WO2014074559A1 - Catalyst containing oxygen transport membrane - Google Patents
Catalyst containing oxygen transport membrane Download PDFInfo
- Publication number
- WO2014074559A1 WO2014074559A1 PCT/US2013/068657 US2013068657W WO2014074559A1 WO 2014074559 A1 WO2014074559 A1 WO 2014074559A1 US 2013068657 W US2013068657 W US 2013068657W WO 2014074559 A1 WO2014074559 A1 WO 2014074559A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- porous
- porous support
- support layer
- oxygen
- Prior art date
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- 239000001301 oxygen Substances 0.000 title claims abstract description 152
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 152
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000011148 porous material Substances 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 58
- 239000002131 composite material Substances 0.000 claims abstract description 44
- -1 oxygen ions Chemical class 0.000 claims abstract description 37
- 239000004020 conductor Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 31
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 27
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 27
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 29
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 28
- 239000010436 fluorite Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 19
- 229910052684 Cerium Inorganic materials 0.000 claims description 14
- 229910052727 yttrium Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- 229910021526 gadolinium-doped ceria Inorganic materials 0.000 claims description 5
- 230000001737 promoting effect Effects 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(III) nitrate Inorganic materials [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 230000035699 permeability Effects 0.000 abstract description 3
- 230000032258 transport Effects 0.000 description 33
- 239000012071 phase Substances 0.000 description 20
- 239000000446 fuel Substances 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- 239000010416 ion conductor Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 6
- 230000037427 ion transport Effects 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000758789 Juglans Species 0.000 description 4
- 235000009496 Juglans regia Nutrition 0.000 description 4
- 239000011532 electronic conductor Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- 235000020234 walnut Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002114 biscuit porcelain Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000011533 mixed conductor Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002194 La0.8Sr0.2FeO3–δ Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006194 liquid suspension Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
- B01D67/00411—Inorganic membrane manufacture by agglomeration of particles in the dry state by sintering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1212—Coextruded layers
-
- 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
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
Definitions
- the present invention relates to a composite oxygen transport membrane in which catalyst particles, selected to promote oxidation of a combustible substance, are located within an intermediate porous layer that is in turn located between a dense layer and a porous support layer and within the porous support and a method of applying the catalyst to the intermediate porous layer and the porous support layer through wicking of catalyst precursors through the porous support layer to the intermediate porous layer.
- Oxygen transport membranes function by transporting oxygen ions through a material that is capable of conducting oxygen ions and electrons at elevated temperatures.
- Such materials can be mixed conducting in that they conduct both oxygen ions and electrons or a mixture of materials that include an ionic conductor capable of primarily conducting oxygen ions and an electronic conductor with the primary function of transporting the electrons.
- Typical mixed conductors are formed from doped perovskite structured materials.
- the ionic conductor can be yttrium or scandium stabilized zirconia and the electronic conductor can be a perovskite structured material that will transport electrons, a metal or metal alloy or a mixture of the perovskite type material, the metal or metal alloy.
- the partial pressure difference can be produced by providing the oxygen containing feed to the membrane at a positive pressure or by supplying a combustible substance to the side of the membrane opposing the oxygen containing feed or a combination of the two methods.
- oxygen transport membranes are composite structures that include a dense layer composed of the mixed conductor or the two phases of materials and one or more porous supporting layers. Since the resistance to oxygen ion transport is dependent on the thickness of the membrane, the dense layer is made as thin as possible and therefore must be supported.
- Another limiting factor to the performance of an oxygen transport membrane concerns the supporting layers that, although can be active, that is oxygen ion or electron conducting, the layers themselves can consist of a network of interconnected pores that can limit diffusion of the oxygen or fuel or other substance through the membrane to react with the oxygen. Therefore, such support layers are typically fabricated with a graded porosity in which the pore size decreases in a direction taken towards the dense layer or are made highly porous throughout. The high porosity, however, tends to weaken such a structure.
- U.S. Patent No. 7,229,537 attempts to solve such problems by providing a support with cylindrical or conical pores that are not connected and an intermediate porous layer located between the dense layer and the support that distributes the oxygen to the pores within the support.
- Porous supports can also be made by freeze casting techniques, as described in 10, No. 3, Advanced Engineering Materials, "Freeze-Casting of Porous
- the oxygen partial pressure difference can be created by combusting a fuel or other combustible substance with the separated oxygen.
- the resulting heat will heat the oxygen transport membrane up to operational temperature and excess heat can be used for other purposes, for example, heating a fluid, for example, raising steam in a boiler or in the combustible substance itself.
- perovskite structured materials will exhibit a high oxygen flux, such materials tend to be very fragile under operational conditions such as in the heating of a fluid. This is because the perovskite type materials will have a variable stoichiometry with respect to oxygen. In air it will have one value and in the presence of a fuel that is undergoing combustion it will have another value.
- the present invention provides a robust oxygen transport membrane that utilizes a material having a fluorite structure as an ionic conductor and that incorporates a deposit of a catalyst in an intermediate porous layer located between a dense layer and a porous support to promote oxidation of the combustible substance and thereby increase the oxygen flux that would otherwise have been obtained with the use of a fluorite structured material as an ionic conductor.
- the present invention may be characterized as a composite oxygen transport membrane comprising (i) a porous support layer comprised of an fluorite structured ionic conducting material having a porosity of greater than 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer; (ii) an intermediate porous layer often referred to as a fuel oxidation layer disposed adjacent to the porous support layer and capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed and comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; (iii) a dense separation layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the dense layer adjacent to the intermediate porous layer and also comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; and (iv) catalyst particles or a solution containing precursors of the catalyst particles
- the catalyst is preferably gadolinium doped ceria but may also be other catalysts that promote fuel oxidation.
- the composite oxygen transport membrane may also include a porous surface exchange layer or an air activation layer disposed or applied to the dense separation layer on the side opposite to the intermediate porous layer or the fuel oxidation layer. If used, the porous surface exchange layer or an air activation layer preferably has a thickness of between 10 and 40 microns and a porosity of between about 30 and 60 percent.
- the intermediate porous layer or fuel oxidation layer preferably has a thickness of between about 10 and 40 microns and a porosity of between about 20 and 50 percent whereas the dense layer has a thickness of between 10 and 50 microns.
- the porous support layer may be formed from a mixture comprising 3mol% yttria stabilized zirconia, or 3 YSZ and a polymethyl methacrylate based pore forming material or a mixture comprising 3 YSZ having a bi-modal or multimodal particle size distribution. In either embodiment, the porous support layer has a preferred thickness of between about 0.5 and 4 mm and porosity between about 20 and 40 percent.
- the intermediate porous layer comprises a mixture of about 60 percent by weight of (La u Sr v Cei_u-v)wCr x MyV z 03-8 with the remainder Zr x 'Sc y A z O2-8.
- the dense separation layer comprises a mixture of about 40 percent by weight of (La u Sr v Cei_ u _
- u is from 0.7 to 0.9
- v is from 0.1 to 0.3 and (1-u-v) is greater than or equal to zero
- w is from 0.94 to 1
- x is from 0.5 to 0.77
- M is Mn or Fe
- y is from 0.2 to 0.5
- A is Y or Ce or mixtures of Y and Ce.
- one of the preferred embodiments of the composite oxygen transport membrane includes an intermediate porous layer or fuel oxidation layer that comprises about 60 percent by weight of (La 0 .8 2 5Sro.i75)o. 6Cr 0 .76Feo. 22 5Vo.oi503-8 or
- the dense separation layer comprises about 40 percent by weight of
- the porous surface exchange layer or air activation layer is formed by a mixture of about 50 percent by weight of (La 0 . 8 Sr 0 . 2 )o. 8Mn03-8 or La 0 . 8 Sr 0 . 2 FeO 3 - ⁇ , remainder lOSclYSZ or lOSclCeSZ.
- the present invention may also be characterized as a product by process wherein the product is a composite oxygen transport membrane.
- the process comprises: (i) fabricating a porous support layer comprised of an fluorite structured ionic conducting material, the fabricating step including pore forming enhancement step such that the porous support layer has a porosity of greater than about 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer; (ii) applying an intermediate porous layer or fuel oxidation layer on the porous support layer, (iii) applying a dense separation layer on the intermediate porous layer; and (iv) introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer.
- Both the intermediate porous layer and dense separation layer are capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed.
- Both layers comprise a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively.
- the pore forming enhancement process involves several alternative techniques including mixing a polymethyl methacrylate based pore forming material with the fluorite structured ionic conducting material of the porous support layer.
- the pore forming enhancement process may further involve use of bi-modal or multi-modal particle sizes of the polymethyl methacrylate based pore forming material and/or the fluorite structured ionic conducting material of the porous support layer.
- the step of introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer may further comprise either: (a) adding catalyst particles directly to the mixture of materials used in the intermediate porous layer; or (b) applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer so that the solution infiltrates or impregnates the pores within the porous support layer and the intermediate porous layer with the solution containing catalyst precursors and heating the composite oxygen transport membrane after the solution containing catalyst precursors infiltrates the pores and to form the catalyst from the catalyst precursors.
- the present invention may also be characterized as a method of producing a catalyst containing composite oxygen transport membrane comprising the steps of: (i) forming a composite oxygen transport membrane in a sintered state, said composite oxygen transport membrane having a plurality of layers comprising a dense separation layer, a porous support layer, and an intermediate porous layer (i.e.
- the catalyst is gadolinium doped ceria and the solution is an aqueous metal ion solution containing about 20 mol% Gd(N0 3 ) 3 and 80 mol% Ce(N0 3 ) 3 that when sintered forms Gdo.8Ce 0 . 2 0 2- 8.
- Each of the dense layer and the intermediate porous layer capable of conducting oxygen ions and electrons at an elevated operational temperature to separate oxygen from an oxygen containing feed.
- the dense layer and the intermediate porous layer comprising mixtures of a fluorite structured ionic conductive material and electrically conductive materials to conduct oxygen ions and electrons, respectively.
- the porous support layer comprising a fluorite structured ionic conducting material having a porosity of greater than about 20 percent and a microstructure exhibiting
- Pores are formed within the porous support layer using a polymethyl methacrylate based pore forming material mixed with the 3 YSZ material of the porous support layer.
- the pores may be formed using bi-modal or multi-modal particle sizes of the polymethyl methacrylate based pore forming material and/or the 3YSZ material of the porous support layer.
- a pressure may be established on the second side of the porous support layer or the pores of the porous support layer and fuel oxidation layer may first be evacuated of air using a vacuum to further assist in wicking of the solution and prevent the opportunity of trapped air in the pores preventing wicking of the solution all the way through the support structure to the intermediate layer.
- FIG. 1 is a cross-sectional schematic view of a composite oxygen transport membrane element of the present invention that is fabricated in accordance with a method of the present invention
- Fig. 2 is an alternative embodiment of Fig. 1;
- Fig. 3 is an alternative embodiment of Fig. 1;
- Fig. 4 is an SEM micrograph image at lOOOx magnification showing a porous support layer comprised of 3 YSZ with walnut shells as the pore forming material;
- Fig. 5 is an SEM micrograph image at lOOOx magnification showing a porous support layer comprised of 3 YSZ with a polymethyl methacrylate (PMMA) based pore forming material in accordance with the present invention
- Fig. 6 is another SEM micrograph image at 2000x magnification showing a porous support layer comprised of 3 YSZ with a polymethyl methacrylate (PMMA) based pore forming material in accordance with the present invention.
- PMMA polymethyl methacrylate
- Fig. 7 is an SEM micrograph image at 2000x magnification showing a porous support layer comprised of 3 YSZ with multi-modal particle sizes in accordance with the present invention.
- FIG. 1 a sectional view of a composite oxygen transport membrane element 1 in accordance with the present invention is illustrated.
- composite oxygen transport membrane element 1 could be in the form of a tube or a flat plate.
- Such composite oxygen transport membrane element 1 would be one of a series of such elements situated within a device to heat a fluid such as in a boiler or other reactor having such a heating requirement.
- Composite oxygen transport membrane element 1 is provided with a dense layer 10, a porous support layer 12 and an intermediate porous layer 14 located between the dense layer 10 and the porous support layer 12.
- a preferable option is, as illustrated, to also include a porous surface exchange layer 16 in contact with the dense layer 10, opposite to the intermediate porous layer 14.
- Catalyst particles 18 are located in the intermediate porous layer 14 that are formed of a catalyst selected to promote oxidation of a combustible substance in the presence of oxygen separated by the composite membrane element 1.
- combustion substance means any substance that is capable of being oxidized, including, but not limited, to a fuel in case of a boiler, a hydrocarbon containing substance for purposes of oxidizing such substance for producing a hydrogen and carbon monoxide containing synthesis gas or the synthesis gas itself for purposes of supplying heat to, for example, a reformer.
- oxidizing as used herein and in the claims encompasses both partial and full oxidation of the substance.
- air or other oxygen containing fluid is contacted on one side of the composite oxygen transport membrane element 1 and more specifically, against the porous surface exchange layer 16 in the direction of arrowhead "A".
- the porous surface exchange layer 16 is porous and is capable of mixed conduction of oxygen ions and electrons and functions to ionize some of the oxygen.
- the oxygen ions are transported through the dense layer 10 to intermediate porous layer 14 to be distributed to pores 20 of the porous support layer 12. It should be noted that in Figs.
- the pores 20 within the porous support layer 12 are shown in an exaggerated manner.
- Some of the oxygen ions, upon passage through the dense layer will recombine into elemental oxygen.
- the recombination of the oxygen ions into elemental oxygen is accompanied by the loss of electrons that flow back through the dense layer to ionize the oxygen at the opposite surface thereof.
- a combustible substance for example a hydrogen and carbon monoxide containing synthesis gas, is contacted on one side of the porous support layer 12 located opposite to the intermediate porous layer 14 as indicated by arrowhead "B".
- the combustible substance enters pores 20, contacts the oxygen and burns through combustion supported by oxygen. The combustion is promoted by the catalyst that is present by way of catalyst particles 18.
- the presence of combustible fuel on the side of the composite oxygen ion transport membrane element 1, specifically the side of the dense layer 10 located adjacent to the intermediate porous layer 14 provides a lower partial pressure of oxygen.
- This lower partial pressure drives the oxygen ion transport as discussed above and also generates heat to heat the dense layer 10, the intermediate porous layer 14 and the porous surface exchange layer 16 up to an operational temperature at which the oxygen ions will be conducted.
- the incoming oxygen containing stream can also be pressurized to enhance the oxygen partial pressure difference between opposite sides of the composite oxygen ion transport membrane element 1. Excess heat that is generated by combustion of the combustible substance will be used in the specific application, for example, the heating of water into steam within a boiler or to meet the heating requirements for other endothermic reactions.
- the use of a single phase mixed conducting material such as a perovskite structured materials has the disadvantage of exhibiting chemical expansion, or in other words, one side of a layer, at which the oxygen ions recombine into elemental oxygen, will expand relative to the opposite side thereof. This resulting stress can cause failure of such a layer or separation of the layer from adjacent layers.
- the dense layer, the intermediate porous layer, and the porous surface exchange layer were all formed of a two phase system comprising a fluorite structured material in one phase as the ionic conductor of the oxygen ions and an electronic conducting phase that in the illustrated embodiment is a perovskite type material.
- the porous support layer 12, 12', 12" have a thickness of between about 0.5 mm and about 4.0 mm, and more preferably about 1.0 mm and are preferably formed of a fluorite structured material only with a PMMA based pore former material.
- the porous support layers 12; 12' and 12" preferably do not exhibit significant mixed conduction.
- the material used in forming the porous support layer preferably have a thermal expansion coefficient in the range 9 x 10 "6 cm/cm x K "1 and 12 x 10 "6 cm/cm x K "1 in the temperature range of 20°C to 1000°C; where "K” is the temperature in Kelvin.
- dense layers 10, 10', 10" or dense separation layers function to separate oxygen from an oxygen containing feed exposed to one surface of the oxygen ion transport membrane 10 and contains an electronic and ionic conducting phases.
- the dense separation layer also serves as a barrier of sorts to prevent mixing of the fuel on one side of the membrane with the air or oxygen containing feed stream on the other side of the membrane.
- the ionic phase is Zr x Sc y A z .0 2 - 8 ("YScZ"), where y * is from about 0.08 to about 0.3, z' is from about 0.01 to about 0.03, x'+y'+z -1 and A is Y or Ce or mixtures of Y and Ce.
- YScZ Zr x Sc y A z .0 2 - 8
- y * is from about 0.08 to about 0.3
- z' is from about 0.01 to about 0.03
- x'+y'+z -1 Y or Ce or mixtures of Y and Ce.
- the variable " ⁇ " as used in the formulas set forth below for the indicated substances, as would be known in the art would have a value that would render such substances charge neutral. It is to be noted, that since the quantity (1-u-v) can be equal to zero, cerium may not be present within an electronic phase of the present invention.
- the dense separation layer contains a mixture of 40 percent by weight
- the dense layer should be made as thin as possible and in the described embodiment has a thickness of between about 10 microns and about 50 microns.
- Porous surface exchange layers 16, 16', 16" or air activation layers are designed to enhance the surface exchange rate by enhancing the surface area of the dense layers 10, 10', 10" while providing a path for the resulting oxygen ions to diffuse through the mixed conducting oxide phase to the dense layer and for oxygen molecules to diffuse through the open pore spaces to the same.
- the porous surface exchange layer 16, 16', 16" therefore, reduces the loss of driving force in the surface exchange process and thereby increases the achievable oxygen flux.
- porous surface exchange layer is formed of a mixture of about 50 percent by weight of
- the porous surface exchange layer is a porous layer and preferably has a thickness of between about 10 microns and about 40 microns, a porosity of between about 30 percent and about 60 percent and an average pore diameter of between about 1 microns and about 4 microns.
- the intermediate porous layer 14, 14', 14" is a fuel oxidation layer and is a preferably formed of the same mixture as the dense layer 10, 10', 10" and preferably has an applied thickness of between about 10 microns and about 40 microns, a porosity of between about 25 percent and about 40 percent and an average pore diameter of between about 0.5 microns and about 3 microns.
- catalyst particles 18, 18', 18" incorporated within the intermediate porous layer 14, 14', 14" are catalyst particles 18, 18', 18".
- the catalyst particles 18, 18', 18" in the described embodiments are preferably gadolinium doped ceria ("CGO") that have a size of between about 0.1 and about 1 microns.
- the intermediate porous layers contain a mixture of about 60 percent by weight of (La 0 .825Sro.i75)o. 6Cr 0 .76Feo.225Vo.oi503-8, remainder lOSclYSZ.
- intermediate porous layer as compared with the dense layer preferably may contain iron in lieu of or in place of manganese, a lower A-site deficiency, a lower transition metal (iron) content on the B-site, and a slightly lower concentration of vanadium on the B-site.
- the porous support layer 12, 12', 12" can be formed from a past mixture by known forming techniques including extrusion techniques and freeze casting techniques. Although pores 20, 20', 20" in the porous support layer are indicated as being a regular network of non-interconnected pores, in fact there exists some degree of connection between pores towards the intermediate porous layer. In any event, the porous network and microstructure of the porous support layer should be controlled so as to promote or optimize the diffusion of the combustible substance to the intermediate porous layer and the flow of combustion products such as steam and carbon dioxide from the pores in a direction opposite to that of arrowhead "B". The porosity of porous support layers 14, 14', 14" should preferably be greater than about 20 percent for the described embodiment as well as other possible embodiments of the present invention.
- porous support layers 12, 12', 12" are preferably fabricated from 3YSZ material commercially available from various suppliers including Tosoh Corporation and its affiliates, including Tosoh USA, with an address at 3600 Gantz Road, Grove City, Ohio.
- the porous support layer 12, 12', 12" are preferably fabricated from 67wt% 3YSZ mixed together with 33wt% of a PMMA based pore forming material.
- the pore forming material is preferably a mixture comprising 30wt% carbon black with an average particle size less than or equal to about 1 micron combined with 70wt% PMMA pore formers having a narrow particle size distribution and an average particle size of between about 0.8 microns and 5.0 microns
- PMMA pore formers with a narrow particle size distribution
- further pore optimization and microstructure optimization may be realized using hollow, spherical particles as well as bi-modal or multi-modal particle size distributions of either or both of the 3YSZ materials and the PMMA based pore formers.
- bi- modal or multimodal particle size distribution of PMMA pore formers including PMMA particles with average particle diameters of 0.8 microns, 1.5 microns 3.0 microns and 5.0 microns are contemplated.
- the preferred fabrication process of the oxygen transport membrane is to form the porous support via an extrusion process and subsequently bisque firing of the extruded porous support.
- the porous support is then coated with the active membrane layers, including the intermediate porous layer and the dense layer, after which the coated porous support assembly is dried and fired.
- the coated porous support assembly is then co-sintered at a final optimized sintering temperature and conditions.
- An important aspect or characteristic of the materials or combination of materials selected for the porous support is its ability to mitigate creep while providing enough strength to be used in the oxygen transport membrane applications, which can reach temperatures above 1000°C and very high loads. It is also important to select porous support materials that when sintered will demonstrate shrinkages that match or closely approximate the shrinkage of the other layers of the oxygen transport membrane, including the dense separation layer, and intermediate porous layer.
- the final optimized sintering temperature and conditions are selected so as to match or closely approximate the shrinkage profiles of the porous support to the shrinkage profiles of the dense separation layer while minimizing any chemical interaction between the materials of the active membrane layers, the materials in the porous support layer, and the sintering atmosphere.
- Too high of a final optimized sintering temperature tends to promote unwanted chemical interactions between the membrane materials, the porous support, and surrounding sintering atmosphere.
- Reducing atmospheres during sintering using blends of hydrogen and nitrogen gas atmosphere can be used to reduce unwanted chemical reactions but tend to be more costly techniques compared to sintering in air.
- an advantage to the oxygen transport membrane of the disclosed embodiments is that some may be fully sintered in air.
- a dense separation layer comprising (Lao. 8 Sro.2)o. 5 Cr 0 . 5 Feo.503_8 and lOSclCeSZ appears to sinters to full density in air at about 1400°C tol430°C.
- Fig. 6 and Fig. 7 also show SEM micrographs (2000x magnification) of a porous support microstructure comprised of a single average particle size 3YSZ material with PMMA based pore forming material of 1.5 micron particle size (Fig. 6) and a porous support comprised of 3YSZ having different (e.g. bi-modal or multi-modal) average particle sizes (Fig. 7).
- Both porous support microstructures shown in Figs. 6 and 7 exhibited higher strength, lower creep, and improved diffusion efficiency compared to a 3YSZ porous support having a single average particle size 3YSZ particle size and larger size walnut shell pore formers (see Fig. 4).
- porous support layers 12, 12', 12" preferably have a permeability of between about 0.25 Darcy and about 0.5 Darcy. Standard procedures for measuring the permeability of a substrate in terms of Darcy number are outlined in ISO 4022. Porous support layers 12, 12', 12" also preferably have a thickness of between about 0.5 mm and about 4 mm and an average pore size diameter of no greater than about 50 microns. Additionally, the porous support layers also have catalyst particles 18, 18', 18" located within pores 20, 20', 20" and preferably adjacent to the intermediate porous layer for purposes of also promoting combustible substance oxidation.
- catalyst particles both within the intermediate porous layer and within the porous support layer provides enhancement of oxygen flux and therefore generation of more heat via combustion that can be obtained by either providing catalyst particles within solely the intermediate porous layer or the porous support layer alone. It is to be noted that to a lesser extent, catalyst particles can also be located in region of the pores that are more remote from the intermediate porous layer, and therefore do not participate in promoting fuel oxidation. However, the bulk of catalyst in a composite oxygen transport element of the present invention is, however, preferably located in the intermediate porous layer and within the pores adjacent or proximate to the intermediate porous layer.
- the porous support 12, 12', 12" is first formed in a manner known in the art and as set forth in the references discussed above.
- standard ceramic extrusion techniques can be employed to produce a porous support layer or structure in a tube configuration in a green state and then subjected to a bisque firing at 1050°C for about 4 hours to achieve reasonable strength for further handling.
- the resulting tube can be checked or tested for targeted porosity, strength, creep resistance and, most importantly, diffusivity characteristics.
- a freeze cast supporting structure could be formed as discussed in "Freeze-Casting of Porous Ceramics: A Review of Current
- intermediate porous layer 14, 14', 14" is then formed.
- a mixture of about 34 grams of powders having electronic and ionic phases, LSCMV and lOSclYSZ, respectively, is prepared so that the mixture contains generally equal proportions by volume of LSCMV and lOSclYSZ.
- the catalyst particles such as CGO
- the catalyst particles are so incorporated into the electronic phase LSCMV by forming deposits of such particles on the electronic phase, for example, by precipitation.
- it is more preferable to form the catalyst particles within the intermediate porous layer by wicking a solution containing catalyst precursors through the porous support layer towards the intermediate porous layer after application of the membrane active layers as described in more detail below.
- the electronic phase particles are each about 0.3 microns prior to firing and the catalyst particles are about 0.1 microns or less and are present in a ratio by weight of about 10wt%.
- 100 grams of toluene, 20 grams of the binder of the type mentioned above, 400 grams of 1.5 mm diameter YSZ grinding media are added.
- the mixture is then milled for about 6 hours to form a slurry (d 5 o of about 0.34 ⁇ ).
- the dense layer 10, 10', 10" is then applied.
- a mixture weighing about 40 grams is prepared that contains the same powders as used in forming the intermediate porous layer, discussed above, except that the ratio between LSCMV and lOSclYSZ is about 40/60 by volume, 2.4 grams of cobalt nitrate ⁇ Co(N0 3 )2.6H 2 0 ⁇ , 95 grams of toluene, 5 grams of ethanol, 20 grams of the binder identified above, 400 grams of 1.5 mm diameter YSZ grinding media are then added to the mixture and the same is milled for about 10 hours to form a slurry (d 5 o ⁇ 0.34 ⁇ ).
- toluene and binder are added to the slurry and mixed for about 1.5 and about 2 hours.
- the inner wall of the tube is then coated by pouring the slurry, holding once for about 10 seconds and pouring out the residual back to the bottle.
- the coated green tube is then stored dry prior to firing the layers in a controlled environment.
- the coated green tube is then placed on a C-setter in a horizontal tube furnace and porous alumina tubes impregnated with chromium nitrate are placed close to the coated tube to saturate the environment with chromium vapor.
- the tubes are heated in static air to about 800°C for binder burnout and, if necessary, the sintering environment is switched to an atmosphere of a saturated nitrogen mixture (nitrogen and water vapor) that contains about 4 percent by volume of hydrogen to allow the vanadium containing electronic conducting perovskite structured materials to properly sinter.
- the tube is held at about 1350°C to 1430°C for about 8 hours and then cooled in nitrogen to complete the sintering of the materials.
- the sintered tube is then checked for leaks wherein the helium leak rates should be lower than 10 ⁇ 7 Pa.
- Surface exchange layer 16 is then applied.
- a mixture of powders is prepared that contains about 35g of equal amounts of ionic and electronic phases having chemical formulas of Zr 0 .8oSco.i8Yo.o202-8 and Lao.8Sr 0 .2Fe0 3 _8, respectively.
- To this mixture about 100 grams of toluene, 20 grams of the binder identified above, about 400 grams of 1.5 mm diameter YSZ grinding media are added and the resultant mixture is milled for about 14 hours to form a slurry (d 50 ⁇ 0.4 ⁇ ). About six grams of carbon black are added to the slurry and milled for additional 2 hours.
- a mixture of about 10 grams of toluene and about 10 grams of the binder are then added to the slurry and mixed for between about 1.5 and about 2 hours.
- the inner wall of the tube is then coated by pouring the slurry, holding twice for about 10 seconds and then pouring out the residual back to the bottle.
- the coated tube is then dried and fired at 1100°C for two hours in air.
- the structure formed in the manner described above is in a fully sintered state and the catalyst is then further applied by wicking a solution containing catalyst precursors in the direction of arrowhead B at the side of the porous support opposite to the intermediate porous layer.
- the solution can be an aqueous metal ion solution containing about 20 mol%
- a pressure can be established on the side of the porous support layer to assist in the infiltration of the solution.
- the pores can first be evacuated of air using a vacuum to further assist in wicking of the solution and prevent the opportunity of trapped air in the pores preventing wicking of the solution all the way through the porous support layer to the intermediate porous layer.
- the resulting composite oxygen transport membrane 1 in such state can be directly placed into service or further fired prior to being placed into service so that the catalyst particles, in this case Ce 0 .8Gdo. 2 0 2- 8 are formed in the porous support layer adjacent to the intermediate porous layer and as described above, within the intermediate porous layer itself.
- the firing to form Ce 0 .8Gdo. 2 0 2- 8 would take place at a temperature of about 850°C and would take about 1 hour to form the catalyst particles.
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Abstract
A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a microstructure exhibiting substantially uniform pore size distribution as a result of using PMMA pore forming materials or a bi-modal particle size distribution of the porous support layer materials. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.
Description
CATALYST CONTAINING OXYGEN TRANSPORT MEMBRANE
U.S. Government Rights
[0001] The invention disclosed and claimed herein was made with United States Government support under Cooperative Agreement number DE-FC26-07NT43088 awarded by the U.S. Department of Energy. The United States Government has certain rights in this invention.
Field of the Invention
[0002] The present invention relates to a composite oxygen transport membrane in which catalyst particles, selected to promote oxidation of a combustible substance, are located within an intermediate porous layer that is in turn located between a dense layer and a porous support layer and within the porous support and a method of applying the catalyst to the intermediate porous layer and the porous support layer through wicking of catalyst precursors through the porous support layer to the intermediate porous layer.
Background
[0003] Oxygen transport membranes function by transporting oxygen ions through a material that is capable of conducting oxygen ions and electrons at elevated temperatures. Such materials can be mixed conducting in that they conduct both oxygen ions and electrons or a mixture of materials that include an ionic conductor capable of primarily conducting oxygen ions and an electronic conductor with the primary function of transporting the electrons. Typical mixed conductors are formed from doped perovskite structured materials. In case of a mixture of materials, the ionic conductor can be yttrium or scandium stabilized zirconia and the electronic conductor can be a perovskite structured material that will transport electrons, a metal or metal alloy or a mixture of the perovskite type material, the metal or metal alloy.
[0004] When a partial pressure difference of oxygen is applied on opposite sides of such a membrane, oxygen ions will ionize on one surface of the membrane and emerge on the opposite side of the membrane and recombine into elemental oxygen. The free electrons resulting from the combination will be transported back through the membrane to ionize the oxygen. The partial pressure difference can be produced by providing the oxygen containing feed to the membrane at a positive pressure or by supplying a combustible substance to the
side of the membrane opposing the oxygen containing feed or a combination of the two methods.
[0005] Typically, oxygen transport membranes are composite structures that include a dense layer composed of the mixed conductor or the two phases of materials and one or more porous supporting layers. Since the resistance to oxygen ion transport is dependent on the thickness of the membrane, the dense layer is made as thin as possible and therefore must be supported. Another limiting factor to the performance of an oxygen transport membrane concerns the supporting layers that, although can be active, that is oxygen ion or electron conducting, the layers themselves can consist of a network of interconnected pores that can limit diffusion of the oxygen or fuel or other substance through the membrane to react with the oxygen. Therefore, such support layers are typically fabricated with a graded porosity in which the pore size decreases in a direction taken towards the dense layer or are made highly porous throughout. The high porosity, however, tends to weaken such a structure.
[0006] U.S. Patent No. 7,229,537 attempts to solve such problems by providing a support with cylindrical or conical pores that are not connected and an intermediate porous layer located between the dense layer and the support that distributes the oxygen to the pores within the support. Porous supports can also be made by freeze casting techniques, as described in 10, No. 3, Advanced Engineering Materials, "Freeze-Casting of Porous
Ceramics: A Review of Current Achievements and Issues" (2008) by Deville, pp. 155-169. In freeze casting, a liquid suspension is frozen. The frozen liquid phase is then sublimated from a solid to a vapor under reduced pressure. The resulting structure is sintered to consolidate and density the structure. This leads to a porous structure having pores extending in one direction and that have a low toruosity. Such supports have been used to form electrode layers in solid oxide fuel cells. In addition to the porous support layers, a porous surface exchange layer can be located on the opposite side of the dense layer to enhance reduction of the oxygen into oxygen ions. Such a composite membrane is illustrated in US Patent No. 7,556,676 that utilizes two phase materials for the dense layer, the porous surface exchange layer and the intermediate porous layer. These layers are supported on a porous support that can be formed of zirconia.
[0007] As mentioned above, the oxygen partial pressure difference can be created by combusting a fuel or other combustible substance with the separated oxygen. The resulting
heat will heat the oxygen transport membrane up to operational temperature and excess heat can be used for other purposes, for example, heating a fluid, for example, raising steam in a boiler or in the combustible substance itself. While perovskite structured materials will exhibit a high oxygen flux, such materials tend to be very fragile under operational conditions such as in the heating of a fluid. This is because the perovskite type materials will have a variable stoichiometry with respect to oxygen. In air it will have one value and in the presence of a fuel that is undergoing combustion it will have another value. The end result is that at the fuel side, the material will tend to expand relative to the air side and a dense layer will therefore, tend to fracture. In order to overcome this problem, a mixture of materials can be used in which an ionic conductor is provided to conduct the oxygen ions and an electronic conductor is used to conduct the electrons. Where the ionic conductor is a fluorite structured material, this chemical expansion is restrained, and therefore the membrane will be less susceptible to structural failure. However, the problem with the use of a fluorite structure material, such as a stabilized zirconia, is that such a material has lower oxygen ion conductivity. As a result, far more oxygen transport membrane elements are required for such a dual phase type of membrane as compared with one that is formed from a single phase perovskite type material.
[0008] As will be discussed, the present invention provides a robust oxygen transport membrane that utilizes a material having a fluorite structure as an ionic conductor and that incorporates a deposit of a catalyst in an intermediate porous layer located between a dense layer and a porous support to promote oxidation of the combustible substance and thereby increase the oxygen flux that would otherwise have been obtained with the use of a fluorite structured material as an ionic conductor.
Summary of the Invention
[0009] The present invention may be characterized as a composite oxygen transport membrane comprising (i) a porous support layer comprised of an fluorite structured ionic conducting material having a porosity of greater than 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer; (ii) an intermediate porous layer often referred to as a fuel oxidation layer disposed adjacent to the porous support layer and capable of conducting oxygen ions and electrons to separate
oxygen from an oxygen containing feed and comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; (iii) a dense separation layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the dense layer adjacent to the intermediate porous layer and also comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; and (iv) catalyst particles or a solution containing precursors of the catalyst particles located in pores of the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer. The catalyst is preferably gadolinium doped ceria but may also be other catalysts that promote fuel oxidation. The composite oxygen transport membrane may also include a porous surface exchange layer or an air activation layer disposed or applied to the dense separation layer on the side opposite to the intermediate porous layer or the fuel oxidation layer. If used, the porous surface exchange layer or an air activation layer preferably has a thickness of between 10 and 40 microns and a porosity of between about 30 and 60 percent.
[0010] The intermediate porous layer or fuel oxidation layer preferably has a thickness of between about 10 and 40 microns and a porosity of between about 20 and 50 percent whereas the dense layer has a thickness of between 10 and 50 microns. The porous support layer may be formed from a mixture comprising 3mol% yttria stabilized zirconia, or 3 YSZ and a polymethyl methacrylate based pore forming material or a mixture comprising 3 YSZ having a bi-modal or multimodal particle size distribution. In either embodiment, the porous support layer has a preferred thickness of between about 0.5 and 4 mm and porosity between about 20 and 40 percent.
[0011] Broadly characterizing the preferred embodiments of the composite oxygen transport membrane, the intermediate porous layer comprises a mixture of about 60 percent by weight of (LauSrvCei_u-v)wCrxMyVz03-8 with the remainder Zrx'ScyAzO2-8. Similarly, the dense separation layer comprises a mixture of about 40 percent by weight of (LauSrvCei_u_
v)wCrxMyVz03-8 with the remainder ZrxScy'AzO2-8. In the above formulations, u is from 0.7 to 0.9, v is from 0.1 to 0.3 and (1-u-v) is greater than or equal to zero, w is from 0.94 to 1, x is
from 0.5 to 0.77, M is Mn or Fe, y is from 0.2 to 0.5, z is from 0 to 0.03, and x+y+z =1, where y' is from 0.08 to 0.3, z' is from 0.01 to 0.03, x'+y'+z -1 and A is Y or Ce or mixtures of Y and Ce. The porous surface exchange layer or air activation layer, if employed, can be is formed by a mixture of about 50 percent by weight of (Lax"'Sri_x"')y"'M03_8, where x'" is from 0.2 to 0.9, y'" is from 0.95 to 1, M is Mn or Fe, with the remainder Zrx iv Scy ivAz iv02_8, where yiv is from 0.08 to 0.3, ziv is from 0.01 to 0.03, xiv+yiv+ziv=l and A is Y, Ce or mixtures thereof.
[0012] More specifically, one of the preferred embodiments of the composite oxygen transport membrane includes an intermediate porous layer or fuel oxidation layer that comprises about 60 percent by weight of (La0.825Sro.i75)o. 6Cr0.76Feo.225Vo.oi503-8 or
(La0.8Sro.2)o. 5Cr0.7Feo.303-8 with the remainder lOSclYSZ or lOSclCeSZ. Similarly, the dense separation layer comprises about 40 percent by weight of
(La0.825Sro.i75)o.94Cro.72Mn0.26Vo.o203-8 or (La0.8Sr0.2)0.95Cr0.5Fe0.5O3-8, with the remainder lOSclYSZ or lOSclCeYSZ. The porous surface exchange layer or air activation layer is formed by a mixture of about 50 percent by weight of (La0.8Sr0.2)o. 8Mn03-8 or La0.8Sr0.2FeO3- δ, remainder lOSclYSZ or lOSclCeSZ.
[0013] The present invention may also be characterized as a product by process wherein the product is a composite oxygen transport membrane. The process comprises: (i) fabricating a porous support layer comprised of an fluorite structured ionic conducting material, the fabricating step including pore forming enhancement step such that the porous support layer has a porosity of greater than about 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer; (ii) applying an intermediate porous layer or fuel oxidation layer on the porous support layer, (iii) applying a dense separation layer on the intermediate porous layer; and (iv) introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer.
[0014] Both the intermediate porous layer and dense separation layer are capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed.
Both layers comprise a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively.
[0015] The pore forming enhancement process involves several alternative techniques including mixing a polymethyl methacrylate based pore forming material with the fluorite structured ionic conducting material of the porous support layer. In addition or alternatively, the pore forming enhancement process may further involve use of bi-modal or multi-modal particle sizes of the polymethyl methacrylate based pore forming material and/or the fluorite structured ionic conducting material of the porous support layer.
[0016] The step of introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer may further comprise either: (a) adding catalyst particles directly to the mixture of materials used in the intermediate porous layer; or (b) applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer so that the solution infiltrates or impregnates the pores within the porous support layer and the intermediate porous layer with the solution containing catalyst precursors and heating the composite oxygen transport membrane after the solution containing catalyst precursors infiltrates the pores and to form the catalyst from the catalyst precursors.
[0017] Finally, the present invention may also be characterized as a method of producing a catalyst containing composite oxygen transport membrane comprising the steps of: (i) forming a composite oxygen transport membrane in a sintered state, said composite oxygen transport membrane having a plurality of layers comprising a dense separation layer, a porous support layer, and an intermediate porous layer (i.e. fuel oxidation layer) located between the dense separation layer and the porous support layer; (ii) applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer, the catalyst precursors selected to produce a catalyst capable of promoting oxidation of the combustible substance in the presence of the separated oxygen; (iii) infiltrating or impregnating the porous support layer with the solution so that the solution wicks through the pores of the porous support layer and at least partially infiltrates or impregnates the intermediate porous layer (i.e. fuel oxidation layer), and (iv) heating the composite oxygen transport membrane after infiltrating the pores within the porous support layer and the intermediate porous layer such that the catalyst is formed from the catalyst
precursors. Preferably, the catalyst is gadolinium doped ceria and the solution is an aqueous metal ion solution containing about 20 mol% Gd(N03)3 and 80 mol% Ce(N03)3 that when sintered forms Gdo.8Ce0.202-8.
[0018] Each of the dense layer and the intermediate porous layer capable of conducting oxygen ions and electrons at an elevated operational temperature to separate oxygen from an oxygen containing feed. The dense layer and the intermediate porous layer comprising mixtures of a fluorite structured ionic conductive material and electrically conductive materials to conduct oxygen ions and electrons, respectively.
[0019] The porous support layer comprising a fluorite structured ionic conducting material having a porosity of greater than about 20 percent and a microstructure exhibiting
substantially uniform pore size distribution throughout the porous support layer. Pores are formed within the porous support layer using a polymethyl methacrylate based pore forming material mixed with the 3 YSZ material of the porous support layer. In addition or alternatively, the pores may be formed using bi-modal or multi-modal particle sizes of the polymethyl methacrylate based pore forming material and/or the 3YSZ material of the porous support layer.
[0020] To aid in the infiltration or impregnation process, a pressure may be established on the second side of the porous support layer or the pores of the porous support layer and fuel oxidation layer may first be evacuated of air using a vacuum to further assist in wicking of the solution and prevent the opportunity of trapped air in the pores preventing wicking of the solution all the way through the support structure to the intermediate layer.
Brief Description of the Drawings
[0021] While the specification concludes with claims distinctly pointing out the subject matter that Applicants regard as their invention, it is believed that the invention will be better understood when taken in connection with the accompanying drawings in which:
[0022] Fig. 1 is a cross-sectional schematic view of a composite oxygen transport membrane element of the present invention that is fabricated in accordance with a method of the present invention;
[0023] Fig. 2 is an alternative embodiment of Fig. 1;
[0024] Fig. 3 is an alternative embodiment of Fig. 1;
[0025] Fig. 4 is an SEM micrograph image at lOOOx magnification showing a porous support layer comprised of 3 YSZ with walnut shells as the pore forming material;
[0026] Fig. 5 is an SEM micrograph image at lOOOx magnification showing a porous support layer comprised of 3 YSZ with a polymethyl methacrylate (PMMA) based pore forming material in accordance with the present invention;
[0027] Fig. 6 is another SEM micrograph image at 2000x magnification showing a porous support layer comprised of 3 YSZ with a polymethyl methacrylate (PMMA) based pore forming material in accordance with the present invention; and
[0028] Fig. 7 is an SEM micrograph image at 2000x magnification showing a porous support layer comprised of 3 YSZ with multi-modal particle sizes in accordance with the present invention.
Detailed Description
[0029] With reference to Fig. 1, a sectional view of a composite oxygen transport membrane element 1 in accordance with the present invention is illustrated. As could be appreciated by those skilled in the art, such composite oxygen transport membrane element 1 could be in the form of a tube or a flat plate. Such composite oxygen transport membrane element 1 would be one of a series of such elements situated within a device to heat a fluid such as in a boiler or other reactor having such a heating requirement.
[0030] Composite oxygen transport membrane element 1 is provided with a dense layer 10, a porous support layer 12 and an intermediate porous layer 14 located between the dense layer 10 and the porous support layer 12. A preferable option is, as illustrated, to also include a porous surface exchange layer 16 in contact with the dense layer 10, opposite to the intermediate porous layer 14. Catalyst particles 18 are located in the intermediate porous layer 14 that are formed of a catalyst selected to promote oxidation of a combustible substance in the presence of oxygen separated by the composite membrane element 1. It is to be noted that the term "combustible substance" as used herein and in the claims means any substance that is capable of being oxidized, including, but not limited, to a fuel in case of a boiler, a hydrocarbon containing substance for purposes of oxidizing such substance for producing a hydrogen and carbon monoxide containing synthesis gas or the synthesis gas itself for purposes of supplying heat to, for example, a reformer. As such the term,
"oxidizing" as used herein and in the claims encompasses both partial and full oxidation of the substance.
[0031] Operationally, air or other oxygen containing fluid is contacted on one side of the composite oxygen transport membrane element 1 and more specifically, against the porous surface exchange layer 16 in the direction of arrowhead "A". The porous surface exchange layer 16 is porous and is capable of mixed conduction of oxygen ions and electrons and functions to ionize some of the oxygen. The oxygen that is not ionized at and within the porous surface exchange layer 16, similarly, also ionizes at the adjacent surface of the dense layer 10 which is also capable of such mixed conduction of oxygen ions and electrons. The oxygen ions are transported through the dense layer 10 to intermediate porous layer 14 to be distributed to pores 20 of the porous support layer 12. It should be noted that in Figs. 1-3, the pores 20 within the porous support layer 12 are shown in an exaggerated manner. Some of the oxygen ions, upon passage through the dense layer will recombine into elemental oxygen. The recombination of the oxygen ions into elemental oxygen is accompanied by the loss of electrons that flow back through the dense layer to ionize the oxygen at the opposite surface thereof.
[0032] At the same time, a combustible substance, for example a hydrogen and carbon monoxide containing synthesis gas, is contacted on one side of the porous support layer 12 located opposite to the intermediate porous layer 14 as indicated by arrowhead "B". The combustible substance enters pores 20, contacts the oxygen and burns through combustion supported by oxygen. The combustion is promoted by the catalyst that is present by way of catalyst particles 18.
[0033] The presence of combustible fuel on the side of the composite oxygen ion transport membrane element 1, specifically the side of the dense layer 10 located adjacent to the intermediate porous layer 14 provides a lower partial pressure of oxygen. This lower partial pressure drives the oxygen ion transport as discussed above and also generates heat to heat the dense layer 10, the intermediate porous layer 14 and the porous surface exchange layer 16 up to an operational temperature at which the oxygen ions will be conducted. In specific applications, the incoming oxygen containing stream can also be pressurized to enhance the oxygen partial pressure difference between opposite sides of the composite oxygen ion transport membrane element 1. Excess heat that is generated by combustion of the
combustible substance will be used in the specific application, for example, the heating of water into steam within a boiler or to meet the heating requirements for other endothermic reactions.
[0034] In the embodiments described with reference to Figs. 1-3, the use of a single phase mixed conducting material such as a perovskite structured materials has the disadvantage of exhibiting chemical expansion, or in other words, one side of a layer, at which the oxygen ions recombine into elemental oxygen, will expand relative to the opposite side thereof. This resulting stress can cause failure of such a layer or separation of the layer from adjacent layers. In order to avoid this, the dense layer, the intermediate porous layer, and the porous surface exchange layer were all formed of a two phase system comprising a fluorite structured material in one phase as the ionic conductor of the oxygen ions and an electronic conducting phase that in the illustrated embodiment is a perovskite type material. In the described embodiments, the porous support layer 12, 12', 12" have a thickness of between about 0.5 mm and about 4.0 mm, and more preferably about 1.0 mm and are preferably formed of a fluorite structured material only with a PMMA based pore former material. As such, the porous support layers 12; 12' and 12" preferably do not exhibit significant mixed conduction. The material used in forming the porous support layer preferably have a thermal expansion coefficient in the range 9 x 10"6 cm/cm x K"1 and 12 x 10"6 cm/cm x K"1 in the temperature range of 20°C to 1000°C; where "K" is the temperature in Kelvin.
[0035] As discussed above, dense layers 10, 10', 10" or dense separation layers function to separate oxygen from an oxygen containing feed exposed to one surface of the oxygen ion transport membrane 10 and contains an electronic and ionic conducting phases. The dense separation layer also serves as a barrier of sorts to prevent mixing of the fuel on one side of the membrane with the air or oxygen containing feed stream on the other side of the membrane. As discussed above, the electronic phase in the dense layer is (LauSrvCei_u_ v)wCrxMyVz03-8 where u is from about 0.7 to about 0.9, v is from about 0.1 to about 0.3 and (1-u-v) is greater than or equal to zero, w is from about 0.94 to about 1, x is from about 0.5 to about 0.77, M is Mn or Fe, y is from about 0.2 to about 0.5, z is from about 0 to about 0.03, and x+y+z =1 ("LSCMV"). The ionic phase is Zrx ScyAz.02-8 ("YScZ"), where y* is from about 0.08 to about 0.3, z' is from about 0.01 to about 0.03, x'+y'+z -1 and A is Y or Ce or mixtures of Y and Ce. The variable "δ" as used in the formulas set forth below for the
indicated substances, as would be known in the art would have a value that would render such substances charge neutral. It is to be noted, that since the quantity (1-u-v) can be equal to zero, cerium may not be present within an electronic phase of the present invention.
Preferably, the dense separation layer contains a mixture of 40 percent by weight
(La0.8Sro.2)o. 5Cr0.5Feo.503-8, remainder lOSclCeYSZ; or alternatively about 40 percent by weight of (Lao.825Sro.i75)o.94Cro.72Mn0.26Vo.o203-8, remainder lOSclYSZ. As also mentioned above, in order to reduce the resistance to oxygen ion transport, the dense layer should be made as thin as possible and in the described embodiment has a thickness of between about 10 microns and about 50 microns.
[0036] Porous surface exchange layers 16, 16', 16" or air activation layers are designed to enhance the surface exchange rate by enhancing the surface area of the dense layers 10, 10', 10" while providing a path for the resulting oxygen ions to diffuse through the mixed conducting oxide phase to the dense layer and for oxygen molecules to diffuse through the open pore spaces to the same. The porous surface exchange layer 16, 16', 16" therefore, reduces the loss of driving force in the surface exchange process and thereby increases the achievable oxygen flux. As indicated above, it also can be a two-phase mixture containing an electronic conductor composed of (Lax"'Sri_x"')y"'M03-8, where x'" is from about 0.2 to about 0.9, y'" is from about 0.95 to 1 , M is Mn or Fe; and an ionic conductor composed of Zrx lv Scy ινΑζ ινθ2_δ, where ylv is from about 0.08 to about 0.3, zlv is from about 0.01 to about 0.03, xlv+ylv+zlv=l and A is Y, Ce or mixtures of Y and Ce. In the described embodiments, porous surface exchange layer is formed of a mixture of about 50 percent by weight of
(La0.8Sr0.2)o. 8Mn03-8, remainder lOSclYSZ. The porous surface exchange layer is a porous layer and preferably has a thickness of between about 10 microns and about 40 microns, a porosity of between about 30 percent and about 60 percent and an average pore diameter of between about 1 microns and about 4 microns.
[0037] The intermediate porous layer 14, 14', 14" is a fuel oxidation layer and is a preferably formed of the same mixture as the dense layer 10, 10', 10" and preferably has an applied thickness of between about 10 microns and about 40 microns, a porosity of between about 25 percent and about 40 percent and an average pore diameter of between about 0.5 microns and about 3 microns.
[0038] In addition, incorporated within the intermediate porous layer 14, 14', 14" are catalyst particles 18, 18', 18". The catalyst particles 18, 18', 18" in the described embodiments are preferably gadolinium doped ceria ("CGO") that have a size of between about 0.1 and about 1 microns. Preferably, the intermediate porous layers contain a mixture of about 60 percent by weight of (La0.825Sro.i75)o. 6Cr0.76Feo.225Vo.oi503-8, remainder lOSclYSZ. It is to be noted that intermediate porous layer as compared with the dense layer preferably may contain iron in lieu of or in place of manganese, a lower A-site deficiency, a lower transition metal (iron) content on the B-site, and a slightly lower concentration of vanadium on the B-site. It has been found that the presence of iron in the intermediate porous layer aids the combustion process and that the presence of manganese at higher concentration and a higher A-site deficiency in the dense layer improves electronic conductivity and sintering kinetics. If needed, a higher concentration of vanadium should be present in the dense layer because vanadium functions as a sintering aid, and is required to promote densification of the dense layer. Vanadium, if any, is required in lesser extent in the intermediate porous layer in order to match the shrinkage and thermal expansion
characteristics with the dense layer.
[0039] The porous support layer 12, 12', 12" can be formed from a past mixture by known forming techniques including extrusion techniques and freeze casting techniques. Although pores 20, 20', 20" in the porous support layer are indicated as being a regular network of non-interconnected pores, in fact there exists some degree of connection between pores towards the intermediate porous layer. In any event, the porous network and microstructure of the porous support layer should be controlled so as to promote or optimize the diffusion of the combustible substance to the intermediate porous layer and the flow of combustion products such as steam and carbon dioxide from the pores in a direction opposite to that of arrowhead "B". The porosity of porous support layers 14, 14', 14" should preferably be greater than about 20 percent for the described embodiment as well as other possible embodiments of the present invention.
[0040] The porous support layers 12, 12', 12" are preferably fabricated from 3YSZ material commercially available from various suppliers including Tosoh Corporation and its affiliates, including Tosoh USA, with an address at 3600 Gantz Road, Grove City, Ohio.
Advancements in the performance of the porous support layers have been realized when
combining the Tosoh 3YSZ materials with fugitive organic pore former materials, specifically polymethyl methacrylate (PMMA). In the preferred embodiments, the porous support layer 12, 12', 12" are preferably fabricated from 67wt% 3YSZ mixed together with 33wt% of a PMMA based pore forming material. The pore forming material is preferably a mixture comprising 30wt% carbon black with an average particle size less than or equal to about 1 micron combined with 70wt% PMMA pore formers having a narrow particle size distribution and an average particle size of between about 0.8 microns and 5.0 microns Although use of the PMMA pore formers with a narrow particle size distribution have shown promising results, further pore optimization and microstructure optimization may be realized using hollow, spherical particles as well as bi-modal or multi-modal particle size distributions of either or both of the 3YSZ materials and the PMMA based pore formers. For example, bi- modal or multimodal particle size distribution of PMMA pore formers, including PMMA particles with average particle diameters of 0.8 microns, 1.5 microns 3.0 microns and 5.0 microns are contemplated.
[0041] As described in more detail below, the preferred fabrication process of the oxygen transport membrane is to form the porous support via an extrusion process and subsequently bisque firing of the extruded porous support. The porous support is then coated with the active membrane layers, including the intermediate porous layer and the dense layer, after which the coated porous support assembly is dried and fired. The coated porous support assembly is then co-sintered at a final optimized sintering temperature and conditions.
[0042] An important aspect or characteristic of the materials or combination of materials selected for the porous support is its ability to mitigate creep while providing enough strength to be used in the oxygen transport membrane applications, which can reach temperatures above 1000°C and very high loads. It is also important to select porous support materials that when sintered will demonstrate shrinkages that match or closely approximate the shrinkage of the other layers of the oxygen transport membrane, including the dense separation layer, and intermediate porous layer.
[0043] In a preferred embodiment, the final optimized sintering temperature and conditions are selected so as to match or closely approximate the shrinkage profiles of the porous support to the shrinkage profiles of the dense separation layer while minimizing any chemical interaction between the materials of the active membrane layers, the materials in the porous
support layer, and the sintering atmosphere. Too high of a final optimized sintering temperature tends to promote unwanted chemical interactions between the membrane materials, the porous support, and surrounding sintering atmosphere. Reducing atmospheres during sintering using blends of hydrogen and nitrogen gas atmosphere can be used to reduce unwanted chemical reactions but tend to be more costly techniques compared to sintering in air. Thus, an advantage to the oxygen transport membrane of the disclosed embodiments is that some may be fully sintered in air. For example, a dense separation layer comprising (Lao.8Sro.2)o. 5Cr0.5Feo.503_8 and lOSclCeSZ appears to sinters to full density in air at about 1400°C tol430°C.
[0044] As shown in Fig. 5, the use of PMMA pore former produced oxygen transport membranes with both high porosity and a substantially uniform pore size distribution throughout the porous support layer. Helium leak rates were consistently lower for coated porous supports comprised of 3YSZ with PMMA based pore forming materials (i.e. as low as 4x 10~9 atm'cc/sec) compared to helium leak rates for prior art coated porous supports comprised of 3YSZ and walnut shell pore formers. Figs. 4 and 5 are SEM micrographs
(lOOOx magnification) which show greater pore uniformity and overall porous support layer microstructure uniformity when using a porous support comprised of 3 YSZ with PMMA based pore forming material (Fig. 5) than a porous support comprised of 3YSZ and walnut shell pore formers (Fig. 4).
[0045] Fig. 6 and Fig. 7 also show SEM micrographs (2000x magnification) of a porous support microstructure comprised of a single average particle size 3YSZ material with PMMA based pore forming material of 1.5 micron particle size (Fig. 6) and a porous support comprised of 3YSZ having different (e.g. bi-modal or multi-modal) average particle sizes (Fig. 7). Both porous support microstructures shown in Figs. 6 and 7 exhibited higher strength, lower creep, and improved diffusion efficiency compared to a 3YSZ porous support having a single average particle size 3YSZ particle size and larger size walnut shell pore formers (see Fig. 4).
[0046] It has also been observed that the disclosed porous support layers 12, 12', 12" preferably have a permeability of between about 0.25 Darcy and about 0.5 Darcy. Standard procedures for measuring the permeability of a substrate in terms of Darcy number are outlined in ISO 4022. Porous support layers 12, 12', 12" also preferably have a thickness of between about 0.5 mm and about 4 mm and an average pore size diameter of no greater than
about 50 microns. Additionally, the porous support layers also have catalyst particles 18, 18', 18" located within pores 20, 20', 20" and preferably adjacent to the intermediate porous layer for purposes of also promoting combustible substance oxidation. The presence of the catalyst particles both within the intermediate porous layer and within the porous support layer provides enhancement of oxygen flux and therefore generation of more heat via combustion that can be obtained by either providing catalyst particles within solely the intermediate porous layer or the porous support layer alone. It is to be noted that to a lesser extent, catalyst particles can also be located in region of the pores that are more remote from the intermediate porous layer, and therefore do not participate in promoting fuel oxidation. However, the bulk of catalyst in a composite oxygen transport element of the present invention is, however, preferably located in the intermediate porous layer and within the pores adjacent or proximate to the intermediate porous layer.
[0047] In forming a composite oxygen transport membrane element in accordance with the present invention, the porous support 12, 12', 12" is first formed in a manner known in the art and as set forth in the references discussed above. For example, standard ceramic extrusion techniques can be employed to produce a porous support layer or structure in a tube configuration in a green state and then subjected to a bisque firing at 1050°C for about 4 hours to achieve reasonable strength for further handling. After bisque firing, the resulting tube can be checked or tested for targeted porosity, strength, creep resistance and, most importantly, diffusivity characteristics. Alternatively, a freeze cast supporting structure could be formed as discussed in "Freeze-Casting of Porous Ceramics: A Review of Current
Achievements and Issues" (2008) by Deville, pp. 155-169.
[0048] After forming the green tube, intermediate porous layer 14, 14', 14" is then formed. A mixture of about 34 grams of powders having electronic and ionic phases, LSCMV and lOSclYSZ, respectively, is prepared so that the mixture contains generally equal proportions by volume of LSCMV and lOSclYSZ. Prior to forming the mixture, the catalyst particles, such as CGO, are so incorporated into the electronic phase LSCMV by forming deposits of such particles on the electronic phase, for example, by precipitation. However, it is more preferable to form the catalyst particles within the intermediate porous layer by wicking a solution containing catalyst precursors through the porous support layer towards the intermediate porous layer after application of the membrane active layers as described in
more detail below. As such, there is no requirement to deposit particles of catalyst on the electronic phase. The electronic phase particles are each about 0.3 microns prior to firing and the catalyst particles are about 0.1 microns or less and are present in a ratio by weight of about 10wt%. To the mixture, 100 grams of toluene, 20 grams of the binder of the type mentioned above, 400 grams of 1.5 mm diameter YSZ grinding media are added. The mixture is then milled for about 6 hours to form a slurry (d5o of about 0.34μιη). About 6 grams of carbon black having a particle size of about d50 = 0.8μιη is then added to the slurry and milled for additional 2 hours. An additional 10 grams of toluene and about 10 grams of additional binder is added to the slurry and mixed for between about 1.5 and about 2 hours. The inner wall of the green tube formed above is then coated by pouring the slurry, holding once for about 5 seconds and pouring out the residual back to the bottle. The coated green tube is then dried and fired at 850°C for 1 hour in air.
[0049] The dense layer 10, 10', 10" is then applied. A mixture weighing about 40 grams is prepared that contains the same powders as used in forming the intermediate porous layer, discussed above, except that the ratio between LSCMV and lOSclYSZ is about 40/60 by volume, 2.4 grams of cobalt nitrate {Co(N03)2.6H20}, 95 grams of toluene, 5 grams of ethanol, 20 grams of the binder identified above, 400 grams of 1.5 mm diameter YSZ grinding media are then added to the mixture and the same is milled for about 10 hours to form a slurry (d5o ~ 0.34μιη). Again, about 10 grams of toluene and about 10 grams of binder are added to the slurry and mixed for about 1.5 and about 2 hours. The inner wall of the tube is then coated by pouring the slurry, holding once for about 10 seconds and pouring out the residual back to the bottle. The coated green tube is then stored dry prior to firing the layers in a controlled environment.
[0050] The coated green tube is then placed on a C-setter in a horizontal tube furnace and porous alumina tubes impregnated with chromium nitrate are placed close to the coated tube to saturate the environment with chromium vapor. The tubes are heated in static air to about 800°C for binder burnout and, if necessary, the sintering environment is switched to an atmosphere of a saturated nitrogen mixture (nitrogen and water vapor) that contains about 4 percent by volume of hydrogen to allow the vanadium containing electronic conducting perovskite structured materials to properly sinter. The tube is held at about 1350°C to 1430°C for about 8 hours and then cooled in nitrogen to complete the sintering of the
materials. The sintered tube is then checked for leaks wherein the helium leak rates should be lower than 10~7 Pa.
[0051] Surface exchange layer 16 is then applied. A mixture of powders is prepared that contains about 35g of equal amounts of ionic and electronic phases having chemical formulas of Zr0.8oSco.i8Yo.o202-8 and Lao.8Sr0.2Fe03_8, respectively. To this mixture, about 100 grams of toluene, 20 grams of the binder identified above, about 400 grams of 1.5 mm diameter YSZ grinding media are added and the resultant mixture is milled for about 14 hours to form a slurry (d50 ~ 0.4μιη). About six grams of carbon black are added to the slurry and milled for additional 2 hours. A mixture of about 10 grams of toluene and about 10 grams of the binder are then added to the slurry and mixed for between about 1.5 and about 2 hours. The inner wall of the tube is then coated by pouring the slurry, holding twice for about 10 seconds and then pouring out the residual back to the bottle. The coated tube is then dried and fired at 1100°C for two hours in air.
[0052] The structure formed in the manner described above is in a fully sintered state and the catalyst is then further applied by wicking a solution containing catalyst precursors in the direction of arrowhead B at the side of the porous support opposite to the intermediate porous layer. The solution can be an aqueous metal ion solution containing about 20 mol%
Gd(N03)3 and 80 mol% Ce(N03)3. A pressure can be established on the side of the porous support layer to assist in the infiltration of the solution. In addition, the pores can first be evacuated of air using a vacuum to further assist in wicking of the solution and prevent the opportunity of trapped air in the pores preventing wicking of the solution all the way through the porous support layer to the intermediate porous layer. The resulting composite oxygen transport membrane 1 in such state can be directly placed into service or further fired prior to being placed into service so that the catalyst particles, in this case Ce0.8Gdo.202-8 are formed in the porous support layer adjacent to the intermediate porous layer and as described above, within the intermediate porous layer itself. The firing to form Ce0.8Gdo.202-8 would take place at a temperature of about 850°C and would take about 1 hour to form the catalyst particles.
[0053] Although the present invention has been described with reference to a preferred embodiment, as will occur to those skilled in the art, changes and additions to such embodiment can be made without departing from the spirit and scope of the present invention as set forth in the appended claims.
Claims
1. A composite oxygen transport membrane, said composite oxygen transport membrane comprising:
a porous support layer comprised of an fluorite structured ionic conducting material having a porosity of greater than 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer;
an intermediate porous layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the intermediate porous layer applied adjacent to the porous support layer and comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively;
a dense layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the dense layer applied adjacent to the intermediate porous layer and also comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; and catalyst particles or a solution containing precursors of the catalyst particles located in pores of the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer.
2. The composite oxygen transport membrane of claim 1, wherein the catalyst is gadolinium doped ceria.
3. The composite oxygen transport membrane of claim 1, further comprising a porous surface exchange layer applied to the dense layer opposite to the intermediate porous layer.
4. The composite oxygen transport membrane of claim 1, wherein:
the intermediate porous layer has a thickness of between 10 and 40 microns, a porosity of between 20 percent and 50 percent and an average pore diameter of between 0.5 and 3 microns;
the dense layer has a thickness of between 10 and 50 microns;
the porous surface exchange layer has a thickness of between 10 and 40 microns, a porosity of between 30 percent and 60 percent and a pore diameter of between 1 and 4 microns; and
the porous support layer has a thickness of between 0.5 and 4 mm.
5. The composite oxygen transport membrane of claim 1, wherein:
the intermediate porous layer contains a mixture of about 60 percent by weight of (Lao.825Sro.i75)o. 6Cro.76Feo.225 o.oi503_8 or (Lao.8Sro.2)o. 5Cro.7Feo.303_8
with the remainder lOSclYSZ or lOSclCeSZ;
the dense layer contains a mixture of about 40 percent by weight of
(La0.825Sro.i75)o.94Cro.72Mn0.26Vo.o203-8 or (La0.8Sr0.2)0.95Cr0.5Fe0.5O3-8, with remainder lOSclYSZ or lOSclCeYSZ;
the porous surface exchange layer is formed by a mixture of about 50 percent by weight of (La0.8Sr0.2)o.98Mn03-8 or Lao.8Sr0.2Fe03-8, remainder lOSclYSZ or lOSclCeSZ;
the porous support layer has a thickness of between 0.5 and 4 mm and is formed from a mixture comprising 3YSZ and a polymethyl methacrylate based pore forming material.
6. The composite oxygen transport membrane of claim 1, wherein:
the intermediate porous layer contains a mixture of about 60 percent by weight of (LauSrvCei_u-v)wCrxMyVz03-8 where u is from 0.7 to 0.9, v is from 0.1 to 0.3 and (1-u-v) is greater than or equal to zero, w is from 0.94 to 1, x is from 0.5 to 0.77, M is Mn or Fe, y is from 0.2 to 0.5, z is from 0 to 0.03, and x+y+z =1, with the remainder Zrx'ScyAzO2-8, where y' is from 0.08 to 0.3, z' is from 0.01 to 0.03, x'+y'+z -1 and A is Y or Ce or mixtures of Y and Ce, and the intermediate porous layer has a thickness of between 10 and 40 microns, and a porosity of between 25 percent and 40 percent;
the dense layer contains a mixture of about 40 percent by weight of (LauSrvCei_u- v)wCrxMyVz03-8 where u is from 0.7 to 0.9, v is from 0.1 to 0.3 and (1-u-v) is greater than or
equal to zero, w is from 0.94 to 1, x is from 0.5 to 0.77, M is Mn or Fe, y is from 0.2 to 0.5, z is from 0 to 0.03, and x+y+z =1, with the remainder Zrx'ScyAzO2-8, where y' is from 0.08 to 0.3, z' is from 0.01 to 0.03, x'+y'+z -1 and A is Y or Ce or mixtures of Y and Ce, and the dense layer has a thickness of between 10 and 50 microns;
the porous surface exchange layer is formed by a mixture of about 50 percent by weight of (Lax<<<Sri_x<<<)y'''M03-8, where x'" is from 0.2 to 0.9, y'" is from 0.95 to 1 , M is Mn or Fe, with the remainder Zrx lv Scy 1VAZ ιν02_δ, where ylv is from 0.08 to 0.3, zlv is from 0.01 to 0.03, xlv+ylv+zlv=l and A is Y, Ce or mixtures of Y and Ce; and
the porous support layer has a thickness of between 0.5 and 4 mm and is formed from
3YSZ.
7. A composite oxygen transport membrane made by the process comprising:
fabricating a porous support layer comprised of an fluorite structured ionic conducting material, the fabricating step including a pore forming enhancement step such that the porous support layer has a porosity of greater than about 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer;
applying an intermediate porous layer on the porous support layer, the intermediate porous layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the intermediate porous layer comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively;
applying a dense layer on the intermediate porous layer, the dense layer capable of conducting oxygen ions and electrons to separate oxygen from an oxygen containing feed, the dense layer also comprising a mixture of a fluorite structured ionic conductive material and electrically conductive materials to conduct the oxygen ions and electrons, respectively; and introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer, the catalyst particles containing a catalyst selected to promote oxidation of a combustible substance in the presence of the separated oxygen transported through the dense layer and the intermediate porous layer to the porous support layer.
8. The composite oxygen transport membrane of claim 7, wherein the pore forming enhancement process comprises mixing a polymethyl methacrylate based pore forming material with the fluorite structured ionic conducting material of the porous support layer.
9. The composite oxygen transport membrane of claim 7, wherein the pore forming enhancement process comprises use of hollow spherical particles of the fluorite structured ionic conducting material of the porous support layer.
10. The composite oxygen transport membrane of claim 7, further comprising the step of applying a porous surface exchange layer to the dense layer opposite to the intermediate porous layer.
11. The composite oxygen transport membrane of claim 7, wherein the step of introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer further comprises adding catalyst particles to the mixture of fluorite structured ionic conductive material and electrically conductive materials in the intermediate porous layer.
12. The composite oxygen transport membrane of claim 7, wherein the step of introducing catalyst particles or a solution containing precursors of the catalyst particles to the porous support layer and intermediate porous layer further comprises:
applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer so that the solution infiltrates pores within the porous support layer and the intermediate porous layer with the solution containing catalyst precursors; and
heating the composite oxygen transport membrane after the solution containing catalyst precursors infiltrates the pores and to form the catalyst from the catalyst precursors.
13. A method of producing a catalyst containing composite oxygen transport membrane, said method comprising:
forming a composite oxygen transport membrane in a sintered state, said composite oxygen transport membrane having a plurality of layers comprising a dense separation layer, a porous support layer, and an intermediate porous layer located between the dense separation layer and the porous support layer;
applying a solution containing catalyst precursors to the porous support layer on a side thereof opposite to the intermediate porous layer, the catalyst precursors selected to produce a catalyst capable of promoting oxidation of the combustible substance in the presence of the separated oxygen;
infiltrating or impregnating the porous support layer with the solution containing catalyst precursors so that the solution containing catalyst precursors wicks through the pores of the porous support layer and at least partially infiltrates or impregnates the intermediate porous layer; and
heating the composite oxygen transport membrane after infiltrating or impregnating the porous support layer and the intermediate porous layer such that the catalyst is formed from the catalyst precursors
wherein each of the dense separation layer and the intermediate porous layer are capable of conducting oxygen ions and electrons at an elevated operational temperature to separate oxygen from an oxygen containing feed;
wherein the dense separation layer and the intermediate porous layer comprising mixtures of a fluorite structured ionic conductive material and electrically conductive materials to conduct oxygen ions and electrons, respectively;
wherein the porous support layer comprises a fluorite structured ionic conducting material having a porosity of greater than about 20 percent and a microstructure exhibiting substantially uniform pore size distribution throughout the porous support layer.
14. The method of claim 13, wherein the solution containing catalyst precursors is an aqueous metal ion solution containing 20 mol% Gd(N03)3 and 80 mol% Ce(N03)3 that when sintered forms Gdo.8Ce0.202-8.
15. The method of claim 13, wherein the catalyst is gadolinium doped ceria.
16. The method of claim 13, wherein a pressure is established on the second side of the support layer to assist in the infiltration or impregnation of porous support layer and intermediate porous layer with the solution containing catalyst precursors or wherein the pores can first be evacuated of air using a vacuum to further assist in wicking of the solution containing catalyst precursors and prevent the opportunity of trapped air in the pores preventing or inhibiting wicking of the solution containing catalyst precursors through the porous support layer to the intermediate porous layer.
17. The method of claim 13, wherein the pores in the porous support layer are formed using a polymethyl methacrylate based pore forming material mixed with the fluorite structured ionic conducting material of the porous support layer.
18. The method of claim 13, wherein the pores in the porous support layer are formed using of hollow spherical particles of the polymethyl methacrylate based pore forming material or the fluorite structured ionic conducting material of the porous support layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/672,975 US9561476B2 (en) | 2010-12-15 | 2012-11-09 | Catalyst containing oxygen transport membrane |
| US13/672,975 | 2012-11-09 |
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| Publication Number | Publication Date |
|---|---|
| WO2014074559A1 true WO2014074559A1 (en) | 2014-05-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US2013/068657 WO2014074559A1 (en) | 2012-11-09 | 2013-11-06 | Catalyst containing oxygen transport membrane |
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| WO (1) | WO2014074559A1 (en) |
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| US9452401B2 (en) | 2013-10-07 | 2016-09-27 | Praxair Technology, Inc. | Ceramic oxygen transport membrane array reactor and reforming method |
| US9453644B2 (en) | 2012-12-28 | 2016-09-27 | Praxair Technology, Inc. | Oxygen transport membrane based advanced power cycle with low pressure synthesis gas slip stream |
| US9452388B2 (en) | 2013-10-08 | 2016-09-27 | Praxair Technology, Inc. | System and method for air temperature control in an oxygen transport membrane based reactor |
| US9486735B2 (en) | 2011-12-15 | 2016-11-08 | Praxair Technology, Inc. | Composite oxygen transport membrane |
| US9492784B2 (en) | 2011-12-15 | 2016-11-15 | Praxair Technology, Inc. | Composite oxygen transport membrane |
| US9556027B2 (en) | 2013-12-02 | 2017-01-31 | Praxair Technology, Inc. | Method and system for producing hydrogen using an oxygen transport membrane based reforming system with secondary reforming |
| US9561476B2 (en) | 2010-12-15 | 2017-02-07 | Praxair Technology, Inc. | Catalyst containing oxygen transport membrane |
| US9562472B2 (en) | 2014-02-12 | 2017-02-07 | Praxair Technology, Inc. | Oxygen transport membrane reactor based method and system for generating electric power |
| US9611144B2 (en) | 2013-04-26 | 2017-04-04 | Praxair Technology, Inc. | Method and system for producing a synthesis gas in an oxygen transport membrane based reforming system that is free of metal dusting corrosion |
| WO2017172238A1 (en) * | 2016-04-01 | 2017-10-05 | Praxair Technology, Inc. | Catalyst-containing oxygen transport membrane |
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| US9573094B2 (en) | 2013-10-08 | 2017-02-21 | Praxair Technology, Inc. | System and method for temperature control in an oxygen transport membrane based reactor |
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| US9789445B2 (en) | 2014-10-07 | 2017-10-17 | Praxair Technology, Inc. | Composite oxygen ion transport membrane |
| WO2016057164A1 (en) * | 2014-10-07 | 2016-04-14 | Praxair Technology, Inc | Composite oxygen ion transport membrane |
| US10441922B2 (en) | 2015-06-29 | 2019-10-15 | Praxair Technology, Inc. | Dual function composite oxygen transport membrane |
| US10118823B2 (en) | 2015-12-15 | 2018-11-06 | Praxair Technology, Inc. | Method of thermally-stabilizing an oxygen transport membrane-based reforming system |
| US9938146B2 (en) | 2015-12-28 | 2018-04-10 | Praxair Technology, Inc. | High aspect ratio catalytic reactor and catalyst inserts therefor |
| WO2017172238A1 (en) * | 2016-04-01 | 2017-10-05 | Praxair Technology, Inc. | Catalyst-containing oxygen transport membrane |
| CN109070014A (en) * | 2016-04-01 | 2018-12-21 | 普莱克斯技术有限公司 | Oxygen transport membrane containing catalyst |
| US11052353B2 (en) | 2016-04-01 | 2021-07-06 | Praxair Technology, Inc. | Catalyst-containing oxygen transport membrane |
| US11136238B2 (en) | 2018-05-21 | 2021-10-05 | Praxair Technology, Inc. | OTM syngas panel with gas heated reformer |
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