the cold trap car to be transported to the user; And tripping device technology of the present invention is simple, Miniaturizable, saving separated space, can not only satisfy as extensive oxygen supply demand such as steel-making enterprise, chemical enterprise, also can make be easy to move, convenient, flexible medium and small direct apparatus of oxygen supply, satisfying as the medium-scale oxygen supply demand of industrial burner, and as family health care and hospital small-scale oxygen supply demand such as give emergency treatment to a patient.
(3) existing oxygen tripping device does not have the effect of recycling heat energy in the industrial gaseous waste; And the tripping device among the present invention can utilize the useless flue gas of Industrial Stoves to add warm air because of adopting heat exchanger, therefore has the effect of recycling the heat energy in the industrial gaseous waste.
(4) during oxygen, separation efficiency is low, isolates the second-rate of product, generally all needs former air is carried out purifying treatment in directly separating former air for existing oxygen tripping device; And tripping device of the present invention is because to the selectivity 100% of separated oxygen in the warm air, therefore can use not treated former air and do not influence the separation efficiency of separator, and reduce cost.
(5) existing ceramic oxygen separator based on solid electrolyte, when separated oxygen, need additional circuit, therefore need on separatory membrane, to increase electrode, the increase of electrode makes membrane structure complicated, need to adopt the sandwich type laminate structure of difficult preparation, and be vulnerable to the destruction of electric current and voltage effect, thereby shortened the work-ing life of oxygen tripping device; And the enhancement type separatory membrane that tripping device of the present invention adopts itself has internal circuit in because of ceramic body in the oxygen flow process, therefore make except not needing additional circuit membrane structure simple, easy and simple to handle, also make ceramic membrane avoid the effect of voltage and current, thereby prolonged the work-ing life of tripping device greatly.
(6) existing reported in literature uses the high intermediate temperature sealing agent at the oxygen tripping device mostly to be ceramic seal agent or the noble metals such as gold, platinum that glassy phase is the master, glass sealing agent loose product layer of meeting and oxygen permeable film reaction generation interface under the isolating operational condition of oxygen causes air leaking, and adopts noble metal can make the cost increase of oxygen tripping device; In the tripping device among the present invention, the high intermediate temperature sealing of tubulose oxygen permeable film adopts by glass powder, the second phase powder and the Terpineol 350 that contains ethyl cellulose and is in harmonious proportion the pug that forms or the ceramic seal agent or the high-temperature stable alloy annulus sealing-in agent of thick mud, so that the thermal expansivity of second phase and oxygen permeable film are complementary; Adopt a large amount of second phases the ceramic seal agent can with oxygen permeable film in heating and cooling process synchronously; High-temperature stable alloy annulus sealing-in agent can offset with the thermal distortion of oxygen permeable film in heat-processed; The thermal expansion that above-mentioned effect can compensate oxygen permeable film makes oxygen permeable film avoid mechanical stress destruction in thermal process, and between high intermediate temperature sealing agent and the tubulose oxygen film chemical reaction does not take place, therefore under big pressure difference, has good sealing-in ability, the oxygen flow pipe is remained intact in the process of room temperature at normal cooling, thereby can satisfy the discontinuous operation demand of tripping device.
(7) the existing oxygen separator that utilizes the mixed type oxygen permeable film to separate oxygen in the high-pressure air needs an air compressor machine and a resistant to elevated temperatures high pressure vessel; And oxygen tripping device of the present invention adopts the mode of vacuumizing to obtain the oxygen flow motivating force, adopts a minipump to replace the large-scale air compressor machine and the high pressure vessel of existing tripping device, and the cost of tripping device own and the cost of oxygen separation are greatly reduced.
Description of drawings:
Accompanying drawing 1 fine and close tubulose enhancement type oxygen permeable film is the tube furnace heating atmospheric oxygen tripping device synoptic diagram on basis;
Accompanying drawing 2 fine and close tubulose enhancement type oxygen permeable films are the heat exchanger heats atmospheric oxygen tripping device synoptic diagram on basis;
Accompanying drawing 3 (SrCo 0.89Fe 0.11O 3-δ) 0.9(SrZrO 3) 0.1Enhancement type oxygen permeable film material XRD figure;
Accompanying drawing 4 (SrCo 0.89Fe 0.11O 3-δ) 0.9(SrZrO 3) 0.1Enhancement type oxygen permeable film oxygen permeability and temperature relation figure;
Accompanying drawing 5 (SrCo 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) z(z=0.025-0.2) enhancement type oxygen permeable film material XRD figure;
Accompanying drawing 6 (SrCo 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) z(z=0.025-0.15) enhancement type oxygen permeable film oxygen permeability and temperature relation figure;
Accompanying drawing 7 (SrCo 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) z(z=0.05-0.2) thermal expansion of enhancement type oxygen permeable film material and temperature relation figure;
Accompanying drawing 8 (SrCo 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) z(z=0.1) the SEM photo after the thermal shocking of enhancement type oxygen permeable film;
Accompanying drawing 9 (La 0.2Ba 0.8Co 0.8Fe 0.2O 3-δ) 1-z(BaZrO 3) z(z=0.025-0.1) enhancement type oxygen permeable film material XRD figure;
Accompanying drawing 10 (La 0.2Ba 0.8Co 0.8Fe 0.2O 3-δ) 1-z(BaZrO 3) z(z=0.025-0.1) enhancement type oxygen permeable film oxygen permeability and temperature relation figure;
Accompanying drawing 11 (Sr 0.9M 0.1Co 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1The XRD figure of (M=Ca, Ba) enhancement type oxygen permeable film material;
Accompanying drawing 12 (Sr 0.9M 0.1Co 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1(M=Ca, Ba) enhancement type oxygen permeable film oxygen permeability and temperature relation figure;
Accompanying drawing 13 (SrCo 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Tubulose enhancement type oxygen permeable film is isolated the chromatogram detection figure of oxygen for the tripping device on basis;
Accompanying drawing 14 (SrCo 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Surfaces externally and internally XRD figure before and after tubulose enhancement type oxygen permeable film oxygen separates.
Embodiment:
Below in conjunction with description of drawings the specific embodiment of the present invention.
Embodiment 1:(SrCo 0.89Fe 0.11O 3-δ) 0.9(SrZrO 3) 0.1The enhancement type oxygen permeable film material
Adopt solid phase method to prepare sample; The raw materials used analytical pure (＞99%) that is calculates 0.12 mole of (SrCo by stoichiometric ratio 0.89Fe 0.11O 3-δ) 0.9(SrZrO 3) 0.1Batching form and to take by weighing: the SrCO of 17.895 grams 3, 8.041 the gram Co 2O 3, 0.968 the gram Fe 2O 3, 1.479 the gram ZrO2; After ball milling mixed 24 hours in the alcohol medium with the raw material that taken by weighing, flash baking was carried out twice pre-burning at 950 ℃ and 1050 ℃ then and is promptly obtained preparing the pottery powder, and pre-burning is incubated 10 hours in top temperature at every turn; Adopt the single shaft dry pressing with pressed by powder slabbing ceramic body, pressure 550 MPas; The sample that 1～2 mm thick that suppresses, diameter are 13 millimeters is warming up to 1250 ℃ and carried out sintering in 10～15 hours in this temperature insulation with 1.5 ℃ of per minutes, and then reduces to room temperature for 1～2 ℃ with per minute, promptly obtains the enhancement type oxygen permeable film.
The XRD figure of accompanying drawing 3 shows that above sample has tangible SrCo 0.89Fe 0.11O 3-δ(SCF) and SrZrO 3(SZ) the phase composite characteristic peak of two kinds of structures of matter.
Oxygen permeability evaluation test method and device can be referring to " solid state ionics " (Solid State Ionics, 1999,133,23-28) middle method and the devices of introducing.The oxygen partial pressure of test condition control low oxygen partial pressure end obtains (SrCo between 0.0125～0.0165 crust 0.89Fe 0.11O 3-δ) 0.9(SrZrO 3) 0.1Enhancement type oxygen permeable film oxygen permeability and temperature relation accompanying drawing 4.As can be seen from the figure: when 750-1000 ℃, oxygen partial pressure gradient were 0.209 crust/0.014 crust, the oxygen permeability of the enhancement type sheet oxygen permeable film of 1.5 mm thick was a 0.4-2 milliliter centimetre -2Minute -1This shows that the oxygen transmission rate of the enhancement type oxygen permeable film that present embodiment obtains doubles above than the oxygen permeable film applicating limit oxygen transmission rate of reported in literature.
Embodiment 2:(SrCo 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) z(z=0.025-0.2) enhancement type oxygen permeable film material
Adopt solid phase method to prepare sample; Calculate (SrCo by stoichiometric ratio 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) z(z=0.025-0.2) batching composition carries out weighing, and the raw materials used analytical pure (＞99%) that is is respectively: SrCO 3, Co 2O 3, Fe 2O 3, SnO; After ball milling mixed 24 hours in the alcohol medium with the raw material that takes by weighing, flash baking was carried out twice pre-burning at 920 ℃ and 1050 ℃ respectively then and is promptly obtained preparing the pottery powder, and pre-burning is incubated 10 hours in top temperature at every turn; Adopt the single shaft dry pressing with pressed by powder slabbing ceramic body, pressure 500 MPas; The base substrate that suppress thick 1～2 millimeter, diameter are 13 millimeters is warming up to 1120～1300 ℃ and carried out sintering in 10～15 hours in this temperature insulation with 1.5 ℃ of per minutes, and then reduces to room temperature with 1～2 ℃ of per minute and obtain sheet enhancement type oxygen permeable film.
Accompanying drawing 5 shows that the XRD figure of above sample has tangible SrCo 0.8Fe 0.2O 3-δ(SCF) and SrSnO 3(SS) the phase composite characteristic peak of two kinds of structures of matter.
Oxygen permeability evaluation test device and testing method are with the apparatus and method among the embodiment 1; Test condition: control low oxygen partial pressure end oxygen partial pressure is between 0.0125～0.0165 crust; Range of measuring temp; 560 ℃～1000 ℃.
The sample oxygen permeability reflects that with the variation of temperature relation oxygen permeability of enhancement type oxygen permeable film surpasses 1.0 milliliters centimetres of oxygen transmission rates in the accompanying drawing 6 -2Minute -1Applicating limit, this boundary value is equivalent to 0.67 * 10 -6The mole centimetre -2Second -1Wherein, the second phase mol ratio is that sample oxygen permeability in the time of 1000 ℃ of 2.5% reaches 2.2 * 10 -6The mole centimetre -2Second -1, this oxygen transmission rate value is higher than removes Japan's " chemical communication " (Chem.Lett., 1985, the 1743-1746) SrCo that reports at first 0.8Fe 0.2O 3-δThe oxygen transmission rate of all mixed conductors in addition; The second phase mol ratio is that the oxygen permeability of 560 ℃ in 15% sample is 0.5 * 10 -7The mole centimetre -2Second -1, the most mixed type oxygen permeable films during this temperature have lost the oxygen flow ability.
Accompanying drawing 7 has reflected (SrCo 0.8Fe 0.2O 3-δ) 1-z(SrSnO 3) zThe coefficient of expansion of enhancement type oxygen flow material reduces situation: enhancement type oxygen flow material has the thermal expansivity of obvious reduction than single matrix phase material, wherein the 0-1000 of z=0.2 sample ℃ evenly heat rate of expansion has reduced about 30% than the single phase sample of z=0, make like this present embodiment obtain the enhancement type oxygen permeable film can be well and on the separator other parts be complementary.
The good resistance thermal shock resistance properties of the SEM photo of z=0.1 sample reflection enhancement type sample behind the thermal shock experiment in the accompanying drawing 8; When to the sheet sample of z=0.1 speed with 10 ℃/minute, in 100-1000 ℃ of temperature range, carry out to see that the microstructure of sample is identical with fresh sample after rapid heat cycle impacts 16 times, and the defective that does not have tiny crack etc. to influence the sample structure integrity occurs, and shows that present embodiment obtains the enhancement type oxygen permeable film and has higher thermal shock resistance; And the higher ceramic membrane of other oxygen permeability of known reported in literature is all less than the introduction about the thermal shock resistance aspect.
Embodiment 3:(La 0.2Ba 0.8Co 0.8Fe 0.2O 3-δ) 1-z(BaZrO 3) z(z=0.025-0.1) enhancement type oxygen permeable film material
Adopt solid phase method to prepare sample; Calculate (La by stoichiometric ratio 0.2Ba 0.8Co 0.8Fe 0.2O 3-δ) 1-z(BaZrO 3) zBatching form and to take by weighing raw material, the raw materials used analytical pure (＞99%) that is is respectively: La 2O 3, BaCO 3, Co 2O 3, Fe 2O 3, ZrO 2Alleged raw material ball milling in the alcohol medium mixed after 24 hours, and flash baking is carried out twice pre-burning at 920 ℃ and 1050 ℃ then and promptly obtained preparing the pottery powder, and each pre-burning was top temperature insulation 10 hours; Adopt the single shaft dry pressing with pressed by powder slabbing ceramic body, pressure is 500 MPas; The base substrate that 1～2 mm thick that suppresses, diameter are 13 millimeters is warming up to 1190～1200 ℃ and carried out sintering in 10～15 hours in this temperature insulation with 1.5 ℃ of per minutes, and then reduces to room temperature with 1～2 ℃ of per minute and promptly obtain the enhancement type oxygen permeable film.
The XRD figure of accompanying drawing 9 shows that above sample has tangible La 0.2Ba 0.8Co 0.8Fe 0.2O 3-δ(LBCF) and BaZrO 3(BZ) the constitutional features peak of two kinds of phase composites.
Oxygen permeability evaluation test device and testing method are with the apparatus and method among the embodiment 1; Test condition: control low oxygen partial pressure end oxygen partial pressure is between 0.0125～0.0165 crust.The improvement of oxygen permeability is reflected in (La shown in the accompanying drawing 10 0.2Ba 0.8Co 0.8Fe 0.2O 3-δ) 1-z(BaZrO 3) z(z=0.025-0.1) on enhancement type oxygen permeable film oxygen permeability and the temperature relation figure: the oxygen permeability of thick 1.2 millimeters z=0.05 sheet sample in the time of 1000 ℃ up to 2 * 10 -6The mole centimetre -2Second -1, it still has higher oxygen permeability at 550 ℃; And China's " catalysis journal " (2000,5,505-509) the single uhligite phase La of report 0.2Ba 0.8Co 0.8Fe 0.2O 3-δCan not generate from calculation of thermodynamics, in the present embodiment by the second phase enhanced mode this name form obtain on basis oxygen permeability very high the enhancement type oxygen permeable film material.
Embodiment 4:(M 0.1Sr 0.9Co 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1(M=Ca, Ba) enhancement type oxygen permeable film material
Adopt solid phase method to prepare sample; Calculate (M by stoichiometric ratio 0.1Sr 0.9Co 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1The batching composition of (M=Ca, Ba) takes by weighing raw material, and the raw materials used analytical pure (＞99%) that is is respectively: BaCO 3, CaCO 3, SrCO 3, Co 2O 3, Fe 2O 3, SnO; Alleged raw material ball milling in the alcohol medium mixed after 24 hours, and flash baking is carried out twice pre-burning at 920 ℃ and 1050 ℃ then and promptly obtained preparing the pottery powder, and each pre-burning was top temperature insulation 10 hours; Adopt the single shaft dry pressing with pressed by powder slabbing ceramic body, pressure 500 MPas; The ceramic body that 1～2 mm thick that suppresses, diameter are 13 millimeters is warming up to 1250 ℃ and carried out sintering in 10～15 hours in this temperature insulation with 1.5 ℃ of per minutes, and then reduces to room temperature with 1～2 ℃ of per minute and promptly obtain the enhancement type oxygen permeable film.
The XRD figure of accompanying drawing 11 shows that above sample has tangible M 0.1Sr 0.9Co 0.89Fe 0.11O 3-δ(MSCF, M=Ca, Ba) and SrSnO 3The phase composite characteristic peak of two kinds of structures of matter.
Oxygen permeability evaluation test device and testing method are with the apparatus and method described in the embodiment 1; Test condition: control low oxygen partial pressure end oxygen partial pressure is between 0.0125～0.0165 crust; (Sr from accompanying drawing 12 0.9M 0.1Co 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Among (M=Ca, Ba) enhancement type oxygen permeable film oxygen permeability and the temperature relation figure as can be seen: the oxygen permeability of sample is higher mutually than the high oxygen flow of reported in literature to obtain the enhancement type oxygen permeable film in the present embodiment; The M=Ca sample at 1000 ℃ oxygen permeability up to 2.9 milliliters centimetres -2Minute -1
Embodiment 5:(SrCo 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1The enhancement type oxygen permeable film material
Adopt Pei Qini (Pechini) legal system to be equipped with sample; Calculate (SrCo by stoichiometric ratio 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Batching form, the raw materials used analytical pure (＞99%) that is is respectively: Sr (NO 3) 2, Co 2O 3, Fe 2O 3, Sn (NO 3) 4Alleged raw material is used dense HNO at 100 ℃ 3Dissolving adds citric acid and ethylene glycol in above nitrate solution, stir at 80 ℃ then and made stable sol in 5 hours, and it is the metal ion sum that institute adds above material molar ratio example: citric acid: ethylene glycol=1: 1.5: 1; To obtain colloidal sol and continue stir dehydration at 80 ℃ and made gel in 12 hours, gel will be heated into dry powder at 350 ℃, then with dry powder 950 ℃ of pre-burnings 5 hours, promptly obtain (SrCo 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Enhancement type oxygen permeable film powder adopts method moulding and the sintering introduced among the embodiment 3 promptly to obtain sheet enhancement type oxygen permeable film this powder; This oxygen permeable film has SrCo 0.89Fe 0.11O 3-δAnd SrSnO 3Two kinds of phase composite constitutional featuress.
Oxygen permeability evaluation test device and testing method are with the apparatus and method described in the embodiment 1; Test condition: the oxygen partial pressure of control low oxygen partial pressure end is between 0.0125～0.0165 crust; It is higher than the oxygen permeability of the high oxygen flow phase sample of reported in literature to obtain the enhancement type oxygen permeable film in the present embodiment; The sample of 1 mm thick at 950 ℃ oxygen permeability up to 3.5 milliliters centimetres -2Minute -1This enhancement type oxygen permeable film is better than the thermal shock resistance of the high oxygen flow phase sample of reported in literature, the structure that under 20 ℃/minute the heating and cooling condition more than 20 times, can remain intact, and each here heating and cooling amplitude is 1000 ℃.
Embodiment 6: fine and close tubulose enhancement type oxygen permeable film is the tube furnace heating atmospheric oxygen tripping device on basis
Adopt solid phase method to prepare sample; Calculate (SrCo by stoichiometric ratio 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Batching form and to take by weighing raw material, the raw materials used analytical pure (＞99%) that is is respectively: SrCO 3, Co 2O 3, Fe 2O 3, SnO; Behind the ball milling mixing 24h, carry out twice pre-burning at 920 ℃ and 1050 ℃ then and promptly obtain to prepare the pottery powder by flash baking in the alcohol medium for alleged raw material, and each pre-burning was top temperature insulation 10 hours; The plasticity roll-in method moulding that powder adopts traditional ceramics preparation technology will be obtained, to account for the ceramic powder, 4% glycerine of system gross weight 70% and 1% oleic acid before the moulding earlier, 25% the ethyl cellulose weight concentration per-cent that contains is 20% terpineol solution, mix stirring 4 hours at 60～80 ℃, be used to strengthen mobile organism with exclusive segment, the organic pug of exclusive segment is cooled to room temperature, promptly gets ceramic material.
(China Construction Industry Press publishes to adopt " ceramic process ", 1980,82-84) rolling process of Jie Shaoing is pressed into ceramic body with the ceramic material that obtains, in the baking oven of cross-ventilated, temperature programmed control, a ℃ baking made the pipe demoulding and got rid of organic solvent in 48 hours in room temperature～160, i.e. plastic removal; Be warmed up to 1050 ℃ of insulations with 0.75 ℃ of per minute again and slowly discharged the carbon that organism decomposites in the base substrate in 10 hours, promptly arrange carbon; Sample is warmed up to 1250 ℃ and be incubated 20 hours and carry out sintering with 1 ℃ of per minute behind row's carbon, reduces to room temperature for 1 ℃ with per minute subsequently, promptly obtains the oxygen flow pipe 2 that the fine and close enhancement type oxygen permeable film material of an end closure is formed.
By the tube furnace heating atmospheric oxygen tripping device that is assembled into shown in the accompanying drawing 1 based on fine and close tubulose enhancement type oxygen permeable film, go up end closure, fine and close enhancement type oxygen permeable film material (SrCo with one 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1The opening end of the oxygen flow pipe of forming 2 is built by laying bricks or stones on single pass vitrified pipe pedestal 4 with pyroceramic sealing-in agent 3, puts into the burner hearth of tube furnace 1; After vitrified pipe pedestal 4 stretches out tube furnace 1 outside part and cool metal pipe 5 links to each other, receive oilless vacuum pump 8 through buffering gas-holder 6; Be connected to vacuum meter 7 on the gas-holder 6; Metal tube 5 makes isolated oxygen 10 be cooled through before the oilless vacuum pump 8 by contacting with air, with protection separation system works better; Described pyroceramic sealing-in agent 3 is by 95 material glass powders, SrSnO 3Be in harmonious proportion the pug form with the Terpineol 350 that contains ethyl cellulose.
During work, be heated to earlier 1000 ℃ of the sintering temperatures of high intermediate temperature sealing agent 3 with tube furnace 1, the sintering of high intermediate temperature sealing agent 3 is linked as oxygen flow pipe 2 and vitrified pipe pedestal 4 integral body, the air 9 in oxygen flow pipe 2 inner chambers and the burner hearth is separated; After this tube furnace 1 continuation heating is kept and is entered the interior air 9 of burner hearth at 800-1000 ℃; Thereby utilize 8 pairs of oxygen flow pipes 2 of vacuum pump to vacuumize to form the inside and outside oxygen partial pressure of oxygen flow pipe 2 poor, can from oxygen flow pipe 2, extract isolated oxygen 10 from air 9 out thus; Extract vacuum pump 8 outlets the oxygen 10 of 1.5 crust out directly for using.Under 1000 ℃ service temperature, adopt oxygen tripping device in the present embodiment on the tubular specimen of 7.4 millimeters * 2.1 millimeters of long * internal diameter * thickness=5.5 cm x, can obtain 1 crust oxygen for invalid 40 ml/min.
Figure 13 is the chromatogram detection figure that isolates oxygen purity, and the result of gas chromatographic analysis isolates oxygen purity greater than 99%; Vacuum system keeps the identical pressure of oxygen partial pressure with 0.209 crust in the air for a long time after pump quits work, this shows that the purity that obtains oxygen in the present embodiment is 100%.
Figure 14 is the XRD result of tubular specimen surfaces externally and internally before and after the oxygen separation, and it reflects that the phase composite of this sample surfaces externally and internally under 950 ℃ of high temperature oxygen separation conditions is identical with fresh sample, and structure and chemical property are stable; And sample can use repeatedly.
Compare for the small oxygen pump on basis with existing solid electrolyte oxygen permeable film, the oxygen tripping device of present embodiment has reduced additional circuit than existing small oxygen pump, the membrane structure of using is simple, therefore the cost that needs under same scale is lower than adopting the oxygen pump with the cost of isolating oxygen, and has prolonged the work-ing life of tripping device because film is not subjected to the current/voltage effect.
Oxygen tripping device in the present embodiment is small and exquisite flexibly, can move to any one on a small scale aerobic place on the spot separated oxygen use is provided, and existing air alternating temperature separated oxygen device does not have this function because of not moving.
Existing porous ceramics and polymkeric substance oxygen permeable film are the oxygen-rich air that the oxygen tripping device on basis can only obtain oxygen concn 30～40%, and the oxygen tripping device in the present embodiment can be isolated 100% pure oxygen.
The high intermediate temperature sealing of the oxygen permeable film of oxygen tripping device has adopted the ceramic seal agent that can compensate the tubular film thermal expansion in the present embodiment, thereby makes oxygen permeable film and ceramic seal agent can keep deform in same pace in thermal process, avoids mechanical stress and destroys; Adopt conventional ceramic or the glass sealing agent that does not have above compensate function and existing tripping device based on solid electrolyte film and mixed type film, have a power failure suddenly and during long-time running can because oxygen permeable film and the sealing-in agent coefficient of expansion does not match and and the sealing-in agent in alkalimetal ion reaction and sealing-in is failed, reduce and lose separating power.
Embodiment 7: fine and close tubulose enhancement type oxygen permeable film is the heat exchanger heats atmospheric oxygen tripping device on basis
Earlier make plastic mud material with obtaining powder among the embodiment 6: to be 20% cellulose aqueous solution, 5% plastic agent, 5% deaerating agent with 20% deionized water join ceramic powder, 30% the concentration expressed in percentage by weight that will account for system gross weight 40% that ball milling becomes to stablize mud in the ball grinder that zirconia balls is housed, slurry vacuum is stirred the dehydration deaeration, make ceramic material through pugging again; Methylcellulose gum in the described cellulose aqueous solution and polyvinyl alcohol respectively account for 50%.
The ceramic material that obtains adopts " ceramic process ", and (China Construction Industry Press publishes, 1980,80-81) extrusion molding of Jie Shaoing is made tubular ceramic film base substrate, with base substrate in the baking oven of temperature programmed control by room temperature to 120 ℃ oven dry after 10 hours, be warming up to 1270 ℃ and be incubated 20 hours and carry out sintering with 1 ℃ of per minute, reduce to (the SrCo that room temperature promptly obtains both ends open for 1 ℃ with per minute subsequently 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1The fine and close tubulose enhancement type oxygen permeable film of forming 2 specifically is of a size of: 7.4 millimeters * 2.1 millimeters of length * internal diameters * thickness=50 cm x.
Press the heat exchanger heats atmospheric oxygen tripping device synoptic diagram assembling oxygen tripping device of the fine and close tubulose enhancement type oxygen permeable film shown in the accompanying drawing 2 for the basis, one with ceramic plate 13 for its bottom, in have in the metal vessel 12 of high-temperature-resistant layer, with vitrified pipe 19 vertical insert and add the crack with refractory inorganic adhesive be fixed in the ceramic plate 13 intermediary circular holes; Upwards pile up high-temperature stable alloy annulus sealing-in agent 20 successively from vitrified pipe 19 tops, by the fine and close enhancement type oxygen permeable film material (SrCo of both ends open 0.89Fe 0.11O 3-δ) 0.9(SrSnO 3) 0.1Oxygen flow pipe 2, annulus sealing-in agent 21, ceramic of compact disk 22, zirconia ceramic ball 23 and the vitrified pipe 24 formed, the circular hole that vitrified pipe 24 passes in the middle of the ceramic plate 14 and caliber is complementary, its gap is stifled real with high temperature resistant rock wool, and these ceramic plate 14 usefulness refractory inorganic adhesives are fixed on spacing in the metal vessel 12 and are divided into cold house, top 15 and bottom inlet plenum 16; Pile up normal temperature soft metal nahlock 25, hard metal nahlock 26 successively at vitrified pipe 24 tops of stretching out ceramic plate 14, by the screw mandrel 27 that holds out against that is positioned in the metal vessel 12 top screws above-mentioned parts integral body is held out against at last, and screw mandrel 27 and vitrified pipe 19,24 are kept with one heart; Normal temperature soft metal nahlock 25 and hard metal nahlock 26 are arranged in cold house 15, and annulus sealing-in agent 20 and 21, oxygen flow pipe 2, ceramic of compact disk 22, ceramic spheres 23 are arranged in inlet plenum 16; Vitrified pipe 19 stretches out part outside metal vessel 12 with after a branch road metal tube 5 links to each other, and links on the main gas circuit pipe 5 through vacuum valve 28, and main gas circuit pipe 5 is linked air compressor machine 11 through vacuum pump 8; Inlet plenum 16 is provided with inlet mouth 17 and air outlet 18, and this inlet mouth 17 is connected in heated air 9 outlets 31 of heat exchanger 30, and air outlet 18 is connected on the inlet mouth 32 of heat exchanger 30 heating with medium air 9.
Constitute the permeation unit 29 of 29,200 groups of permeation units according to being connected in parallel on upper type on the main gas circuit pipe 5 by holding out against screw mandrel 27, hard metal nahlock 26, soft metal nahlock 25, vitrified pipe 24 and 19, ceramic spheres 23, ceramic of compact disk 22, annulus sealing-in agent 20 and 21,50 cm long oxygen flow pipes 2, branch road metal tube 5 and vacuum valve 28.
Behind the 9 feeding inlet plenums 16 of warm air more than 950 ℃ that heat exchanger 30 provides, heating oxygen flow pipe 2 is to working temperature, the pyroplastic deformation that utilizes high-temperature stable alloy annulus sealing-in agent 20 and 21 is with 2 inside and outside separating of oxygen flow pipe, utilize the some contact between ceramic spheres 23 and the ceramic disks 22 to keep oxygen flow pipe 2 stressed even, increase sealing-in effects, suffered stress rupture when utilizing the low-temperature deformation of soft metal piece 25 to reduce 2 high temperature deformations of oxygen flow pipe, what the high-temperature stable alloy annulus sealing-in agent 18 in the present embodiment was adopted is the alumel annulus; Utilize vacuum pump 8 to vacuumize to obtain the inside and outside oxygen partial pressure differences of tubular film 2 and extract out after the oxygen 10 of from air 9, isolating 1.5 crust, with air compressor machine 11 oxygen 10 is pressurized to oxygen 10 in 5 Palestine and Israels for use again.Utilize the oxygen tripping device in the present embodiment can isolate 800 liters/minute 1 crust oxygen, enough provide the kiln burner of various models to use.
The oxygen tripping device of present embodiment than existing based on the mixed type oxygen permeable film, be used for having reduced a large-scale air compressor machine and resistant to elevated temperatures high pressure vessel from the tripping device of high-pressure air oxygen separation, and with a small-sized vacuum pump for it, so installation cost and isolate the oxygen cost and greatly reduce than the latter.
Oxygen tripping device in the present embodiment does not need institute's separation of air is purified, and its heat exchanger can utilize heat energy in the industrial gaseous waste; And the oxygen tripping device that adopts existing air temperature-switching method, pressure swing adsorption process needs earlier isolating air to be purified, and it can not utilize heat energy in the industrial gaseous waste.
The oxygen tripping device of present embodiment has adopted and can compensate tubular film heating process of cooling expansible alumel sealing-in agent, therefore can not destroy the oxygen tripping device if in use shut off power in emergency yet, and the oxygen tripping device that has now based on the mixed type oxygen permeable film adopts conventional ceramic or glass sealing agent more, do not have the ability of compensation oxygen flow tube swelling, can not matching because of the thermal expansivity of ceramic seal agent and oxygen flow pipe when the oxygen flow device has a power failure suddenly causes separatory membrane cracked.
Embodiment 8: the fibrous enhancement type oxygen permeable film of hollow ceramic is the tube furnace heating atmospheric oxygen tripping device on basis
Adopt " solid state ionics " (Solid State Ionics with obtaining ceramic material among the embodiment 7,2000,135,637-632) the spin processes moulding of Jie Shaoing, make the fibrous enhancement type oxygen permeable film 2 of hollow ceramic of an end closure by embodiment 7 described sintering methods, below also claim " enhancement type oxygen flow pipe 2 ", specifically be of a size of: 2 millimeters * 0.1 millimeter of length * internal diameter * thickness=20 cm x.
By the tube furnace heating atmospheric oxygen tripping device that is assembled into shown in the accompanying drawing 1 based on the fibrous enhancement type oxygen permeable film of hollow ceramic, the opening end of 10,000 enhancement type oxygen flow pipes 2 of one end closure is built by laying bricks or stones on each the subchannel mouth on the compact alumina pedestal tube 4 with pyroceramic sealing-in agent 3, put into the burner hearth of tube furnace 1; Main channel and each subchannel in the vitrified pipe pedestal 4 communicate, and after the main channel outlet is stretched out tube furnace 1 outside part and cool metal pipe 5 is linked to each other, receive oilless vacuum pump 8 through buffering gas-holder 6; Be connected to vacuum meter 7 on the gas-holder 6; Described pyroceramic sealing-in agent 3 is by glass powder, SrSnO 3Powder and the Terpineol 350 that contains ethyl cellulose are in harmonious proportion the thick mud form.
During work, be heated to earlier 1000 ℃ of the sintering temperatures of high intermediate temperature sealing agent 3 with tube furnace 1, the sintering of high intermediate temperature sealing agent 3 is linked as enhancement type oxygen flow pipe 2 and vitrified pipe pedestal 4 integral body, the air 9 in oxygen flow pipe 2 inner chambers and the burner hearth is separated; After this tube furnace 1 continuation heating is kept and is entered the interior air 9 of burner hearth at 800-1000 ℃; Thereby utilize 8 pairs of oxygen flow pipes 2 of vacuum pump to vacuumize to form the inside and outside oxygen partial pressure of oxygen flow pipe 2 poor, can from oxygen flow pipe 2, extract isolated oxygen 10 from air 9 out thus, by the oilless air compressor 11 that connects vacuum pump 8 outlets oxygen 10 is pressurized in 5 Palestine and Israels for use again.
Adopt the tripping device in the present embodiment can obtain 4.3 meters 3/ minute 1 the crust oxygen; This will make the separating power of enhancement type oxygen permeable film and separation efficiency increase by 100 times with respect to common shape oxygen flow pipe.
Enhancement type oxygen permeable film in the present embodiment has adopted structure enhanced separation membrane material to make, be shaped as the higher hollow ceramic fiber of separation efficiency, therefore the oxygen tripping device in the present embodiment is more stable based on the oxygen tripping device structure of mixed type oxygen permeable film than existing, and separation efficiency is higher.

Claims (9)

1, a kind of perofskite type oxide enhanced compact ceramic oxygen permeable membrane material is characterized in that, it is by the second phase NBO 3Enhanced M 1-yM y' Co 1-xFe xO 3-δBase two-phase composite ceramics oxygen permeable film material, its chemical expression formula is: (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) z, a kind of among N=Sr, Ba, Ca, the Mg wherein, a kind of among B=Sn, the Zr, at least a among M=Sr, Ba, Ca, the Mg, M '=rare earth element; Subscript x, y, z are molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50; Wherein base is M mutually 1-yM y' Co 1-xFe xO 3-δ, be the mixed type ceramic oxygen-permeable membrane material of perovskite structure.
2, a kind of preparation method of powder of compact ceramic oxygen permeable membrane material as claimed in claim 1 adopts solid state reaction synthetic, it is characterized in that, presses chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zIn contained various cationic mol ratios calculate the amount of corresponding raw material, with its analytically pure carbonate, nitrate, oxalate or oxide compound batching, ball milling mixes in the alcohol medium, carry out 2～3 pre-burnings after the flash baking: 850～950 ℃ carry out the 1st time 10～20 hours pre-burning after, through dry ball milling, carry out 1 to 2 pre-burning in 10～20 hours at 1000～1100 ℃ again, again through dry ball milling.
3, a kind of preparation method of powder of the material of compact ceramic oxygen permeable membrane according to claim 1 adopts wet chemical method synthetic, it is characterized in that, presses chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zIn contained various cationic mol ratios calculate raw materials used amount, get analytically pure carbonate, nitrate, oxalate or oxide compound respectively and prepare burden, be dissolved in nitric acid; With the compound nitrate solution that obtains, atomizing sprays into the moisture eliminator of 300～400 ℃ band powder collector, obtains compound nitrate dry powder, 900～1000 ℃ of pre-burnings 5～10 hours.
As the preparation method of the powder of compact ceramic oxygen permeable membrane material as described in the claim 3, be characterised in that 4, described dry powder adopts compound nitrate solution atomizing sprayed in the refrigerator below-10 ℃ and obtains agar earlier, the moisture content volatilization with agar obtains then.
5, a kind of preparation method of perofskite type oxide enhanced sheet compact ceramic oxygen permeable membrane is characterized in that, with chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zEnhancement type oxygen permeable film material powder be raw material, at least a among M=Sr, Ba, Ca, the Mg wherein, M '=rare earth element; A kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr, subscript x, y, z are molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50; Adopt the single shaft dry pressing, be pressed into the flaky pottery base substrate of 13 millimeters of thick 1～2 millimeters, diameter with 350～550 MPa pressure, be warming up to 1120 ℃～1300 ℃ insulations with 1.5 ℃ of per minutes and carried out sintering in 10～20 hours, and then reduce to room temperature for 1～2 ℃ with per minute.
6, a kind of preparation method of perofskite type oxide enhanced tubulose compact ceramic oxygen permeable membrane is characterized in that, with chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zEnhancement type oxygen permeable film material powder be raw material, at least a among M=Sr, Ba, Ca, the Mg wherein, M '=rare earth element; A kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr, subscript x, y, z are molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50; Adopt isostatic pressing method to make the tubular ceramic base substrate, be warming up to 1120 ℃～1300 ℃ insulations with 1.5 ℃ of per minutes then and carried out sintering in 10～20 hours, reduce to room temperature for 1～2 ℃ with per minute again, promptly; Or adopting extrusion molding or rolling process that ceramic material is made the tubular ceramic base substrate of 0.5～2.5 millimeter one end closure of thickness of pipe, the other end opening or both ends open, drying, plastic removal and row's carbon are at 1130～1300 ℃ of sintering.
7, the preparation method of the fibrous compact oxygen permeable film of a kind of perofskite type oxide enhanced hollow ceramic is characterised in that: with chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) zEnhancement type oxygen permeable film material powder be raw material, at least a among M=Sr, Ba, Ca, the Mg wherein, M '=rare earth element; A kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr, subscript x, y, z are molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50; Adopt spin processes that ceramic material is made 0.01 millimeter of thickness of pipe, internal diameter less than 1 millimeter, the hollow ceramic fiber base substrate of an end closure, through super-dry, plastic removal and row's carbon, at 1130～1300 ℃ of sintering promptly at last.
8, a kind of tube furnace heating atmospheric oxygen tripping device based on tubulose enhancement type oxygen permeable film is characterized in that: with end closure on or a group with chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) z, at least a among M=Sr, Ba, Ca, the Mg wherein, M '=rare earth element; A kind of among N=Sr, Ba, Ca, the Mg, a kind of among B=Sn, the Zr, subscript x, y, z are molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50, the opening end of the oxygen flow pipe (2) formed of compact ceramic oxygen permeable membrane material, build by laying bricks or stones respectively on each the subchannel mouth on the corundum ceramic pedestal tube (4) with pyroceramic sealing-in agent (3), put into the burner hearth of tube furnace (1); Main channel and each subchannel in the vitrified pipe pedestal (4) communicate, and it is outer with after cool metal pipe (5) links to each other that tube furnace (1) is stretched out in the main channel outlet, receives oilless vacuum pump (8) through cushioning gas-holder (6); Be connected to vacuum meter (7) on the gas-holder (6); Described pyroceramic sealing-in agent (3) is for being in harmonious proportion pug or the thick mud form by glass powder, the second phase powder and the Terpineol 350 that contains ethyl cellulose; This second phase powder is NBO 3
9, a kind of heat exchanger heats atmospheric oxygen tripping device based on tubulose enhancement type oxygen permeable film, it is characterized in that: with ceramic plate (13) for its bottom, in have in the metal vessel (12) of high-temperature-resistant layer, vitrified pipe (19) is vertically inserted and adds the crack and be fixed in ceramic plate (13) the intermediary circular hole with refractory inorganic adhesive; Upwards pile up successively from vitrified pipe (19) top high-temperature stable alloy annulus sealing-in agent (20), by both ends open with chemical expression formula (M 1-yM y' Co 1-xFe xO 3-δ) 1-z(NBO 3) z,, at least a among M=Sr, Ba, Ca, the Mg wherein, M '=rare earth element; N=Sr, Ba, Ca, a kind of among the Mg, B=Sn, a kind of among the Zr, subscript x, y, z is molar fraction: 0.11≤x≤1.0,0.0≤y≤0.5,0＜z≤0.50, the oxygen flow pipe (2) formed of compact ceramic oxygen permeable membrane material, annulus sealing-in agent (21), ceramic of compact disk (22), corundum matter or zirconia ceramic ball (23) and vitrified pipe (24), the circular hole that vitrified pipe (24) passes in the middle of the ceramic plate (14) and caliber is complementary, its gap is stifled real with high temperature resistant rock wool, and this ceramic plate (14) is fixed on spacing in the metal vessel (12) with refractory inorganic adhesive and is divided into cold house, top (15) and bottom inlet plenum (16); Pile up normal temperature soft metal nahlock (25), hard metal nahlock (26) successively at the vitrified pipe that stretches out ceramic plate (14) (24) top, by the screw mandrel (27) that holds out against that is positioned in the screw of metal vessel (12) top above-mentioned parts integral body is held out against at last, and screw mandrel (27) and vitrified pipe (19), (24) are kept with one heart; Vitrified pipe (19) stretches out part outside metal vessel (12) with after a branch road metal tube (5) links to each other, and links on the main gas circuit pipe (5) through vacuum valve (28), and main gas circuit pipe (5) is linked air compressor machine (11) through vacuum pump (8); Inlet plenum (16) is provided with inlet mouth (17) and air outlet (18), this inlet mouth (17) is connected in heated air (9) outlet (31) of heat exchanger (30), and air outlet (18) are connected on the inlet mouth (32) of heat exchanger (30) heating with medium air (9).
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