CA2093332A1 - Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membrane - Google Patents
Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membraneInfo
- Publication number
- CA2093332A1 CA2093332A1 CA002093332A CA2093332A CA2093332A1 CA 2093332 A1 CA2093332 A1 CA 2093332A1 CA 002093332 A CA002093332 A CA 002093332A CA 2093332 A CA2093332 A CA 2093332A CA 2093332 A1 CA2093332 A1 CA 2093332A1
- Authority
- CA
- Canada
- Prior art keywords
- oxygen
- zone
- membrane
- containing gas
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D59/00—Separation of different isotopes of the same chemical element
- B01D59/10—Separation by diffusion
- B01D59/12—Separation by diffusion by diffusion through barriers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
- C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/0271—Perovskites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/1231—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte with both reactants being gaseous or vaporised
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/0046—Nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
2093332 9205862 PCTABS00011 Oxygen is separated from an oxygen-containing gas by introducing the gas into a first zone (1) of a gas separation apparatus, the apparatus comprising first (1) and second (2) zones separated by a mixed metal oxide membrane (8), the membrane (8) having a first surface (7) open to the first zone (1), a second surface (10) open to the second zone (2), and an empirical formula of Bi Ax My Mz' On, where A is at least one of Mg, Ca, Sr, Ba, Y, Th, U, and the lanthanide elements; M is at least one of Sc, Ti, Cr, Mn, Fe, Ni, Cu and Zn; and M' is at least one of Co, Rh, Pd, Pt or Ru. The oxygen separated from the oxygen-containing gas can be recovered from the second surface (10) of the membrane (8) either as molecular oxygen, or it can be reacted with an oxygen-consuming substance, such as a hydrocarbon gas, which can be introduced into the second zone (2) of the separation apparatus and brought in contact with the second surface (10) of the membrane (8).
Description
W O 9~/0586~ PCT/US91/0739~
.
.
2~)9333~
PROCESS FOR SEPARATIN~a OXYGEN FROM AN
OXYGEN-CONTAINING GAS BY USING A
BI-CONTAINING HIXED METAL OXIDE MEMBRA~I~
~A~ UN~ Ult Tll~ lNV~NrlON
1. Field of the Invention This invention relates.to a process for separatlng oxygen from an oxygen-containing gas, such as air. In one aspect, ~he invention relates to a process in which the oxygen is separated from the oxygen-containing gas by me.~ns.of a Bi-containing mixed metal oxide membrane. In 10 another aspect, the invention relates to a process for providing an oxygen-consuming substance with oxygen extracred from an oxygen-containing gas by means of a Bi-containing mixed metal oxide membrane.
2. Description of the Prior Art5 Bi-containing mixed metal oxide membranes are knovn. For examplet DiCosimo et al. teach in USP 4,571,443 a Bi-con~aining, mixed metal oxide catalyst membrane of the empirical formula Bi La Mb x ~here L is at least one of Y, V, Nb, Ta, U, Mo, Pb, La, Nd, Sm, Er, Yb, Dy and Gd;
M is at least one o Ca, Ba and Sr;
a is 0-1; and b is O-O.:L
...~, . ~ . : ,, .. , .. : .... .. . -. :
W O 92t0586~ P~-r/~lS9l/07391 ~ o ~ 3 ~ -2-The~e c~t~ly.ct meml-r~ne~ ~re use~ to extract oxygen from an oxy~en-containing gas, such as alr, and deliver il ~o substrales, such as propylene, which react with the oxygen in the presence of the catalys~
5 membrane to form dimers and other products. However the best oxygen flux reported for these catalyst membranes was ?7 milliamperes per square centimeter (27 mA/cm2) at 600C.
Yoshisato et al. teach in USP 4,330,633 a solid electrolyte 10 having electron conductivity and oxide ion conductivity, the electrolyte consisting substantially of (a) an oxide of cobalt, (b) an oxide of at least one metal selected from s;rontium and lanthanum, and (c) an oxide of at least one metal selected from bismuth and cerium.
20 The electrolyte is taught as being useful for separating oxygen from a gaseous atmosphere having a high oxygen partial pressure into a gaseous atmosphere having a low oxygen partial pressure. For a sintered body consisting of 25 mol ~ of cobalt oxide, 32.5 mol % of lan~hanum oxide, and 42.5 mol ~ of bismuth oxide, the oxygen flux at 800C was 51 mA/cm2.
Takahashi et al. teach in their article entitled "Oxide Ion Conductors Based on Bismuthsesquioxide", Materials Research Bulletin, Vol 13, pp 1447-1453 (1978) oxide ion conducti~e solid electrolytes based on bismuthsesquioxide. While these materials have high oxide ion 30 conductivity, they are electronic insulators and thus require an external circuit eo return electrons to the oxide source.
While these references and others teach various Bi-containing mixed metal oxides, none teach such compositions as having commercially 35 significant oxide ion flux (greater ehan about lO0 mA/cm2), particularly at relatively low temperatures (less than about 900C).
. , ....... .. . ., ~, . .. . . .
:,,. :,: , . ., . , . .:
,, - . ,:, :: , , . :.. " . . :, : , . , W O 92/05862 PCT/US91/0~391 _3 ~3332 significant oxide ion flux (greater than about 100 mA/cm2), particularly at relatively lov temperatures (less than about 900C)0 SUMMARY OF TH~ INVENTION
According to this invention, oxygen is separated from a first oxygen-containing gas by ~A) Feeding the first oxygen containing gas into a first zone ; of a gas separation apparatus, the apparatus comprisingfirst and second zones separated by a mixed ~etal oxide membrane, the membrane having a first surface open to the :: first zone, a second surface open to the second zone, ~nd ~n empirical formula of:
Bi AX My M Z n where ?O
A is at least one of La, U, Th, Ce, Pr~ Nd, Pm, : Sm, Eu, Gd, Tb, Dy, ~o, Er, Tm, Yb, Lu, -f, Mg, Ca, Sr and Ba;
M is at least one of Sc, Ti, Cr, Mn, Fe, ~i, Cu and Zn;
M is at least one of Co, Rh, Pd, Pt and Ru;
x and y are individually a number bet~een zbout O.Gl and about 10;
- z is a number of 0 to about 0.2; and ` 35 n is a number tha~ satisfies the valence rlequirements of the other elements present; ?
. ' , ' ~'0 92/05862 PCT/~IS9~/073~1 æ~ 3'~ _4~
the first ~one having an equilibrium oxygen partial pressure greater than that of the second zone;
(s) Contacting the first oxygen-containing g25 in the first zone of the separation apparatus with the iirst surface of the membrane such that:
~i) oxygen is extracted from the first oxygen-containing gas at the first surface of the membrane; and (ii) the extracted oxygen is transported across the membrane, in the form of oxide ions, to the second surface of the membrane; and (C) Recovering the extracted oxygen from the second surface of the membrane such that a second oxygen-containing gas is produced in the second zone of the separation apparatus.
20 In one embodiment of this invention, the extracted oxygen is removed from the second surface of the membrane by reaction with an oxygen-consuming substance, such as a hydrocarbon gas, which is present in the second zone of the separation apparatus and is in contact uith the second surface of the membrane. In another embodiment of this ~nvention, the extracted 25 oxygen is removed from the second surface of the membrane as molecular oxygen, 2 The mixed metal oxide membranes used in the process of this invention exhibit unusually high oxygen fluxes at relatively lo~
30 temperatures. These membranes are prepared by conventional techniques, and exhibit other d~esirable properties under process conditions, such as good chemical and thermal stability.
.. . . .. . . . . .. . .
': ' . . ' ' . ' :, ' , - . . ' ' ` ': . ' ':'-: ,':: ,, ,:; ' . ~ " ': .: : . , : ~ , .': ' . .: ' ;.::, ., ' :
'- .' ', ... . '',,,', ' ',',~, . .' .. ~, ' ., 1 ,; . , :'.'': :, ,;. ,.,:j .. '. ,,. : :. :. ~ :,',''.. , ,:,:,:, ,,' ,:, ,. ' ::' . ' :: ,::: . ~:'-- , ,., : :
WO 9~/05862 PC'r/US91/07391 :
~~ 2~33332 BRIEF DESCRIPTION OF T~E DRAWINGS
Figure l is a schematic diagram illustrating one embodiment of 5 the separation apparatus in which the mixed metal oxide ~e~brane is used in the form of a disc.
Figure 2 is a bottom plan vie1- taken along line 2-2 of zone 2 of the separation apparatus illustrated in Figure 1.
Figure 3 is a schematic diagram illustrating one embodiment of the separation apparatus in which the mixed metal oxide ~embrane is used in the form of a hollow tube.
Figures 4, 5 and 6 are plots describing the relationship, - expressed as the natural log of the flux in mA/cm2 vs. the inverse of temperature in degrees Kelvin, between temperature and oxygen flux of various Bi-containing mixed metal oxide membranes.
DETAILED DESCRIPTION OF TE~E INVENTION
l. Process Starting ~aterials The process of this invention is suitable for separating or cx~r~ctjllg oxy~n ~rom essentlally any oxygen-cont~ining gas. As h~re used, the term "oxygen-containing gas" includes both gas ~ixtures where moleculaL- oxygcn is admixed ~ith one or more other gases, and reducible oxygen-containing compounds ~here oxygen is chemically bonded to another 30 element. Air i~ an example of the former, while ~ater (steam), carbon dioxide, carbon monoxide, sulfur dioxide, sulfur trioxide, and the vatious nitrogen oxides (le.g. nitrous oxide, nitric oxide, nitrogen dioxide, etc.) are examples of the latter. The oxygen-containing gas can contain components that are not ~aseous at normal roo~ ~emperature and pressure 35 (e.g. water) but iare gaseous under more severe conditions (e.g. steam), and the oxygen-comtaining gas mixture can comprise more than one source of - .
, .:.,. . , -- ., ., -.. .". . ~ .
.,:
~ .-~ ... . . . .
.. .. .
W O 9~0~62 PCT/V~1/07391 2 ~ ~ 3 3 3 2 -6-oxide ion, e.g. the gas can comprise molecular oxygen and one o~ more reducible oxygen-containing compounds such as carbon dioxide, steam, etc.
The amount of oxygen in the first oxygen-contai~ing gas is not 5 critical to the practice of this invention as such, and it can vary as desired. For those applications where the extracted oxygen is to be reacted with an oxygen-consuming substance, such as a hydrocarbon fuel, typically the oxygen-containin~ gas conl;ains at least about 0.1 mole percent (mol ~), preferably at least about 5 mol ~, of ~olecular oxygen.
10 In this application, air is a particularly preferred oxygen-containing gas. If the source of oxygen in these applications is not molecular oxygen but rather an oxygen-containlng compound, such as carbon dioxide or steam, then the amount of that source in the oxygen-containing gas will be a function o~ the desired efficiency of the application. Horeover, the 15 relative ease by vhich the oxygen-containing compound can be reduced, i.e.
prompted to release one or more oxide ions, ~ill influence the choice of oxygen-containing compound to use. In this regard, less energy is required to remove an oxide ion from carbon dioxide than fro~ carbon monoxide and all other factors (e.g. cost, availability, equipment 20 requiremen~s, etc.) being equal, the former would be preferred over the latter.
In those applications uhere the purpose of separating the oxygen from the oxygen-containing gas is to decrease the amount or eliminate 25 completely the oxygen component, such as removing various nitrogen oxldes from a combustion gas, the amount of the oxygen component in the ~irst oxygen-containing gas will be a function of the source of the oxygen component. Depending upon such factors as convenience, economy and the e, the gas may be used as obtained ~rom the source or it may be first 30 diluted or concentrated.
. .
The mix metal oxide membrane used in the process of this invention is at least a four element composition, i.e. a composition containing bismu~h, at least one component A, at least one component M and 35 oxygen all in designated, proportional amounts~ Preferably, x is a number between about 0.2 and about 5, and y is a number betveen about 0.2 and ... . . . . . . . . . ......
; j.. .- ,. I
.. .. ... ... . ~ .. ,.. ; ~ ...... ,, , ~.
. . .,. , : : . -- . . :: ., , . ,: - :
W O 92/05862 PCT/US9~/0739~
` 20~3332 about 7. Especially preferred are membranes where x is bet~een about 0.5 and 2, y is betYeen about 0.5 and 3, and z is a number grealer than 0, preferably greater than about 0.05.
Certain of the components can be combinations of t~o or more elements, e.g. A can be a combination of strontium and calcium. In such instances, the subscript value (e.g. x, y, etc.) represents the sum of the elements (e.g. for A, the sum of strontium and calcium is equal to a number which is between about 0.01 and about 10).
Preferred membranes are membranes where A is at least one of Sr, La, Ca, Y, Ba, Ce, U, and Gd, N is at least one of Fe, Cu, Cr and Ni, and M' is at least one of Co, Rh, Pd and Ru. Particularly preferred membranes are where A is at least one of Sr, La, Ca and Ba, M is at least one of Fe, 15 Ni and Cr, and ~' is at least one of Co, Ru and Pd.
The exact structure or element arrangement of ~he membranes are not known but the individual elements are present in the form of a mixed oxide which commonly comprises a perovskite structure or a tetragonally 20 distorted perovskite structure or some combination of both. ~owever, the compositions of the membranes are known not to be a mere physical mixture of the components but rather uni~ue solid phases where the individual components are chemically bonded to one another. Not all membranes separate oxygen equally well from all oxygen-containing gases, but the 25 membranes of this invention do exhibit a selectivity for oxygen over the other elements of the gas.
The membranes used in this invention can be used either alone or with a structural support. If a support is used, it can comprise 30 essentially any material that is inert, porous to oxy~en, and retains its physical integrity under the conditions at ~hich the invention is practiced. Representative examples include yttria-stabilized alumina and zirconia, silicon carbide, porous carbon and various polymeric materials.
Particularly preferred supports are those comprised of the same materials 35 from ~hich the membrane itsel~ is made but constituted as a porous solid relative to the dense membrane. The membrane can be applied to the . .. .
:. . : ~ ;. ,. : ~ , ~
U'O 92/OS86~ PCT/~S91/07391 2~s333æ
support in any conventional manner, and it is provided in 2 quantity sufficient to effect separation of oxygen from the oxygen-con~aining gas (typically as a relatively uniform, thin film over the suppor~).
The shape of the membrane (or the support if the Dembrane is used in combination uith a support) is not critical to the practice of this invention, and it can take any shape amenable to the efficient operation of the separation apparatus. Typically, the shape is in the form of a disc or a hollow tube. The dimensions of the me~brane can vary lO to convenience with the understandtng that the ~hickness of the membrane is typically kept to che minimum required for effective separation, structural integrity, and substantial gas-imperviousness to the components of the oxygen-containing gas mixture other than oxygen. "Gas-imperviousness" as here used means substantially gas-tight in that the 15 membrane does not pPrmit a substantial amount of the first oxyge~-containing gas (other than the oxygen component in the forr of an oxide ion) to pass through the membrane as a gas. If an oxygen-consuming gas is used as a substrate in the second zone of the separation apparatus, the membrane should also be gas-impervious to its components as Yell as to the 20 second oxygen-containing gàs formed from the reaction of the oxygen-consuming substrate uith the oxygen on the second surface of the membrane (other than oxygen itself, of course). In some embodiments of this invention, a minor degree of perviousness to gases are acceptable or ~` unavoidable, particularly when hydrogen gas is present.
The membrane can be prepared in any one of a nu~ber of different methods, the particular method employed being a matter of conYenience.
Typically, the membranes are prepared by mixing the desired components in `` the proper proportions to form a solution or slurry, drying the solution 30 or slurry with or ~ithout a reducing agent, calcining the remains of the dried solution or slurry, shaping the produc~ of the calcination, typically ~ith a binder, into the desired shape, and then sintering the shaped, calcined product to the finished membrane. The components -`~ employed can be the oxides, halides, nitrates, ace~ates or other salts of 35 Bi, A, M and H',and particularly preferred is the use of their soluble salts. After the starting ingredients have been combined to form a :`
:`
.
- . -- .. .. . . . . .
: ~- ' ', ' ` : ' ` :, ' , ,, .' .' : ' ' .' :: ' ' : ' ` . ~ : .
~vo 92/0~862 PCT/US91/07391 9 `~9~3~2 solution or slurry (with or without the aid of a dispersant, such as citric acid)t it is dried and the recovered solid is then heated in the presence of a nonreducing gas, such as air, nitrogen, nitric oxide, etc., at a temperature between about 400 and about 1000C. After the dried - 5 slurry has been calcined, the resulting product is crushed, mixed with a binder (e.g. polyethylene glycol, glycerol, polyvinyl alcohol, starch, etc.), shaped, and then sintered in a nonreducing gas at a temperature between about 700 and about 1100C. The calcination continues until essentially all of the physically bound Yater has been re~oved, and the lO sintering continues until the shaped bocly nears its theoretical density.
Alternative methods of membrane preparation include vapor deposition, flame spraying, plasma spraying, coprecipitation, oxide or carbonate sintering and other techniques known to those skilled in the art.
If the membrane is used in combination with a support, the calcined, crushed solids either uith or without a binder, are applied to the support in any convenient manner and then subjected to sintering.
2. Process Apparatus ``
The separation apparatus used in the process of this invention comprises a first and second zone separated by the ~i-con~aining mixed metal oxide membrane of this invention. The membrane forms a 25 substantially gas impervious barrier betveen the two zones of the separation apparatus, although the configuration of the barrier can vary ; to convenience. Typically, the apparatus is constructed in such a manner that each zone can be heated, either as a single unit or independent of - one another. Zone 1 is equipped uith a port ehrough which the oxygen-30 containing gas can be fed in such a manner that it eventually is in contact uith a surface of the membrane that is not in contact with zone 2.
Zone 2 is equipped with means by which the oxygen separated from the oxygen-containin gas in zone 1 can be collected for recovery (eypically by drawing a full or partial vacuum on zone 2) or can be put to immediate 35 use (typically by reacting with an oxygen-consuming substance). If the oxygen that emerges onto the second surface of the membrane is to be ;.
~ , -~ '' .' ". . : ' W O 9~/0~862 PCT/US91tO7391 2~93332 -10- ! :
collected, zone 2 can simply be an oxygen impervious chamber from which oxygen recovered from the second surface can be removed con~eniently and efficiently. If the oxygen is to be immediately consumed by a substrate, then zone 2 can be configured and equipped in a manner that both maximizes 5 the contact betYeen the substrate and the oxygen present on the second surface of the membrane, and at the same time minimizes the contact between the second oxygen-con~alning co~npound and the second surface of the membrane. The use of a sweep gas, i.e. any substantially inert, relatively abundant and inexpensive gas such as nitrogen, argon, helium, lO etc., can be used to accomplish this end. As here used in reference to the second oxygen-containing gas, "oxygen-containing gas" has the same meaning as when used in reference to the first oxygen-containing gas, i.e.
molecular oxygen alone, molecular oxygen in combination ~ith other gases, and reducible oxygen-containing compounds ~here oxygen is chemically 15 bonded to another element.
Recovering molecular oxygen from the second surface of the membrane and removing it from the second zone by dra~ing a vacuum on the second zone is an example of the second oxygen-coneaining gas consisting 20 of simply molecular oxygen. Using a sweep gas, e.g. heliu~, to recover molecular oxygen from the second surface of the membrane and removing it from the second zone is an example of the second oxygen-containing gas consis~ing of a gaseous mixture. Uater, in the form of steam, is an example of the second oxygen-containing gas comprising a reducible oxygen-25 containing compound ~here oxygen is chemically bondPd to another element, here the uater present in the second zone as a product of a reaction betueen hydrogen, an oxygen-consuming substrate, and the oxygen present on the second surface of the membrane.
~' Figure l of the drawings illustrates one embodiment of the ;~ separation apparatus used in the process o~ this invention. Zones l and 2 ` are gas-impervious tubes, 3 and 4 respectively. Tube 3 has open ends 5 and 6 ~ith open end 6 placed in close approximation to first surface 7 of membrane 8 (here illustrated, in lateral cross-section, as a disc slightly 35 larger in diameter than that of tubes 3 and 4). Rim 9 of tube 4 is joined to the second surface lO of membrane 8 by a seal ll ~hich renders the , , , , -, ., .. , .- . , . ,, : .
, : , :.. . . .
. - : .. . . ::: ,: . :
W O 92/0~62 PCT/US91/07391 93~3~
junction of ri~ 9 and second surface 10 gas-impervious. ~ second, gas-impervious tube 12 of smaller diameter ~han tube 4 is coaxially fitted ~ithin tube 4 such that open end 13 of tube 12 is in close apprOXimatiQn to the second sur~ace of membrane 8. Seal 11 ls formed betveen second 5 surface 10 of membrane 8 and the rim ~hich forms open end 9 of tube 4 such that the area of second surface 10 wlthin the rlm of open end 9 ls su~stantlally unobstructed wlth sealant, as deplcted in Figure 2. Tube 12 is fitted ~ithin tube 4 to form a gas-impervious seal at juncture 14. The entire apparatus of this Figure 1 can be enclosed in a gas-impervious 10 housing (not sho~n), and is typically equipped with heating elements (also not shoun) that can independently heat ~ones 1 and 2.
Figure 2 is a bottom plan vieu taken along line 2-2 of zone 2 of the separation apparatus lllustrated in Figure 1. The i.~er~ost, clrcular 15 band ls a cross-section of tube 12 ~hich, as described above, is not in contact with second surface 10 of membrane 8. The next concentric circular band out from the innermost circle is a cross-section of seal 11, - followed by a cross-section of tube 4, follw~ed by another cross-section of seal 11. The outermost circular band is the outer edge of second ~0 surface 10. As this figure illustrates, the surface area of second -`~ surface 10 within the circular band formed by the cross-section of seal 11 is unobstructed to the flow of gaseous hydrocarbon exiting tube 12 by open : end 13.
.
; 25 In one embodiment of the operation of the separation apparatus depicted in Figure 1, an oxygen-containing gas9 e.g. air, enters open end 5 of tube 3, passes through the length of tube 3, and is discharged through open end 6 of tube 3 such that it makes contact uith first surface ~ 7 of membrane 8. Membrane 8 is a bismuth-containing mixed metal oxide of `~ 30 this invention as previously described ~ith a selectivity for oxygen. At `~ or near first surface 7, oxygen is extracted from the o~ygen-containing ` gas as an oxide ion, and transported across membrane 8 to second surface 10 ~here it is reacted ~ith an oxygen-consuming substance, e.g. a gaseous hydrocarbon. The oxygen-consuming gas is introduced to second surface 10 35 through tube 12 in such a manner that it also serves as a s~eep gas, e.g.
nitrogen, argon, helium, etc. The products formed by the reaction of the ~ . . . . . .. ...
~0 9~t05~2 PCT/US~1/0739l 2~3332 -12-oxide ion and hydrocarbon are continuously removed from or near second surface lO and ~he annular space within tube 4 that is defined by the outer surface of tube 12 and the ~nner surface of tube 4, by Yay of tube 15. The air is brought in contact with first surface 7 of membrane ~ in 5 such a manner that the equilibrium oxygen partial pressure of the gas is greater than the equilibrium oxygen partial pressure that exists at or near the second surface 10 within the area defined by seal 11. This difference in equilibrium oxygen partial pressure betveen zones 1 and 2 can be maintained by any one of a number of different means, but it is ~0 typically maintained at a steady state by a constant introduc~ion of the oxygen-containing gas to first surface 7 and the constant consumption of the oxide ion at or near second surface 10 by the oxygen-consuming gas to form a second oxygen-containing gas that is continuously removed from zone 2. "Equilibrium oxygen partial pressure" here means the oxygen 15 pressure calculated at stated conditions when the mixture of components is at thermodynamic equilibrium.
In another embodiment of the operation of the separation apparatus depicted in Figure 1 modified by the deletion of tube 12 and the 20 conversion of tube 4 (zone Z) into a closed, gas-impervious housing with . tube 15 as the only means of exit (other than membrane 8 itself), theoxide ion is recovered from surface 10 in the form of molecular oxygen. A
slight vacuum is drawn on zone 2 (by means not shown), and the oxygen is recovered through tube 15.
~. 25 : Figure 3 is a schematic diagram of another embodiment of the separation apparatus. ~ere, the Bi-containing mixed metal oxide membrane is tube 20 uhich exeends through housing 21 to form chamber 227 a closed space except for its open communication with eube 23. In one mode of : 30 opera~ion of this particular separation apparatus, an oxygen-containing ; gas is fed through the interior of tube 20 (zone 1) under conditions which : oxygen is extracted from the oxygen-containing gas on the inner (first) :~ surface of tube 20, transported across the thickness of eube 20 in the form of an oxide ion to the outer (second) surface of tube Z0, uhere it is 35 recovered in the form of molecular oxygen and removed from chamber 22 (zcne 2) by way of tube 23. In another mode of operation of this same -.: : : : . :. .: .
-, - : . ~: :, :::, . :: : . : -: :.. . . :
- . . . : . : : : : ,, , , , ::
W O 92/~58S2 PCT/US9l/07391 -13- ~93332 apparatus, the oxygen-containing gas is fed into chamber 22 (zone 1) by uay of tube 23, oxygen is extracted at the outer ~first) surface of tube 20, transported aCrOSS the thickness of ~ube 20, recovered as molecular oxygen from the inner (second) surface of tube 20, and then removed from 5 the interior of tube 20 (zone 2). Under either mode of operation, the equilibrium oxygen partial pressure zone 1 is greater than the equilibrium oxygen partial pressure of zone 2. Each zone can be heated to the desired temperature by means not shown and but for the membrane itself (tube 20), the remaining pieces of the separation apparatus and the junctures at 10 uhich they are fitted to one another are substantially gas impervious.
If an oxygen-consuming substrate is used, it is typically a reactant gas. Exemplary reaction gases include hydrogen, carbon monoxide ; and a hydrocarbon such as ethane, ethylene, propane, propylene, butane, 15 butenes, light naphtha, mixtures of parafins, or mixtures of parafins and olefins, mixtures of olefins, or mixtures of parafins, olefins and aromatics. The reacting gas can also contain inerts or diluents, such as nitrogen or steam, or a recycled product stream.
, .
` 20 As noted earlier, oxygen can also be collected and removed from the second surface of the membrane in the absence of an oxygen-consuming substrate, ~ut the effectiveness of this separation ~ill depend upon the oxygen partial pressure difference between the oxygen-containing gas and that of zone 2. The relative pressures of both zone 1 and zone 2 can be 25 subatmospheric, atmospheric or superatmospheric, as long as the oxygen partial pressure of zone 1 is greater than the oxygen partial pressure of zone 2.
:
The process of this invention can be conducted at any 30 temperature at uhich the oxygen-containing gas remains in the gaseous ` state when in contact with the first surface of the membrane. However, since the oxide ion flux of the membrane will vary with ~emperature and since the flux will usually increase with temperature, preferably the process is conducted at an elevated temperature. The exact temperatures 35 at which zones 1 and 2 of the separation apparatus are maintained will vary with the nature of the oxygen-containing gas, the oxygen-consuming - . , ~
. . ' ~
~VO 9'/0~86~ PCr/VS9l/07391 20~3332 -14- " ~
substrate, if any, and the composition of the membrane but uhere the oxygen-containing gas is air and the oxygen-consuming substrate is a reactant gas, particularly a hydrocarbon, a minimum temperature of about 300C, preerably about 400C, is employed in each zone. The maximum 5 temperature of zones 1 and 2 will also vary with the nature of the oxygen-containing gas and oxygen-consuming substrate but where the former is air and the latter is a hydrocarbon, the maximum temperature is typically not greater than about 900C, and preferably not greater than about 800~C, for each zone.
The following examples are illustrative of certain specific embodiments of this invention. Unless otherwise indicated, all parts and percentages are by mol %.
SPECIFIC EMBODIMENTS r .
, _ Example l Ferric nitrate (50.0g), strontium acetate (25.6g), bismuth nitrate (60.03g) and citric acid (35.65g) were slurried in 500 ml of vater and heated to dissolution. The solution was first reduced to near dryness ` under vacuum on a rotary evaporator, and then to dryness in a vacuum oven.
The solids were collected and calcined at 890C for two hours in air. The 25 calcined solid was then crushed to fine powder, admixed with 5 wt %
Carbouax-20M (a polyethylene glycol) pressed into 34.9 mm diameter discs - (1 mm thick), and sintered in air at 970C for 17.5 hours. The empirical formula of the discs was 8il Srl Fel x vith a measured density of 5.66 g/clll3.
One of the discs (#8 in Figure 1) was then fitted and sealed into a separation apparatus as depicted in Figure 1. Glass powder from Corning (No. 816i with a softening point of 6Q0C) ~as mixed with isobutanol to form a thick paste vhich was then placed on the rim (#9) and 35 outer surface of a mullite tube (~4). The second surface ($10) of the disc vas then joined to the mullite tube to form a gas-impervious seal :,, .: . .: . ::, , . , :: .. .... :. . .
t ' , ' . " ' , , ' ::
U O 9~/0~862 P~T/US91/07391 - 2~33332 (~11). Another mullite tube (#3) was then positioned such that it was in close proximity to the first surface (~7) of the disc, and the whole apparatus was ~hen placed in an electric furnace ~not shovn in Figure 1) and heated to 750C over the course of 7-1/2 hours. After holding at thls 5 temperature for 1/2 hour, the temperature was lo~ered at a constant rate to 550C over 6-1/2 hours to obtain a gas tight seal. Air ~as then passed - through mullite tube 3 to the first surface 7 of disc 8, and nitrogen was passed through mullite tube 12 to second surface 10 of disc 8. The temperature was then adjusted to the desired reaction temperature, and the 10 nitrogen was replaced by hydro~en.
The oxygen flux was measured after the separation apparatus reached steady state operation at any given temperature, usually after a minimum of one hour. The gaseous reaction product was cooled to -78C to 15 trap water, which was collected and weighed. The dry vent gas composition was analyzed by gas chromatography. The oxy~en flux was 269 mA/cm2 at 70~C after 5 hours of operation and when the temperature ~as lowered to - 457C, it was 56 mA/cm2 after 11 hours of total operation.
Figure 4 is a plot of these and other data points expressed as the natural log of the flux in mA/cm2 (the ordinate) vs. the inverse of ` temperature in degrees Kelvin (the abscissa). The data points are expressed in these units because the energy of activation can then be obtained from the slope of the resulting line, which in turn permits the 25 determination of the oxygen flux of the membrane at any temperature. As it clearly demonstrates, the flux of the membrane increases exponentially ~ith an increase in temperature. By uay of illustration, followin~ is the calculation for the data point at 457C, i.e. 56 mA/cm2.
mA/cm2 = mA
nr2 ~here r = 0.775 cm, the radius of the disc exposed to ~2~ and mA = cc 2 S, where cc 2 = ~ (F H E) .. - . .. . .
, ~,, - . : .
.
. .. . .
W O 92/058~2 P~r/US9l/07391 ,. ~, 20933~2 where I = 0.0434g of H20 collected over the course of the run, J = 1.017 hr, the duration of the run R = 11.2, a factor relating g of ~0 collected in 1 hr to mols of 2 passed in 1 min.
S = 267, a factor relating current in mh to cc of 2 passed per min.
F = 63.5 cc/min H2 gas flo~ ~
H = 0.005 mol Z N2 in H2 r E = 0.245, a calibration ratio relating the ,~ sensitivity of the gas chromatograph to N2 and 2 The H2 gas flow uas measured beore the start of the run (i.e. before air ~as introduced to zone 1). The product gas flow was measured during the 25 run~ The product gas was analyzed by gas chromatography to determine mol X nitrogen.
~ ExamDle 2 ;" :
`~ 30 ~ --~ A seccnd disc of the membrane prepared in Example 1 ~as tested in the appara~us and ~ith the procedure described in Exa~ple 1 and at 705C vith the reactant gas comprising a 90/5/5 composition of carbon monoxide/carbon dioxide/argon, an oxygen flux of 195 mA/cm2 was obtained 35 after 5 hours of operation. At 465C and after 11 hours of operation, the oxygen flux was equal to 84 mA/cm2. The density of the disc vas 5.70g/cm3. Figure 5 is a plot of this and other data points measured and calculated as described for Figure 4 of Example 1, except the calculation .
. : :: ., , : :: : . : : .. ,: . ~: ~
W O 92~0~862 PCT/VS91/073gl ~ ' ,.
-17- 2 n ~ 3 3 3 2 of cc 2 required the use of a different equation. The folloYing calculation of 84 mA/cm2 is illustrative:
cc 2 = [(B K)+(~ L)l - l(F-M)+(F-N)I - (B-D-E)]
where B = 62.9 cc/min Product Gas Flow K = 5.68 mol X C2 in Product Gas ; L = 88.64 mol % C0 in Product Gas F = 62.0 cc~min Fuel Gas Flow ~- 15 M = 4.97 mol Z C02 in Fùel Gas N = 88.76 mol X C0 in Fuel Gas D = 0.89 mol % N2 in Product Gas E = 0.245, a calibration ratio relating the sensitivity of the gas chromatograph to N2 and 2 25 Example 3 :`
A membrane of the composition Bil Sr1 Ca1 Fe2 n vas prepared from a slurry of nitrates of bismuth (60.0g), calcium (29.2'g) and iron 30 (99.94g), and strontium ace~ate (25.45g) by the procedure described in Example 1. The solid was coll-ected and then calcined at 820C for 16 hours in air. The solid was crushed, pressed into 34.9 mm diameter discs (using 5 wt Z Carbowax-20M as a bi~der) witb a thickness of 1 mm and sintered in air at 1010C for 15 hours. The density of the disc was 35 4.83g/cm3.
The disc was charged to the furnace and sealed vith glass as described in Examplle 1, and the temperature was increased sloYly to 650C.
At 650C, the oxide ion flux was measured at 40 mA/cm2 after 5.5 hours of 40 operation by checking for water formation.
:, , , ~ , :
. -~
.:-~ . : . ., .; . . - : --W O 92/0~86' PCT/US91/07391 2~'~33~% -18-E.Ya~ple 4 A mixture of bismuth nltrate (50g), yttrium nltrate (31.6g) and 5 cobalt nitrate (5.14g) was slurried in 500 ml of water with citric acid and as in Example 1, the water was removed under vacuum and then oven dried to leave a solid. The solids were collected and calcined in air at 850C for 9 hours. The resulting solid ~las crushed to a fine powder, pressed into 34.9 mm diameter discs, mixed vith 5 wt Z Carbovax-20M, and 10 sintered in air for 12 hours at 970C. The disc had an empirical formula of Bil Yo.8 C00.2 n with a measured density of 7.26g/c~3.
The disc ~as then sealed into place in the furnace as described in Example 1, and a 90/5/5 carbon monoxide/carbon dioxide/argon mixture 15 was used as the reactant gas. After 2 hours operation at 550C, the flux ` ~as measured at 63 mA/cm2. The temperature ~as then raised to 700C and ; after 8 hours of operation, the flux was 558 mA/cm2. The temperature was then lowered, this time to 450C, and the reactant gas s~itched to ; hydrogen. After 80 hours of total elapsed time on stream (including time 20 on stream with C02/CO!Ar mixture), the flux was 17 mA/cm2. Figure 6 is a plot of the tuo C0/C02/Ar daca points, and another, measured and calculated as described for Figure 5 of Example 2.
ExamDle 5 Bismuth nitrate (76.64g), ferric nitrate (95.74g), lan~hanum acetate (27.10g) and strontium acetate (65.0g) were slurried with citric acid in 500 ml of water. The ~ater ~as removed under vacuu~, the solids 30 dried in an oven, collected and then calcined at 900C for 24 hours; the resulting solid crushed to a fine powder, mixed with 5 vt Z Carbowax-20M, pressed into 34.9 mM discs, and sintered in air at 1200C for 5 hours.
The disc which had an empirical formula of Bi1 Fe1 5 Lao 5 Sr2 n and a density of 6.21 g/CM3, was sealed into the reactor as in Example 1, and 35 tested at 550-6S0C using the 90/5/5 carbon monoxide/carbon dioxide/argon mixture as a reactant gas. The flux was 12 mA/cm2 at 550C after 2 hours W O 92/0586~ 2 ~ 3 2 PCT/US91/07391 --19-- ;`
of operation, while the highest flux was 39 mA/cm2 at 650~C after 3 hours of operation.
Although the invention has been described in considerable detail : 5 through the preceding Examples, these Examples are for the purpose of illustration only and it is understood that variations and modifications : can be made by one skilled in the art w:ithout departing from the spirit and scope of the invention.
. . .
PROCESS FOR SEPARATIN~a OXYGEN FROM AN
OXYGEN-CONTAINING GAS BY USING A
BI-CONTAINING HIXED METAL OXIDE MEMBRA~I~
~A~ UN~ Ult Tll~ lNV~NrlON
1. Field of the Invention This invention relates.to a process for separatlng oxygen from an oxygen-containing gas, such as air. In one aspect, ~he invention relates to a process in which the oxygen is separated from the oxygen-containing gas by me.~ns.of a Bi-containing mixed metal oxide membrane. In 10 another aspect, the invention relates to a process for providing an oxygen-consuming substance with oxygen extracred from an oxygen-containing gas by means of a Bi-containing mixed metal oxide membrane.
2. Description of the Prior Art5 Bi-containing mixed metal oxide membranes are knovn. For examplet DiCosimo et al. teach in USP 4,571,443 a Bi-con~aining, mixed metal oxide catalyst membrane of the empirical formula Bi La Mb x ~here L is at least one of Y, V, Nb, Ta, U, Mo, Pb, La, Nd, Sm, Er, Yb, Dy and Gd;
M is at least one o Ca, Ba and Sr;
a is 0-1; and b is O-O.:L
...~, . ~ . : ,, .. , .. : .... .. . -. :
W O 92t0586~ P~-r/~lS9l/07391 ~ o ~ 3 ~ -2-The~e c~t~ly.ct meml-r~ne~ ~re use~ to extract oxygen from an oxy~en-containing gas, such as alr, and deliver il ~o substrales, such as propylene, which react with the oxygen in the presence of the catalys~
5 membrane to form dimers and other products. However the best oxygen flux reported for these catalyst membranes was ?7 milliamperes per square centimeter (27 mA/cm2) at 600C.
Yoshisato et al. teach in USP 4,330,633 a solid electrolyte 10 having electron conductivity and oxide ion conductivity, the electrolyte consisting substantially of (a) an oxide of cobalt, (b) an oxide of at least one metal selected from s;rontium and lanthanum, and (c) an oxide of at least one metal selected from bismuth and cerium.
20 The electrolyte is taught as being useful for separating oxygen from a gaseous atmosphere having a high oxygen partial pressure into a gaseous atmosphere having a low oxygen partial pressure. For a sintered body consisting of 25 mol ~ of cobalt oxide, 32.5 mol % of lan~hanum oxide, and 42.5 mol ~ of bismuth oxide, the oxygen flux at 800C was 51 mA/cm2.
Takahashi et al. teach in their article entitled "Oxide Ion Conductors Based on Bismuthsesquioxide", Materials Research Bulletin, Vol 13, pp 1447-1453 (1978) oxide ion conducti~e solid electrolytes based on bismuthsesquioxide. While these materials have high oxide ion 30 conductivity, they are electronic insulators and thus require an external circuit eo return electrons to the oxide source.
While these references and others teach various Bi-containing mixed metal oxides, none teach such compositions as having commercially 35 significant oxide ion flux (greater ehan about lO0 mA/cm2), particularly at relatively low temperatures (less than about 900C).
. , ....... .. . ., ~, . .. . . .
:,,. :,: , . ., . , . .:
,, - . ,:, :: , , . :.. " . . :, : , . , W O 92/05862 PCT/US91/0~391 _3 ~3332 significant oxide ion flux (greater than about 100 mA/cm2), particularly at relatively lov temperatures (less than about 900C)0 SUMMARY OF TH~ INVENTION
According to this invention, oxygen is separated from a first oxygen-containing gas by ~A) Feeding the first oxygen containing gas into a first zone ; of a gas separation apparatus, the apparatus comprisingfirst and second zones separated by a mixed ~etal oxide membrane, the membrane having a first surface open to the :: first zone, a second surface open to the second zone, ~nd ~n empirical formula of:
Bi AX My M Z n where ?O
A is at least one of La, U, Th, Ce, Pr~ Nd, Pm, : Sm, Eu, Gd, Tb, Dy, ~o, Er, Tm, Yb, Lu, -f, Mg, Ca, Sr and Ba;
M is at least one of Sc, Ti, Cr, Mn, Fe, ~i, Cu and Zn;
M is at least one of Co, Rh, Pd, Pt and Ru;
x and y are individually a number bet~een zbout O.Gl and about 10;
- z is a number of 0 to about 0.2; and ` 35 n is a number tha~ satisfies the valence rlequirements of the other elements present; ?
. ' , ' ~'0 92/05862 PCT/~IS9~/073~1 æ~ 3'~ _4~
the first ~one having an equilibrium oxygen partial pressure greater than that of the second zone;
(s) Contacting the first oxygen-containing g25 in the first zone of the separation apparatus with the iirst surface of the membrane such that:
~i) oxygen is extracted from the first oxygen-containing gas at the first surface of the membrane; and (ii) the extracted oxygen is transported across the membrane, in the form of oxide ions, to the second surface of the membrane; and (C) Recovering the extracted oxygen from the second surface of the membrane such that a second oxygen-containing gas is produced in the second zone of the separation apparatus.
20 In one embodiment of this invention, the extracted oxygen is removed from the second surface of the membrane by reaction with an oxygen-consuming substance, such as a hydrocarbon gas, which is present in the second zone of the separation apparatus and is in contact uith the second surface of the membrane. In another embodiment of this ~nvention, the extracted 25 oxygen is removed from the second surface of the membrane as molecular oxygen, 2 The mixed metal oxide membranes used in the process of this invention exhibit unusually high oxygen fluxes at relatively lo~
30 temperatures. These membranes are prepared by conventional techniques, and exhibit other d~esirable properties under process conditions, such as good chemical and thermal stability.
.. . . .. . . . . .. . .
': ' . . ' ' . ' :, ' , - . . ' ' ` ': . ' ':'-: ,':: ,, ,:; ' . ~ " ': .: : . , : ~ , .': ' . .: ' ;.::, ., ' :
'- .' ', ... . '',,,', ' ',',~, . .' .. ~, ' ., 1 ,; . , :'.'': :, ,;. ,.,:j .. '. ,,. : :. :. ~ :,',''.. , ,:,:,:, ,,' ,:, ,. ' ::' . ' :: ,::: . ~:'-- , ,., : :
WO 9~/05862 PC'r/US91/07391 :
~~ 2~33332 BRIEF DESCRIPTION OF T~E DRAWINGS
Figure l is a schematic diagram illustrating one embodiment of 5 the separation apparatus in which the mixed metal oxide ~e~brane is used in the form of a disc.
Figure 2 is a bottom plan vie1- taken along line 2-2 of zone 2 of the separation apparatus illustrated in Figure 1.
Figure 3 is a schematic diagram illustrating one embodiment of the separation apparatus in which the mixed metal oxide ~embrane is used in the form of a hollow tube.
Figures 4, 5 and 6 are plots describing the relationship, - expressed as the natural log of the flux in mA/cm2 vs. the inverse of temperature in degrees Kelvin, between temperature and oxygen flux of various Bi-containing mixed metal oxide membranes.
DETAILED DESCRIPTION OF TE~E INVENTION
l. Process Starting ~aterials The process of this invention is suitable for separating or cx~r~ctjllg oxy~n ~rom essentlally any oxygen-cont~ining gas. As h~re used, the term "oxygen-containing gas" includes both gas ~ixtures where moleculaL- oxygcn is admixed ~ith one or more other gases, and reducible oxygen-containing compounds ~here oxygen is chemically bonded to another 30 element. Air i~ an example of the former, while ~ater (steam), carbon dioxide, carbon monoxide, sulfur dioxide, sulfur trioxide, and the vatious nitrogen oxides (le.g. nitrous oxide, nitric oxide, nitrogen dioxide, etc.) are examples of the latter. The oxygen-containing gas can contain components that are not ~aseous at normal roo~ ~emperature and pressure 35 (e.g. water) but iare gaseous under more severe conditions (e.g. steam), and the oxygen-comtaining gas mixture can comprise more than one source of - .
, .:.,. . , -- ., ., -.. .". . ~ .
.,:
~ .-~ ... . . . .
.. .. .
W O 9~0~62 PCT/V~1/07391 2 ~ ~ 3 3 3 2 -6-oxide ion, e.g. the gas can comprise molecular oxygen and one o~ more reducible oxygen-containing compounds such as carbon dioxide, steam, etc.
The amount of oxygen in the first oxygen-contai~ing gas is not 5 critical to the practice of this invention as such, and it can vary as desired. For those applications where the extracted oxygen is to be reacted with an oxygen-consuming substance, such as a hydrocarbon fuel, typically the oxygen-containin~ gas conl;ains at least about 0.1 mole percent (mol ~), preferably at least about 5 mol ~, of ~olecular oxygen.
10 In this application, air is a particularly preferred oxygen-containing gas. If the source of oxygen in these applications is not molecular oxygen but rather an oxygen-containlng compound, such as carbon dioxide or steam, then the amount of that source in the oxygen-containing gas will be a function o~ the desired efficiency of the application. Horeover, the 15 relative ease by vhich the oxygen-containing compound can be reduced, i.e.
prompted to release one or more oxide ions, ~ill influence the choice of oxygen-containing compound to use. In this regard, less energy is required to remove an oxide ion from carbon dioxide than fro~ carbon monoxide and all other factors (e.g. cost, availability, equipment 20 requiremen~s, etc.) being equal, the former would be preferred over the latter.
In those applications uhere the purpose of separating the oxygen from the oxygen-containing gas is to decrease the amount or eliminate 25 completely the oxygen component, such as removing various nitrogen oxldes from a combustion gas, the amount of the oxygen component in the ~irst oxygen-containing gas will be a function of the source of the oxygen component. Depending upon such factors as convenience, economy and the e, the gas may be used as obtained ~rom the source or it may be first 30 diluted or concentrated.
. .
The mix metal oxide membrane used in the process of this invention is at least a four element composition, i.e. a composition containing bismu~h, at least one component A, at least one component M and 35 oxygen all in designated, proportional amounts~ Preferably, x is a number between about 0.2 and about 5, and y is a number betveen about 0.2 and ... . . . . . . . . . ......
; j.. .- ,. I
.. .. ... ... . ~ .. ,.. ; ~ ...... ,, , ~.
. . .,. , : : . -- . . :: ., , . ,: - :
W O 92/05862 PCT/US9~/0739~
` 20~3332 about 7. Especially preferred are membranes where x is bet~een about 0.5 and 2, y is betYeen about 0.5 and 3, and z is a number grealer than 0, preferably greater than about 0.05.
Certain of the components can be combinations of t~o or more elements, e.g. A can be a combination of strontium and calcium. In such instances, the subscript value (e.g. x, y, etc.) represents the sum of the elements (e.g. for A, the sum of strontium and calcium is equal to a number which is between about 0.01 and about 10).
Preferred membranes are membranes where A is at least one of Sr, La, Ca, Y, Ba, Ce, U, and Gd, N is at least one of Fe, Cu, Cr and Ni, and M' is at least one of Co, Rh, Pd and Ru. Particularly preferred membranes are where A is at least one of Sr, La, Ca and Ba, M is at least one of Fe, 15 Ni and Cr, and ~' is at least one of Co, Ru and Pd.
The exact structure or element arrangement of ~he membranes are not known but the individual elements are present in the form of a mixed oxide which commonly comprises a perovskite structure or a tetragonally 20 distorted perovskite structure or some combination of both. ~owever, the compositions of the membranes are known not to be a mere physical mixture of the components but rather uni~ue solid phases where the individual components are chemically bonded to one another. Not all membranes separate oxygen equally well from all oxygen-containing gases, but the 25 membranes of this invention do exhibit a selectivity for oxygen over the other elements of the gas.
The membranes used in this invention can be used either alone or with a structural support. If a support is used, it can comprise 30 essentially any material that is inert, porous to oxy~en, and retains its physical integrity under the conditions at ~hich the invention is practiced. Representative examples include yttria-stabilized alumina and zirconia, silicon carbide, porous carbon and various polymeric materials.
Particularly preferred supports are those comprised of the same materials 35 from ~hich the membrane itsel~ is made but constituted as a porous solid relative to the dense membrane. The membrane can be applied to the . .. .
:. . : ~ ;. ,. : ~ , ~
U'O 92/OS86~ PCT/~S91/07391 2~s333æ
support in any conventional manner, and it is provided in 2 quantity sufficient to effect separation of oxygen from the oxygen-con~aining gas (typically as a relatively uniform, thin film over the suppor~).
The shape of the membrane (or the support if the Dembrane is used in combination uith a support) is not critical to the practice of this invention, and it can take any shape amenable to the efficient operation of the separation apparatus. Typically, the shape is in the form of a disc or a hollow tube. The dimensions of the me~brane can vary lO to convenience with the understandtng that the ~hickness of the membrane is typically kept to che minimum required for effective separation, structural integrity, and substantial gas-imperviousness to the components of the oxygen-containing gas mixture other than oxygen. "Gas-imperviousness" as here used means substantially gas-tight in that the 15 membrane does not pPrmit a substantial amount of the first oxyge~-containing gas (other than the oxygen component in the forr of an oxide ion) to pass through the membrane as a gas. If an oxygen-consuming gas is used as a substrate in the second zone of the separation apparatus, the membrane should also be gas-impervious to its components as Yell as to the 20 second oxygen-containing gàs formed from the reaction of the oxygen-consuming substrate uith the oxygen on the second surface of the membrane (other than oxygen itself, of course). In some embodiments of this invention, a minor degree of perviousness to gases are acceptable or ~` unavoidable, particularly when hydrogen gas is present.
The membrane can be prepared in any one of a nu~ber of different methods, the particular method employed being a matter of conYenience.
Typically, the membranes are prepared by mixing the desired components in `` the proper proportions to form a solution or slurry, drying the solution 30 or slurry with or ~ithout a reducing agent, calcining the remains of the dried solution or slurry, shaping the produc~ of the calcination, typically ~ith a binder, into the desired shape, and then sintering the shaped, calcined product to the finished membrane. The components -`~ employed can be the oxides, halides, nitrates, ace~ates or other salts of 35 Bi, A, M and H',and particularly preferred is the use of their soluble salts. After the starting ingredients have been combined to form a :`
:`
.
- . -- .. .. . . . . .
: ~- ' ', ' ` : ' ` :, ' , ,, .' .' : ' ' .' :: ' ' : ' ` . ~ : .
~vo 92/0~862 PCT/US91/07391 9 `~9~3~2 solution or slurry (with or without the aid of a dispersant, such as citric acid)t it is dried and the recovered solid is then heated in the presence of a nonreducing gas, such as air, nitrogen, nitric oxide, etc., at a temperature between about 400 and about 1000C. After the dried - 5 slurry has been calcined, the resulting product is crushed, mixed with a binder (e.g. polyethylene glycol, glycerol, polyvinyl alcohol, starch, etc.), shaped, and then sintered in a nonreducing gas at a temperature between about 700 and about 1100C. The calcination continues until essentially all of the physically bound Yater has been re~oved, and the lO sintering continues until the shaped bocly nears its theoretical density.
Alternative methods of membrane preparation include vapor deposition, flame spraying, plasma spraying, coprecipitation, oxide or carbonate sintering and other techniques known to those skilled in the art.
If the membrane is used in combination with a support, the calcined, crushed solids either uith or without a binder, are applied to the support in any convenient manner and then subjected to sintering.
2. Process Apparatus ``
The separation apparatus used in the process of this invention comprises a first and second zone separated by the ~i-con~aining mixed metal oxide membrane of this invention. The membrane forms a 25 substantially gas impervious barrier betveen the two zones of the separation apparatus, although the configuration of the barrier can vary ; to convenience. Typically, the apparatus is constructed in such a manner that each zone can be heated, either as a single unit or independent of - one another. Zone 1 is equipped uith a port ehrough which the oxygen-30 containing gas can be fed in such a manner that it eventually is in contact uith a surface of the membrane that is not in contact with zone 2.
Zone 2 is equipped with means by which the oxygen separated from the oxygen-containin gas in zone 1 can be collected for recovery (eypically by drawing a full or partial vacuum on zone 2) or can be put to immediate 35 use (typically by reacting with an oxygen-consuming substance). If the oxygen that emerges onto the second surface of the membrane is to be ;.
~ , -~ '' .' ". . : ' W O 9~/0~862 PCT/US91tO7391 2~93332 -10- ! :
collected, zone 2 can simply be an oxygen impervious chamber from which oxygen recovered from the second surface can be removed con~eniently and efficiently. If the oxygen is to be immediately consumed by a substrate, then zone 2 can be configured and equipped in a manner that both maximizes 5 the contact betYeen the substrate and the oxygen present on the second surface of the membrane, and at the same time minimizes the contact between the second oxygen-con~alning co~npound and the second surface of the membrane. The use of a sweep gas, i.e. any substantially inert, relatively abundant and inexpensive gas such as nitrogen, argon, helium, lO etc., can be used to accomplish this end. As here used in reference to the second oxygen-containing gas, "oxygen-containing gas" has the same meaning as when used in reference to the first oxygen-containing gas, i.e.
molecular oxygen alone, molecular oxygen in combination ~ith other gases, and reducible oxygen-containing compounds ~here oxygen is chemically 15 bonded to another element.
Recovering molecular oxygen from the second surface of the membrane and removing it from the second zone by dra~ing a vacuum on the second zone is an example of the second oxygen-coneaining gas consisting 20 of simply molecular oxygen. Using a sweep gas, e.g. heliu~, to recover molecular oxygen from the second surface of the membrane and removing it from the second zone is an example of the second oxygen-containing gas consis~ing of a gaseous mixture. Uater, in the form of steam, is an example of the second oxygen-containing gas comprising a reducible oxygen-25 containing compound ~here oxygen is chemically bondPd to another element, here the uater present in the second zone as a product of a reaction betueen hydrogen, an oxygen-consuming substrate, and the oxygen present on the second surface of the membrane.
~' Figure l of the drawings illustrates one embodiment of the ;~ separation apparatus used in the process o~ this invention. Zones l and 2 ` are gas-impervious tubes, 3 and 4 respectively. Tube 3 has open ends 5 and 6 ~ith open end 6 placed in close approximation to first surface 7 of membrane 8 (here illustrated, in lateral cross-section, as a disc slightly 35 larger in diameter than that of tubes 3 and 4). Rim 9 of tube 4 is joined to the second surface lO of membrane 8 by a seal ll ~hich renders the , , , , -, ., .. , .- . , . ,, : .
, : , :.. . . .
. - : .. . . ::: ,: . :
W O 92/0~62 PCT/US91/07391 93~3~
junction of ri~ 9 and second surface 10 gas-impervious. ~ second, gas-impervious tube 12 of smaller diameter ~han tube 4 is coaxially fitted ~ithin tube 4 such that open end 13 of tube 12 is in close apprOXimatiQn to the second sur~ace of membrane 8. Seal 11 ls formed betveen second 5 surface 10 of membrane 8 and the rim ~hich forms open end 9 of tube 4 such that the area of second surface 10 wlthin the rlm of open end 9 ls su~stantlally unobstructed wlth sealant, as deplcted in Figure 2. Tube 12 is fitted ~ithin tube 4 to form a gas-impervious seal at juncture 14. The entire apparatus of this Figure 1 can be enclosed in a gas-impervious 10 housing (not sho~n), and is typically equipped with heating elements (also not shoun) that can independently heat ~ones 1 and 2.
Figure 2 is a bottom plan vieu taken along line 2-2 of zone 2 of the separation apparatus lllustrated in Figure 1. The i.~er~ost, clrcular 15 band ls a cross-section of tube 12 ~hich, as described above, is not in contact with second surface 10 of membrane 8. The next concentric circular band out from the innermost circle is a cross-section of seal 11, - followed by a cross-section of tube 4, follw~ed by another cross-section of seal 11. The outermost circular band is the outer edge of second ~0 surface 10. As this figure illustrates, the surface area of second -`~ surface 10 within the circular band formed by the cross-section of seal 11 is unobstructed to the flow of gaseous hydrocarbon exiting tube 12 by open : end 13.
.
; 25 In one embodiment of the operation of the separation apparatus depicted in Figure 1, an oxygen-containing gas9 e.g. air, enters open end 5 of tube 3, passes through the length of tube 3, and is discharged through open end 6 of tube 3 such that it makes contact uith first surface ~ 7 of membrane 8. Membrane 8 is a bismuth-containing mixed metal oxide of `~ 30 this invention as previously described ~ith a selectivity for oxygen. At `~ or near first surface 7, oxygen is extracted from the o~ygen-containing ` gas as an oxide ion, and transported across membrane 8 to second surface 10 ~here it is reacted ~ith an oxygen-consuming substance, e.g. a gaseous hydrocarbon. The oxygen-consuming gas is introduced to second surface 10 35 through tube 12 in such a manner that it also serves as a s~eep gas, e.g.
nitrogen, argon, helium, etc. The products formed by the reaction of the ~ . . . . . .. ...
~0 9~t05~2 PCT/US~1/0739l 2~3332 -12-oxide ion and hydrocarbon are continuously removed from or near second surface lO and ~he annular space within tube 4 that is defined by the outer surface of tube 12 and the ~nner surface of tube 4, by Yay of tube 15. The air is brought in contact with first surface 7 of membrane ~ in 5 such a manner that the equilibrium oxygen partial pressure of the gas is greater than the equilibrium oxygen partial pressure that exists at or near the second surface 10 within the area defined by seal 11. This difference in equilibrium oxygen partial pressure betveen zones 1 and 2 can be maintained by any one of a number of different means, but it is ~0 typically maintained at a steady state by a constant introduc~ion of the oxygen-containing gas to first surface 7 and the constant consumption of the oxide ion at or near second surface 10 by the oxygen-consuming gas to form a second oxygen-containing gas that is continuously removed from zone 2. "Equilibrium oxygen partial pressure" here means the oxygen 15 pressure calculated at stated conditions when the mixture of components is at thermodynamic equilibrium.
In another embodiment of the operation of the separation apparatus depicted in Figure 1 modified by the deletion of tube 12 and the 20 conversion of tube 4 (zone Z) into a closed, gas-impervious housing with . tube 15 as the only means of exit (other than membrane 8 itself), theoxide ion is recovered from surface 10 in the form of molecular oxygen. A
slight vacuum is drawn on zone 2 (by means not shown), and the oxygen is recovered through tube 15.
~. 25 : Figure 3 is a schematic diagram of another embodiment of the separation apparatus. ~ere, the Bi-containing mixed metal oxide membrane is tube 20 uhich exeends through housing 21 to form chamber 227 a closed space except for its open communication with eube 23. In one mode of : 30 opera~ion of this particular separation apparatus, an oxygen-containing ; gas is fed through the interior of tube 20 (zone 1) under conditions which : oxygen is extracted from the oxygen-containing gas on the inner (first) :~ surface of tube 20, transported across the thickness of eube 20 in the form of an oxide ion to the outer (second) surface of tube Z0, uhere it is 35 recovered in the form of molecular oxygen and removed from chamber 22 (zcne 2) by way of tube 23. In another mode of operation of this same -.: : : : . :. .: .
-, - : . ~: :, :::, . :: : . : -: :.. . . :
- . . . : . : : : : ,, , , , ::
W O 92/~58S2 PCT/US9l/07391 -13- ~93332 apparatus, the oxygen-containing gas is fed into chamber 22 (zone 1) by uay of tube 23, oxygen is extracted at the outer ~first) surface of tube 20, transported aCrOSS the thickness of ~ube 20, recovered as molecular oxygen from the inner (second) surface of tube 20, and then removed from 5 the interior of tube 20 (zone 2). Under either mode of operation, the equilibrium oxygen partial pressure zone 1 is greater than the equilibrium oxygen partial pressure of zone 2. Each zone can be heated to the desired temperature by means not shown and but for the membrane itself (tube 20), the remaining pieces of the separation apparatus and the junctures at 10 uhich they are fitted to one another are substantially gas impervious.
If an oxygen-consuming substrate is used, it is typically a reactant gas. Exemplary reaction gases include hydrogen, carbon monoxide ; and a hydrocarbon such as ethane, ethylene, propane, propylene, butane, 15 butenes, light naphtha, mixtures of parafins, or mixtures of parafins and olefins, mixtures of olefins, or mixtures of parafins, olefins and aromatics. The reacting gas can also contain inerts or diluents, such as nitrogen or steam, or a recycled product stream.
, .
` 20 As noted earlier, oxygen can also be collected and removed from the second surface of the membrane in the absence of an oxygen-consuming substrate, ~ut the effectiveness of this separation ~ill depend upon the oxygen partial pressure difference between the oxygen-containing gas and that of zone 2. The relative pressures of both zone 1 and zone 2 can be 25 subatmospheric, atmospheric or superatmospheric, as long as the oxygen partial pressure of zone 1 is greater than the oxygen partial pressure of zone 2.
:
The process of this invention can be conducted at any 30 temperature at uhich the oxygen-containing gas remains in the gaseous ` state when in contact with the first surface of the membrane. However, since the oxide ion flux of the membrane will vary with ~emperature and since the flux will usually increase with temperature, preferably the process is conducted at an elevated temperature. The exact temperatures 35 at which zones 1 and 2 of the separation apparatus are maintained will vary with the nature of the oxygen-containing gas, the oxygen-consuming - . , ~
. . ' ~
~VO 9'/0~86~ PCr/VS9l/07391 20~3332 -14- " ~
substrate, if any, and the composition of the membrane but uhere the oxygen-containing gas is air and the oxygen-consuming substrate is a reactant gas, particularly a hydrocarbon, a minimum temperature of about 300C, preerably about 400C, is employed in each zone. The maximum 5 temperature of zones 1 and 2 will also vary with the nature of the oxygen-containing gas and oxygen-consuming substrate but where the former is air and the latter is a hydrocarbon, the maximum temperature is typically not greater than about 900C, and preferably not greater than about 800~C, for each zone.
The following examples are illustrative of certain specific embodiments of this invention. Unless otherwise indicated, all parts and percentages are by mol %.
SPECIFIC EMBODIMENTS r .
, _ Example l Ferric nitrate (50.0g), strontium acetate (25.6g), bismuth nitrate (60.03g) and citric acid (35.65g) were slurried in 500 ml of vater and heated to dissolution. The solution was first reduced to near dryness ` under vacuum on a rotary evaporator, and then to dryness in a vacuum oven.
The solids were collected and calcined at 890C for two hours in air. The 25 calcined solid was then crushed to fine powder, admixed with 5 wt %
Carbouax-20M (a polyethylene glycol) pressed into 34.9 mm diameter discs - (1 mm thick), and sintered in air at 970C for 17.5 hours. The empirical formula of the discs was 8il Srl Fel x vith a measured density of 5.66 g/clll3.
One of the discs (#8 in Figure 1) was then fitted and sealed into a separation apparatus as depicted in Figure 1. Glass powder from Corning (No. 816i with a softening point of 6Q0C) ~as mixed with isobutanol to form a thick paste vhich was then placed on the rim (#9) and 35 outer surface of a mullite tube (~4). The second surface ($10) of the disc vas then joined to the mullite tube to form a gas-impervious seal :,, .: . .: . ::, , . , :: .. .... :. . .
t ' , ' . " ' , , ' ::
U O 9~/0~862 P~T/US91/07391 - 2~33332 (~11). Another mullite tube (#3) was then positioned such that it was in close proximity to the first surface (~7) of the disc, and the whole apparatus was ~hen placed in an electric furnace ~not shovn in Figure 1) and heated to 750C over the course of 7-1/2 hours. After holding at thls 5 temperature for 1/2 hour, the temperature was lo~ered at a constant rate to 550C over 6-1/2 hours to obtain a gas tight seal. Air ~as then passed - through mullite tube 3 to the first surface 7 of disc 8, and nitrogen was passed through mullite tube 12 to second surface 10 of disc 8. The temperature was then adjusted to the desired reaction temperature, and the 10 nitrogen was replaced by hydro~en.
The oxygen flux was measured after the separation apparatus reached steady state operation at any given temperature, usually after a minimum of one hour. The gaseous reaction product was cooled to -78C to 15 trap water, which was collected and weighed. The dry vent gas composition was analyzed by gas chromatography. The oxy~en flux was 269 mA/cm2 at 70~C after 5 hours of operation and when the temperature ~as lowered to - 457C, it was 56 mA/cm2 after 11 hours of total operation.
Figure 4 is a plot of these and other data points expressed as the natural log of the flux in mA/cm2 (the ordinate) vs. the inverse of ` temperature in degrees Kelvin (the abscissa). The data points are expressed in these units because the energy of activation can then be obtained from the slope of the resulting line, which in turn permits the 25 determination of the oxygen flux of the membrane at any temperature. As it clearly demonstrates, the flux of the membrane increases exponentially ~ith an increase in temperature. By uay of illustration, followin~ is the calculation for the data point at 457C, i.e. 56 mA/cm2.
mA/cm2 = mA
nr2 ~here r = 0.775 cm, the radius of the disc exposed to ~2~ and mA = cc 2 S, where cc 2 = ~ (F H E) .. - . .. . .
, ~,, - . : .
.
. .. . .
W O 92/058~2 P~r/US9l/07391 ,. ~, 20933~2 where I = 0.0434g of H20 collected over the course of the run, J = 1.017 hr, the duration of the run R = 11.2, a factor relating g of ~0 collected in 1 hr to mols of 2 passed in 1 min.
S = 267, a factor relating current in mh to cc of 2 passed per min.
F = 63.5 cc/min H2 gas flo~ ~
H = 0.005 mol Z N2 in H2 r E = 0.245, a calibration ratio relating the ,~ sensitivity of the gas chromatograph to N2 and 2 The H2 gas flow uas measured beore the start of the run (i.e. before air ~as introduced to zone 1). The product gas flow was measured during the 25 run~ The product gas was analyzed by gas chromatography to determine mol X nitrogen.
~ ExamDle 2 ;" :
`~ 30 ~ --~ A seccnd disc of the membrane prepared in Example 1 ~as tested in the appara~us and ~ith the procedure described in Exa~ple 1 and at 705C vith the reactant gas comprising a 90/5/5 composition of carbon monoxide/carbon dioxide/argon, an oxygen flux of 195 mA/cm2 was obtained 35 after 5 hours of operation. At 465C and after 11 hours of operation, the oxygen flux was equal to 84 mA/cm2. The density of the disc vas 5.70g/cm3. Figure 5 is a plot of this and other data points measured and calculated as described for Figure 4 of Example 1, except the calculation .
. : :: ., , : :: : . : : .. ,: . ~: ~
W O 92~0~862 PCT/VS91/073gl ~ ' ,.
-17- 2 n ~ 3 3 3 2 of cc 2 required the use of a different equation. The folloYing calculation of 84 mA/cm2 is illustrative:
cc 2 = [(B K)+(~ L)l - l(F-M)+(F-N)I - (B-D-E)]
where B = 62.9 cc/min Product Gas Flow K = 5.68 mol X C2 in Product Gas ; L = 88.64 mol % C0 in Product Gas F = 62.0 cc~min Fuel Gas Flow ~- 15 M = 4.97 mol Z C02 in Fùel Gas N = 88.76 mol X C0 in Fuel Gas D = 0.89 mol % N2 in Product Gas E = 0.245, a calibration ratio relating the sensitivity of the gas chromatograph to N2 and 2 25 Example 3 :`
A membrane of the composition Bil Sr1 Ca1 Fe2 n vas prepared from a slurry of nitrates of bismuth (60.0g), calcium (29.2'g) and iron 30 (99.94g), and strontium ace~ate (25.45g) by the procedure described in Example 1. The solid was coll-ected and then calcined at 820C for 16 hours in air. The solid was crushed, pressed into 34.9 mm diameter discs (using 5 wt Z Carbowax-20M as a bi~der) witb a thickness of 1 mm and sintered in air at 1010C for 15 hours. The density of the disc was 35 4.83g/cm3.
The disc was charged to the furnace and sealed vith glass as described in Examplle 1, and the temperature was increased sloYly to 650C.
At 650C, the oxide ion flux was measured at 40 mA/cm2 after 5.5 hours of 40 operation by checking for water formation.
:, , , ~ , :
. -~
.:-~ . : . ., .; . . - : --W O 92/0~86' PCT/US91/07391 2~'~33~% -18-E.Ya~ple 4 A mixture of bismuth nltrate (50g), yttrium nltrate (31.6g) and 5 cobalt nitrate (5.14g) was slurried in 500 ml of water with citric acid and as in Example 1, the water was removed under vacuum and then oven dried to leave a solid. The solids were collected and calcined in air at 850C for 9 hours. The resulting solid ~las crushed to a fine powder, pressed into 34.9 mm diameter discs, mixed vith 5 wt Z Carbovax-20M, and 10 sintered in air for 12 hours at 970C. The disc had an empirical formula of Bil Yo.8 C00.2 n with a measured density of 7.26g/c~3.
The disc ~as then sealed into place in the furnace as described in Example 1, and a 90/5/5 carbon monoxide/carbon dioxide/argon mixture 15 was used as the reactant gas. After 2 hours operation at 550C, the flux ` ~as measured at 63 mA/cm2. The temperature ~as then raised to 700C and ; after 8 hours of operation, the flux was 558 mA/cm2. The temperature was then lowered, this time to 450C, and the reactant gas s~itched to ; hydrogen. After 80 hours of total elapsed time on stream (including time 20 on stream with C02/CO!Ar mixture), the flux was 17 mA/cm2. Figure 6 is a plot of the tuo C0/C02/Ar daca points, and another, measured and calculated as described for Figure 5 of Example 2.
ExamDle 5 Bismuth nitrate (76.64g), ferric nitrate (95.74g), lan~hanum acetate (27.10g) and strontium acetate (65.0g) were slurried with citric acid in 500 ml of water. The ~ater ~as removed under vacuu~, the solids 30 dried in an oven, collected and then calcined at 900C for 24 hours; the resulting solid crushed to a fine powder, mixed with 5 vt Z Carbowax-20M, pressed into 34.9 mM discs, and sintered in air at 1200C for 5 hours.
The disc which had an empirical formula of Bi1 Fe1 5 Lao 5 Sr2 n and a density of 6.21 g/CM3, was sealed into the reactor as in Example 1, and 35 tested at 550-6S0C using the 90/5/5 carbon monoxide/carbon dioxide/argon mixture as a reactant gas. The flux was 12 mA/cm2 at 550C after 2 hours W O 92/0586~ 2 ~ 3 2 PCT/US91/07391 --19-- ;`
of operation, while the highest flux was 39 mA/cm2 at 650~C after 3 hours of operation.
Although the invention has been described in considerable detail : 5 through the preceding Examples, these Examples are for the purpose of illustration only and it is understood that variations and modifications : can be made by one skilled in the art w:ithout departing from the spirit and scope of the invention.
. . .
Claims (40)
1. A progress for separating oxygen from a first oxygen-containing gas, the process comprising:
(A) Feeding the first oxygen-containing gas into a first zone of a gas separation apparatus, the apparatus comprising first and second zones separated by a mixed metal oxide membrane, the membrane having a first surface open to the first zone, a second surface open to the second zone, and an empirical formula of Bi Ax My M' z On where A is at least one of La, U, Th, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Mg, Ca, Sr and Ba;
M is at least one of Sc, Ti, Cr, Mn, Fe, Ni, Cu and Zn;
M' is at least one of Co, Rh, Pd, Pt and Ru;
x and y are individually a number between about 0.01 and about 10;
z is a number of 0 to about 0.2; and n is a number that satisfies the valence requirements of the other elements present;
the first zone having an equilibrium oxygen partial pressure greater than that of the second zone;
(B) Contacting the first oxygen-containing gas in the first zone of the separation apparatus with the first surface of the membrane such that:
(i) oxygen is extracted from the first oxygen-containing gas at the first surface of the membrane; and (ii) the extracted oxygen is transported across the membrane, in the form of oxide ions, to the second surface of the membrane; and (C) Recovering the extracted oxygen from the second surface of the membrane such that a second oxygen-containing gas is produced in the second zone of the separation apparatus.
(A) Feeding the first oxygen-containing gas into a first zone of a gas separation apparatus, the apparatus comprising first and second zones separated by a mixed metal oxide membrane, the membrane having a first surface open to the first zone, a second surface open to the second zone, and an empirical formula of Bi Ax My M' z On where A is at least one of La, U, Th, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Mg, Ca, Sr and Ba;
M is at least one of Sc, Ti, Cr, Mn, Fe, Ni, Cu and Zn;
M' is at least one of Co, Rh, Pd, Pt and Ru;
x and y are individually a number between about 0.01 and about 10;
z is a number of 0 to about 0.2; and n is a number that satisfies the valence requirements of the other elements present;
the first zone having an equilibrium oxygen partial pressure greater than that of the second zone;
(B) Contacting the first oxygen-containing gas in the first zone of the separation apparatus with the first surface of the membrane such that:
(i) oxygen is extracted from the first oxygen-containing gas at the first surface of the membrane; and (ii) the extracted oxygen is transported across the membrane, in the form of oxide ions, to the second surface of the membrane; and (C) Recovering the extracted oxygen from the second surface of the membrane such that a second oxygen-containing gas is produced in the second zone of the separation apparatus.
2. The process of Claim 1 where the second oxygen-containing gas is produced in the second zone of the separation apparatus by reacting the extracted oxygen present on the second surface of the membrane with an oxygen-consuming substance that is present in the second zone and is in contact with the second surface of the membrane.
3. The process of Claim 2 where x is a number between about 0.2 and about 5, and y is a number between about 0.2 and about 7.
4. The process of Claim 2 there x is a number between about 0.5 and about 2, y is a number between about 0.5 and about 3, and z is a number greater than 0.
5. The process of Claim 3 where A is at least one of Sr, La, Ca, Y, Ba, Ce, U and Gd, H is at least one of Fe, Cu, Cr and Ni, and H' is at least one of Co, Rh, Pd and Ru.
6. The process of Claim 3 where A is at least one of Sr, La, Ca and Ba, M is at least one of Fe, Ni and Cr, and H' is at least one of Co, Ru and Pd.
7. The process of Claim 5 where at least a portion of the oxygen in the first oxygen-containing gas is molecular oxygen.
8. The process of Claim 5 where the first oxygen-containing gas comprises at least one of air, sulfur dioxide and a nitrogen oxide.
9. The process of Claim 5 where the first oxygen-containing gas comprises air.
10. The process of Claim 8 where the oxygen-consuming substance comprises at least one of hydrogen gas, a hydrocarbon gas, and a gaseous carbon monoxide/carbon dioxide mixture.
11. The process of Claim 8 where the membrane is used in the absence of a support.
12. The process of Claim 8 where the membrane is used in combination with a support.
13. The process of Claim 10 or 11 where the temperature of each zone is between about 300° and about 900°C.
14. The process of Claim 10 or 11 where the temperature of each zone is between about 400° and about 800°C.
15. The process of Claim 10 or 11 where the second oxygen-containing gas is removed from the second zone by a sweep gas.
16. The process of Claim 1 where the extracted oxygen is recovered from the second surface of the membrane in the form of molecular oxygen.
17. The process of Claim 16 where x is a number between about 0.2 and about 5, and y is a number between about 0.2 and about 7.
18. The process of Claim 16 where x is a number between about 0.5 and about 2, y is a number between about 0.5 and about 3, and z is a number greater than 0.
19. The process of Claim 17 where A is at least one of Sr, La, Ca, Y, Ba, Ce, U and Gd, M is at least one of Fe, Cu, Cr and Ni, and M' is at least one of Co, Rh, Pd and Ru.
20. The process of Claim 17 where A is at least one of Sr, La, Ca and Ba, M is at least one of Fe, Ni and Cr, and M' is at least one of Co, Ru and Pd.
21. The process of Claim 19 where the first oxygen-containing gas comprises molecular oxygen.
22. The process of Claim 19 where the first oxygen-containing gas comprises at least one of air, sulfur dioxide, and a nitrogen oxide.
23. The process of Claim 22 where the membrane is used in the absence of a support.
24. The process of Claim 22 where the membrane is used in combination with a support.
25. The process of Claim 22 where the temperature of zone 1 is between about 300° and about 900°C.
26. The process of Claim 22 where the temperature of zone 1 is between about 400° and about 800°C.
27. The process of Claim 25 where the molecular oxygen in the second zone is removed by drawing a vacuum on the second zone.
28. A process for reacting a hydrocarbon gas with oxygen, the process comprising:
(A) Feeding a first oxygen-containing gas into a first zone of a gas separation apparatus, the apparatus comprising first and second zones separated by a mixed metal oxide membrane, the membrane having a first surface open to the first zone, and a second surface open to the second zone, and an empirical formula of Bi Ax My M z On where A is at least one of La, U, Th, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Hg, Ca, Sr and Ba;
M is at least one of Sc, Ti, Cr, Mn, Fe, Ni, Cu and Zn;
M is at least one of Co, Rh, Pd, Pt and Ru;
x and y are indivldually a number between about 0,01 and about 10;
z is a number of 0 to about 0.2; and n is a number that satisfies the valance requirements of the other elements present;
the first zone having an equilibrium oxygen partial pressure greater than that of the second zone;
(B) Contacting the first oxygen-containing gas in the first zone of the separation apparatus with the first surface of the membrane such that:
(i) oxygen is extracted from the first oxygen-containing gas at the first surface of the membrane; and (ii) the extracted oxygen is transported across the membrane, in the form of oxide ions, to the second surface of the membrane; and (C) Contacting the extracted oxygen present on the second surface of the membrane with the hydrocarbon gas which is present in the second zone and is in contact with the second surface of the membrane such that the extracted oxygen and hydrocarbon gas react to form a second oxygen-containing gas.
(A) Feeding a first oxygen-containing gas into a first zone of a gas separation apparatus, the apparatus comprising first and second zones separated by a mixed metal oxide membrane, the membrane having a first surface open to the first zone, and a second surface open to the second zone, and an empirical formula of Bi Ax My M z On where A is at least one of La, U, Th, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, Hg, Ca, Sr and Ba;
M is at least one of Sc, Ti, Cr, Mn, Fe, Ni, Cu and Zn;
M is at least one of Co, Rh, Pd, Pt and Ru;
x and y are indivldually a number between about 0,01 and about 10;
z is a number of 0 to about 0.2; and n is a number that satisfies the valance requirements of the other elements present;
the first zone having an equilibrium oxygen partial pressure greater than that of the second zone;
(B) Contacting the first oxygen-containing gas in the first zone of the separation apparatus with the first surface of the membrane such that:
(i) oxygen is extracted from the first oxygen-containing gas at the first surface of the membrane; and (ii) the extracted oxygen is transported across the membrane, in the form of oxide ions, to the second surface of the membrane; and (C) Contacting the extracted oxygen present on the second surface of the membrane with the hydrocarbon gas which is present in the second zone and is in contact with the second surface of the membrane such that the extracted oxygen and hydrocarbon gas react to form a second oxygen-containing gas.
29. The process of Claim 28 where x is a number between about 0.2 and about 5, and small y is a number between about 0.2 and about 7.
30. The process of Claim 28 where x is a number between about 0.5 and about 5, small y is a number between about 0.5 and about 3, and z is a number greater than 0.
31. The process of Claim 29 or 30 where A is at least one of Sr, La, Ca, Y, Ba, Ce, U and Gd, M is at least one of Fe, Cu, Cr and Ni, and M' is at least one of Co, Rh, Pd and Ru.
32. The process of Claim 29 or 30 where A is at least one of Sr, La, Ca and Ba, M is at least one of Fe, Ni and Cr, and M' is at least one of Co, Ru and Pd.
33. The process of Claim 31 where the first oxygen-containing gas comprises at least one of air, sulfur dioxide, and a nitrogen oxide.
34. The process of Claim 31 where the firs: oxygen-containing gas comprises air.
35. The process of Claim 33 where the hydrocarbon gas is at least one of ethane, ethylene, propane, propylene, butane, butenes, light naphtha, mixtures of paraffins, mixtures or paraffins and olefins, mixtures of paraffins, olefins and aromatics, and aromatics.
36. The process of Claim 35 where the membrane is used in the absence of support.
WO 92/05862 PCT/US91/07391
38. The process of Claim 35 where the temperature of each zone is between about 300° and about 900° C.
39. The process of Claim 35 where the temperature of each zone is between about 400° and about 800° C.
40. The process of Claim 39 where the second oxygen-containing gas is removed from the second zone by a sweep gas.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/594,247 US5160713A (en) | 1990-10-09 | 1990-10-09 | Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membrane |
| US07/594,247 | 1990-10-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2093332A1 true CA2093332A1 (en) | 1992-04-10 |
Family
ID=24378130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002093332A Abandoned CA2093332A1 (en) | 1990-10-09 | 1991-10-03 | Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membrane |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5160713A (en) |
| JP (1) | JPH05508381A (en) |
| KR (1) | KR930702062A (en) |
| CA (1) | CA2093332A1 (en) |
| WO (1) | WO1992005862A1 (en) |
Families Citing this family (70)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6287432B1 (en) * | 1987-03-13 | 2001-09-11 | The Standard Oil Company | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions |
| US5342431A (en) * | 1989-10-23 | 1994-08-30 | Wisconsin Alumni Research Foundation | Metal oxide membranes for gas separation |
| DE4143331A1 (en) * | 1991-03-06 | 1992-10-08 | Deutsche Forsch Luft Raumfahrt | Gas transport by surface diffusion - through narrow passages in solid body, esp. for atomic oxygen@ prodn. |
| US5441610A (en) * | 1992-02-28 | 1995-08-15 | Renlund; Gary M. | Oxygen supply and removal method and apparatus |
| US5302258A (en) * | 1992-02-28 | 1994-04-12 | Triox Technologies, Inc. | Method and apparatus for separating oxygen from a gaseous mixture |
| US5240480A (en) * | 1992-09-15 | 1993-08-31 | Air Products And Chemicals, Inc. | Composite mixed conductor membranes for producing oxygen |
| FR2698016B1 (en) * | 1992-11-13 | 1995-01-06 | Air Liquide | Process and composition for the separation of oxygen from a gas mixture. |
| US5487774A (en) * | 1993-11-08 | 1996-01-30 | Wisconsin Alumni Research Foundation | Gas phase fractionation method using porous ceramic membrane |
| US6165431A (en) * | 1993-12-08 | 2000-12-26 | Eltron Research, Inc. | Methods for separating oxygen from oxygen-containing gases |
| US6592782B2 (en) | 1993-12-08 | 2003-07-15 | Eltron Research, Inc. | Materials and methods for the separation of oxygen from air |
| US6033632A (en) * | 1993-12-08 | 2000-03-07 | Eltron Research, Inc. | Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them |
| US6355093B1 (en) | 1993-12-08 | 2002-03-12 | Eltron Research, Inc | Two component-three dimensional catalysis |
| US5565017A (en) * | 1993-12-17 | 1996-10-15 | Air Products And Chemicals, Inc. | High temperature oxygen production with steam and power generation |
| US5516359A (en) * | 1993-12-17 | 1996-05-14 | Air Products And Chemicals, Inc. | Integrated high temperature method for oxygen production |
| US5447555A (en) * | 1994-01-12 | 1995-09-05 | Air Products And Chemicals, Inc. | Oxygen production by staged mixed conductor membranes |
| US5439624A (en) * | 1994-02-14 | 1995-08-08 | Wisconsin Alumni Research Foundation | Method for forming porous ceramic materials |
| AU706663B2 (en) * | 1994-09-23 | 1999-06-17 | Standard Oil Company, The | Oxygen permeable mixed conductor membranes |
| US5573737A (en) * | 1994-09-27 | 1996-11-12 | The United States Of America As Represented By The United States Department Of Energy | Functionally gradient material for membrane reactors to convert methane gas into value-added products |
| DE69601041T2 (en) * | 1995-02-09 | 1999-06-24 | Normalair Garrett Ltd | Device for the production of oxygen |
| US5681373A (en) * | 1995-03-13 | 1997-10-28 | Air Products And Chemicals, Inc. | Planar solid-state membrane module |
| US5599383A (en) * | 1995-03-13 | 1997-02-04 | Air Products And Chemicals, Inc. | Tubular solid-state membrane module |
| US5547494A (en) * | 1995-03-22 | 1996-08-20 | Praxair Technology, Inc. | Staged electrolyte membrane |
| US6132693A (en) * | 1995-04-11 | 2000-10-17 | Robert Bosch Gmbh | Process and device for reducing pollutants, especially nitrogen oxides in combustion exhaust gases |
| BR9601078A (en) * | 1995-05-18 | 1998-01-06 | Praxair Technology Inc | Process for removing oxygen from a feed stream to obtain an oxygen-depleted product stream |
| US5888273A (en) * | 1996-09-25 | 1999-03-30 | Buxbaum; Robert E. | High temperature gas purification system |
| US5837125A (en) | 1995-12-05 | 1998-11-17 | Praxair Technology, Inc. | Reactive purge for solid electrolyte membrane gas separation |
| US6471745B1 (en) * | 1996-06-28 | 2002-10-29 | University Of Delaware | Nanoporous carbon catalytic membranes and method for making the same |
| US5972079A (en) * | 1996-06-28 | 1999-10-26 | University Of Delaware | Supported carbogenic molecular sieve membrane and method of producing the same |
| US5938822A (en) * | 1997-05-02 | 1999-08-17 | Praxair Technology, Inc. | Solid electrolyte membrane with porous catalytically-enhancing constituents |
| US5911860A (en) * | 1996-12-31 | 1999-06-15 | Praxair Technology, Inc. | Solid electrolyte membrane with mechanically-enhancing constituents |
| US5820654A (en) * | 1997-04-29 | 1998-10-13 | Praxair Technology, Inc. | Integrated solid electrolyte ionic conductor separator-cooler |
| ID20211A (en) * | 1997-04-29 | 1998-10-29 | Praxair Technology Inc | HYDROGEN PRODUCTION METHOD USING SOLID ELECTROLITE MEMBRANE |
| US5820655A (en) * | 1997-04-29 | 1998-10-13 | Praxair Technology, Inc. | Solid Electrolyte ionic conductor reactor design |
| US6117210A (en) * | 1997-04-29 | 2000-09-12 | Praxair Technology, Inc. | Solid electrolyte systems for producing controlled purity oxygen |
| US5888272A (en) * | 1997-06-05 | 1999-03-30 | Praxair Technology, Inc. | Process for enriched combustion using solid electrolyte ionic conductor systems |
| US6149714A (en) * | 1997-06-05 | 2000-11-21 | Praxair Technology, Inc. | Process for enriched combustion using solid electrolyte ionic conductor systems |
| US6077323A (en) | 1997-06-06 | 2000-06-20 | Air Products And Chemicals, Inc. | Synthesis gas production by ion transport membranes |
| NO308398B1 (en) | 1997-06-06 | 2000-09-11 | Norsk Hydro As | Process for carrying out catalytic or non-catalytic processes in which oxygen is ± n of the reactants |
| US5944874A (en) * | 1997-06-23 | 1999-08-31 | Praxair Technology, Inc. | Solid electrolyte ionic conductor systems for the production of high purity nitrogen |
| US5851266A (en) * | 1997-06-23 | 1998-12-22 | Praxair Technology,Inc. | Hybrid solid electrolyte ionic conductor systems for purifying inert gases |
| US5935533A (en) * | 1997-10-28 | 1999-08-10 | Bp Amoco Corporation | Membrane reactor hollow tube module with ceramic/metal interfacial zone |
| US6059858A (en) * | 1997-10-30 | 2000-05-09 | The Boc Group, Inc. | High temperature adsorption process |
| US5976223A (en) * | 1997-11-18 | 1999-11-02 | Praxair Technology, Inc. | Solid electrolyte ionic conductor systems for oxygen, nitrogen, and/or carbon dioxide production with gas turbine |
| US5964922A (en) * | 1997-11-18 | 1999-10-12 | Praxair Technology, Inc. | Solid electrolyte ionic conductor with adjustable steam-to-oxygen production |
| US5954859A (en) * | 1997-11-18 | 1999-09-21 | Praxair Technology, Inc. | Solid electrolyte ionic conductor oxygen production with power generation |
| US5935298A (en) * | 1997-11-18 | 1999-08-10 | Praxair Technology, Inc. | Solid electrolyte ionic conductor oxygen production with steam purge |
| US6132573A (en) * | 1997-12-05 | 2000-10-17 | Igr Enterprises, Inc. | Ceramic composite electrolytic device and methods for manufacture thereof |
| US6048472A (en) * | 1997-12-23 | 2000-04-11 | Air Products And Chemicals, Inc. | Production of synthesis gas by mixed conducting membranes |
| DE69817749T3 (en) * | 1997-12-23 | 2013-07-18 | Air Products And Chemicals, Inc. | Use of synthesis gas produced by means of conductive mixing membranes |
| NO312342B1 (en) * | 1998-05-20 | 2002-04-29 | Norsk Hydro As | A dense single-phase membrane with both high ionic and high electronic conductivity and application thereof |
| US6153163A (en) * | 1998-06-03 | 2000-11-28 | Praxair Technology, Inc. | Ceramic membrane reformer |
| GB9823651D0 (en) * | 1998-10-29 | 1998-12-23 | Normalair Garrett Ltd | Gas generating system |
| EP1035072B1 (en) * | 1999-03-05 | 2004-05-12 | Haldor Topsoe A/S | Process for autothermal catalytic stream reforming |
| US6464955B2 (en) * | 1999-05-13 | 2002-10-15 | The Boc Group, Inc. | Production of hydrogen and carbon monoxide |
| US6471921B1 (en) | 1999-05-19 | 2002-10-29 | Eltron Research, Inc. | Mixed ionic and electronic conducting ceramic membranes for hydrocarbon processing |
| US6146549A (en) * | 1999-08-04 | 2000-11-14 | Eltron Research, Inc. | Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties |
| NO313493B1 (en) * | 1999-09-28 | 2002-10-14 | Norsk Hydro As | Solid multicomponent membrane comprising a mixed metal oxide for use in a heat or synthesis gas reactor |
| CN1121257C (en) * | 1999-11-08 | 2003-09-17 | 中国科学技术大学 | Ceramic material for making compact oxygen-permeable separation membrane and and its oxygen permeable membrane separator |
| US6779335B2 (en) | 2000-12-07 | 2004-08-24 | Joseph Roger Herdy, Jr. | Burning nitrous oxide and a fuel |
| US6562104B2 (en) * | 2000-12-19 | 2003-05-13 | Praxair Technology, Inc. | Method and system for combusting a fuel |
| US6537465B2 (en) * | 2000-12-29 | 2003-03-25 | Praxair Technology, Inc. | Low pressure steam purged chemical reactor including an oxygen transport membrane |
| US6695983B2 (en) * | 2001-04-24 | 2004-02-24 | Praxair Technology, Inc. | Syngas production method utilizing an oxygen transport membrane |
| US20020179887A1 (en) * | 2001-05-01 | 2002-12-05 | Yongxian Zeng | Supported perovskite-type oxides and methods for preparation thereof |
| US20030039601A1 (en) * | 2001-08-10 | 2003-02-27 | Halvorson Thomas Gilbert | Oxygen ion transport membrane apparatus and process for use in syngas production |
| US6565632B1 (en) * | 2001-12-17 | 2003-05-20 | Praxair Technology, Inc. | Ion-transport membrane assembly incorporating internal support |
| US7122072B2 (en) * | 2003-11-17 | 2006-10-17 | Air Products And Chemicals, Inc. | Controlled heating and cooling of mixed conducting metal oxide materials |
| CN1325149C (en) * | 2005-04-06 | 2007-07-11 | 南京工业大学 | Alumina doped mixed conductive dense oxygen penetrating membrane material |
| US8177884B2 (en) * | 2009-05-20 | 2012-05-15 | United Technologies Corporation | Fuel deoxygenator with porous support plate |
| US8834604B2 (en) | 2010-09-16 | 2014-09-16 | Volt Research, Llc | High temperature gas processing system and method for making the same |
| CN109745987A (en) * | 2018-12-13 | 2019-05-14 | 大连海事大学 | The preparation method and application of strontium cobalt-based properties of perovskite mixed-oxide oxygen carrier |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1113273A (en) * | 1964-05-16 | 1968-05-08 | Kinzoku Zairyo Kenkyusho | A dispersion type metallic oxide silver alloy membrane for use in a device for separating and purifying oxygen |
| US3359705A (en) * | 1966-10-27 | 1967-12-26 | Union Carbide Corp | Oxygen permeable membranes |
| US4092264A (en) * | 1976-12-27 | 1978-05-30 | The Bendix Corporation | Barium oxide coated zirconia particle for use in an oxygen extractor |
| JPS5499405A (en) * | 1978-01-23 | 1979-08-06 | Kanda Tsushin Kogyo Kk | Tape handler mechanism |
| JPS5943401B2 (en) * | 1979-03-23 | 1984-10-22 | 動力炉・核燃料開発事業団 | How to recombine oxygen and hydrogen |
| JPS5624020A (en) * | 1979-08-06 | 1981-03-07 | Teijin Ltd | Oxygen separating membrane and method of oxygen separation |
| JPS5692103A (en) * | 1979-12-27 | 1981-07-25 | Teijin Ltd | Separation of oxygen |
| US4330633A (en) * | 1980-08-15 | 1982-05-18 | Teijin Limited | Solid electrolyte |
| US4571443A (en) * | 1985-07-23 | 1986-02-18 | The Standard Oil Company | Process for effecting oxidative dehydrodimerization |
| JPS6247053A (en) * | 1985-08-26 | 1987-02-28 | Fuji Photo Film Co Ltd | Photosensitive composition |
| JPS6437576A (en) * | 1987-08-03 | 1989-02-08 | Fujitsu Ltd | Developer agitation device |
-
1990
- 1990-10-09 US US07/594,247 patent/US5160713A/en not_active Expired - Lifetime
-
1991
- 1991-10-03 JP JP3518557A patent/JPH05508381A/en active Pending
- 1991-10-03 KR KR1019930701106A patent/KR930702062A/en not_active Application Discontinuation
- 1991-10-03 CA CA002093332A patent/CA2093332A1/en not_active Abandoned
- 1991-10-03 WO PCT/US1991/007391 patent/WO1992005862A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992005862A1 (en) | 1992-04-16 |
| KR930702062A (en) | 1993-09-08 |
| US5160713A (en) | 1992-11-03 |
| JPH05508381A (en) | 1993-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2093332A1 (en) | Process for separating oxygen from an oxygen-containing gas by using a bi-containing mixed metal oxide membrane | |
| JP3212304B2 (en) | Novel solid multi-component membranes, electrochemical reactors, and use of membranes and reactors for oxidation reactions | |
| CA2032994C (en) | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions | |
| US6332968B1 (en) | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions | |
| EP0705790B1 (en) | Oxygen permeable mixed conductor membranes | |
| CA2252539C (en) | Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them | |
| US5306411A (en) | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions | |
| US5693212A (en) | Solid multi-component membranes, electrochemical reactor components, electrochemical reactors and use of membranes, reactor components, and reactor for oxidation reactions | |
| Zeng et al. | Perovskite-type ceramic membrane: synthesis, oxygen permeation and membrane reactor performance for oxidative coupling of methane | |
| US6146549A (en) | Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties | |
| US7588626B2 (en) | Composite mixed oxide ionic and electronic conductors for hydrogen separation | |
| US6949230B2 (en) | Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them | |
| EP0931763B1 (en) | Fluid separation device comprising a mixed conducting multicomponent metallic oxide membrane | |
| US20020022568A1 (en) | Ceramic membranes for use in catalytic membrane reactors with high ionic conductivities and improved mechanical properties | |
| EP0908227A1 (en) | Coated membranes | |
| WO2000059613A1 (en) | Catalytic membrane reactor materials for the separation of oxygen from air | |
| JPH1192961A (en) | Coating film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |