WO2008074181A1 - Membrane de séparation d'oxygène - Google Patents

Membrane de séparation d'oxygène Download PDF

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Publication number
WO2008074181A1
WO2008074181A1 PCT/CN2006/003438 CN2006003438W WO2008074181A1 WO 2008074181 A1 WO2008074181 A1 WO 2008074181A1 CN 2006003438 W CN2006003438 W CN 2006003438W WO 2008074181 A1 WO2008074181 A1 WO 2008074181A1
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WO
WIPO (PCT)
Prior art keywords
oxygen
composition
membrane
oxide
conducting component
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Application number
PCT/CN2006/003438
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English (en)
Inventor
You Cong
Weishen Yang
Xuefen Zhu
Original Assignee
Bp P.L.C.
Dalian Institute Of Chemical Physics Chinese Academy Of Sciences
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Bp P.L.C., Dalian Institute Of Chemical Physics Chinese Academy Of Sciences filed Critical Bp P.L.C.
Priority to PCT/CN2006/003438 priority Critical patent/WO2008074181A1/fr
Priority to EP07733256A priority patent/EP2040822A1/fr
Priority to PCT/GB2007/002252 priority patent/WO2007148057A1/fr
Priority to EA200802401A priority patent/EA200802401A1/ru
Priority to CNA2007800228660A priority patent/CN101479021A/zh
Priority to CA002654364A priority patent/CA2654364A1/fr
Priority to AU2007262755A priority patent/AU2007262755A1/en
Priority to US12/308,511 priority patent/US20100234650A1/en
Publication of WO2008074181A1 publication Critical patent/WO2008074181A1/fr
Priority to NO20090232A priority patent/NO20090232L/no

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/22Separation 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
    • B01D53/228Separation 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
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/20Capture or disposal of greenhouse gases of methane

Definitions

  • Oxygen-permeable membranes may be used to separate oxygen from an oxygen- containing gas, such as air.
  • Typical selective oxygen-permeable membranes comprise a ceramic material that is capable of conducting oxygen ions through the lattice structure at a suitable temperature, and which enables oxygen to permeate through the membrane from one side to the other, from a region of relatively high oxygen partial pressure to a region of relatively low oxygen partial pressure.
  • Ceramic materials suitable for oxygen separation include compounds of formula Sr a (Fe 1-x Co x ) a+b O d , as described in US 5,639,437, and substituted analogues, such as Bao.sSro.sCoo.sFeo ⁇ Os- ⁇ and SrC ⁇ o. 8 Fe 0 . 2 O 3- s as described by Shao et al in Journal of Membrane Science, 2000, vol 172, ppl77-188.
  • a problem with such membrane materials is that they can exhibit poor long term stability, particularly under reducing environments and high pressure gradients, which can limit their applicability.
  • Composite membranes are known, comprising two or more materials, one of which is capable of conducting oxygen ions, the other of which is an electronic conductor, examples being Lao.7Sro. 3 MnO 3- ⁇ mixed with Ceo.sGdQ.2O2- s as reported by Kharton et al in J. Electrochem. Soc, 147, pp2814-21 (2000).
  • a problem with composite membranes is that particles of the different materials must form a continuous network of electronic and oxygen conducting pathways, often requiring a high content of the electron conducting material, which limits oxygen flux (the rate of transport of oxygen through the membrane).
  • oxygen permeability typically occurs at high temperature, different thermal expansion coefficients of the different materials can also lead to degradation of the membrane structure.
  • composition for a selective oxygen-permeable membrane comprising an electron-conducting component and an oxide- conducting component, characterised in that the electron-conducting component is also an oxide-conductor.
  • Oxygen separation membranes typically operate by converting oxygen atoms or molecules at one membrane surface into oxide (O 2" ) ions, and releasing oxygen atoms or molecules at the other surface.
  • the membrane needs not only to conduct oxygen ions, but also needs to conduct electrons in order to correct any charge imbalance caused by the redox reactions on the respective sides of the membrane.
  • improved oxygen flux through the membrane is achieved by using a composite material having oxygen ion conducting and electron conducting components, in which the electron conducting component is also an oxide ion conductor.
  • the electron conducting component which is also capable of conducting oxide ions, is capable of achieving an oxygen flux of greater than 1 x 10 "4 ml cm '2 min "1 , for example greater than 1 x 10 "3 ml cm “2 min “1 , and most preferably greater than 0.01 ml cm “2 min "1 at 95O 0 C.
  • the electron conducting component is also an oxide-conductor
  • oxygen flux through the membrane is improved, while maintaining the necessary electronic conductivity to allow charge stabilisation on both sides of the membrane.
  • the material of the oxide-conducting component is an oxide of the fluorite structure, which is based on the structure OfCaF 2 , and is adopted by substances such as CeO 2 and ZrO 2 .
  • the structure comprises a face centred cubic arrangement of cations, with the anions occupying the tetrahedral interstices, and have a general formula of MX 2 , in which M is the cation and X is the anion.
  • R rare- earth elements
  • R can be substituted to form compounds of general formula Ce 1 -x R x O 2- (x /2).
  • the value of x is typically in the range of from 0.05 to 0.25.
  • the oxide-conducting component comprises cerium. More preferably, the oxide-conducting component comprises cerium in combination with a second lanthanide element, which is preferably a lanthanide element in common with a lanthanide element in the electron-conducting component of the composition.
  • the second lanthanide is preferably selected from one or more of Nd, Sm and Gd, and is more preferably Sm and/or Gd
  • cerium and gadolinium are present, preferably with a Ce:Gd molar ratio in the range of from 2:1 to 20:1, more preferably in the range of from 2:1 to 10:1, and yet more preferably in the range of from 3:1 to 5:1. Most preferably, the ratio is about 4:1, as found for example in the material
  • the electron conducting component is also an oxide conductor, and is preferably an oxide having a perovskite structure.
  • Perovskite materials have a general formula ABO 3- s, wherein A and B represent different lattice sites within the perovskite structure occupied by different elements, wherein elements occupying site A are typically larger than those occupying site B.
  • the value of " ⁇ " in relation to the value "3- ⁇ " for the oxygen stoichiometry is dependent on the charges of the various cations within the perovskite structure, the value being that required to make the structure neutral overall.
  • ABO 3- ⁇ if the A and B cations each have a charge of +3, then ⁇ will equal zero. However, if the A cation has a +2 charge and the B cation has a +3 charge, then ⁇ is equal to 0.5.
  • the electron conducting oxide component is an oxide comprising a lanthanide, an alkaline earth and a first row transition metal.
  • the lanthanide used is the same as a lanthanide element used in the oxide-conducting component, being preferably selected from Nd, Sm and Gd, more preferably Sm and/or Gd, and is most preferably gadolinium.
  • the alkaline earth is preferably strontium.
  • the first row transition metal is preferably iron.
  • the electron conducting component comprises Gd, Sr and Fe, in which the Gd: Sr mole ratio is typically in the range of from 1 :2 to 1:8, preferably from 1 :3 to 1 :5, and is most preferably about 1 :4.
  • the Gd:Fe mole ratio is typically in the range of from 1:1 to 1:10, more preferably in the range of from 1 :3 to 1 :7, and is most preferably about 1:5.
  • the electronic-conducting oxide comprises a Gd:Sr:Fe mole ratio of about 2:8:10, for example in Gdo. 2 Sro. 8 Fe ⁇ 3 . ⁇ , where ⁇ represents the correction required to charge balance the formula.
  • compositions in which the phases of the two different components are the same are typically avoided, as this can result in mixing of the compositions due to migration of the respective elements of the different components. This can result in reduction and even loss of the oxide and/or electronic conducting properties of either or both of the components. Therefore, in a preferred embodiment of the invention, the phases of the two different components are different from each other. More preferably, the phase of the oxide- conducting component is perovskite, and that of the electronic-conducting component is a fluorite.
  • an electron-conducting component and an oxide conducting component each comprising a common lanthanide is advantageous, as any migration of lanthanide between the two components that does take place will less likely result in the alteration of the crystalline structure of the components, which results in less degradation and improved lifetime of the membrane when used in high temperature applications, such as during use as a selective oxygen-permeable membrane for oxygen separation.
  • the weight ratio of the electron-conducting component to the oxide-conducting component is selected so as to give the optimum oxide conductivity, coupled with high oxygen selectivity.
  • the weight ratio of the electron-conducting component to the oxide-conducting component is in the range of from 1:4 to 4:1, preferably in the range of from 1:3 to 1:1, and is most preferably about 2:3.
  • composition of the present invention may be used to form a selective oxygen- permeable membrane for separating oxygen from a mixture comprising oxygen, for example air.
  • the membrane additionally comprises a porous layer of a material that acts to enhance the rate of oxygen exchange at the membrane surface.
  • a material that acts to enhance the rate of oxygen exchange at the membrane surface.
  • An example of such a material is an oxide comprising La, Sr and Co with a perovskite structure, preferably Lao. 6 Sr 0 . 4 Co0 3- ⁇ .
  • Oxygen separation from air can be achieved by feeding air into a first zone of a separation vessel having two zones, which two zones are separated by the selective oxygen-permeable membrane. Conditions are maintained in each of the two zones of the vessel and at the membrane such that oxygen transfers from the first zone, through the membrane and into the second zone. Permeation through the membrane is dependent, inter alia, on the partial pressure of oxygen on each side of the membrane. Thus, to transfer oxygen from the first zone of the vessel to which the air is fed, there must be a lower partial pressure of oxygen in the second zone on the other side of the membrane. To achieve this, the second zone can be free of oxygen before oxygen permeation takes place, or must have a lower partial pressure of oxygen.
  • the oxygen levels in the air in the first zone of the separator vessel are depleted.
  • the membrane when in use, is maintained under conditions that allow the selective permeation of oxygen. Typically, this necessitates a temperature of in excess of 700 0 C, preferably 85O 0 C or more, in order to ensure a sufficient rate of oxygen activation at the surface of the membrane.
  • the temperature of the membrane is also typically maintained below 1400 0 C, preferably HOO 0 C or less, to prevent degradation of the membrane structure, which can negatively impact oxygen flux.
  • the partial pressure of oxygen in the second zone of the permeation vessel is less than the partial pressure in the first zone of the membrane in order to allow a net transfer of oxygen from the first to the second zone.
  • Use of a selective oxygen permeable membrane to provide purified oxygen is less energy intensive than conventional cryogenic techniques, and thus can be operated more viably on a smaller scale. This allows the possibility of providing small-scale, locally situated oxygen generation units for a process that may require purified oxygen, as opposed to either requiring the import of oxygen that has to be transported from a large- scale remote facility, or necessitating locating the process in the vicinity of such a large scale oxygen production unit.
  • the selective oxygen-permeable membrane is part of a reactor comprising two zones, which two zones are separated by the membrane.
  • the reactor can be used for performing reactions in oxygen-consuming reactions, including reactions in which a reducing atmosphere is be present, for example reactions involving syngas, such as the steam reforming and/or partial oxidation of hydrocarbons to produce one or more oxides of carbon.
  • one or more reactants are fed to the second zone of the reactor, which may additionally comprise a catalyst.
  • An oxygen- containing gas, such as air, is fed to the first zone of the reactor. In use, oxygen in the first zone of the reactor permeates through the membrane into the second zone of the reactor, in which the reaction takes place.
  • the second zone of the separation vessel is a reaction zone for the production of syngas by steam reforming and/or partial oxidation of a hydrocarbon.
  • oxygen from air permeates through the membrane from the first zone of the separation vessel and into the second zone for use as a reactant in the partial oxidation and/or steam reaction occurring therein.
  • Such an embodiment is advantageous as oxygen can be distributed throughout the syngas production reaction zone, which can reduce the probability of potentially explosive mixtures with high oxygen concentrations being created in poorly mixed regions of the reaction zone.
  • separating air in situ can reduce or even eliminate the need for a dedicated and expensive air separation unit.
  • Syngas (a mixture of carbon monoxide and hydrogen) is preferably produced from natural gas, which comprises predominantly methane.
  • Reaction temperature is typically similar to or the same as the temperature of the membrane, preferably in the range of from 850 to 1100 0 C.
  • the total pressure within the reaction zone is typically maintained in the range of from 1 to 200 bara (0.1 to 20 MPa).
  • the oxygen partial pressure in the second zone of the reactor must be less than that in the first zone of the reactor.
  • the reaction zone may also comprise a hydrogen separation membrane, in which the hydrogen produced can be selectively separated from the reaction zone and used, for example, to produce energy.
  • Ccompositions in accordance with the present invention can be made by mixing the two separate components in powder form and compressing them together. Typically, the mixed powder is subsequently calcined at high temperature, typically in an oxygen- containing atmosphere at temperatures of up to 1400 0 C, for example in the range of from 700 to 1400 0 C.
  • the separate components may be synthesised by various techniques, for example by high temperature synthesis using mixed oxides of the various constituent elements, or by precipitating an oxide from a solution comprising soluble compounds of the constituent elements, hi the latter case, the resulting precipitate, which maybe amorphous, is typically calcined at high temperature to form the desired crystalline phase.
  • Figure 1 shows X-ray diffraction (XRD) patterns for a membrane made from a composition according to the present invention, in addition to XRD patterns of the constituent components;
  • Figure 2 schematically illustrates the apparatus used for oxygen permeation experiments;
  • Figure 3 is a plot of oxygen flux against time at 95O 0 C for a selective oxygen- permeable membrane made from a composition in accordance with the present invention;
  • Figure 4 is a plot of oxygen flux against time at 1000 0 C for a selective oxygen- permeable membrane made from a composition in accordance with the present invention
  • Figure 5 is a plot of oxygen flux against the reciprocal of temperature at different oxygen partial pressure differentials for a membrane made from a composition in accordance with the present invention
  • Figure 6 is a plot of oxygen flux against the reciprocal of temperature for different thicknesses of a membrane made from a composition in accordance with the present invention
  • Figure 7 is a plot of oxygen flux against the log of the partial pressure differential across a membrane made from a composition in accordance with the present invention.
  • Figure 8 schematically illustrates a process using a reactor with a selective oxygen- permeable membrane, in which oxygen is separated from air in one zone of the reactor and fed into a second zone of the reactor for use as a reactant in the catalytic partial oxidation of methane;
  • Figure 9 is a plot of catalytic performance and oxygen permeation performance in the partial oxidation of methane using a reactor with a selective oxygen-permeable membrane made from a composition in accordance with the present invention
  • a composition in accordance with the present invention was prepared by separately synthesising GdC 2 CeCsOh 9 (GDC) and Gd 0 . 2 Sro. 8 Fe0 3- ⁇ (GSF).
  • GDC GdC 2 CeCsOh 9
  • Nitrate salts of the metals in respective stoichiometric quantities were dissolved in water.
  • a quantity of EDTA and citric acid were each added so that the molar ratio of each of the EDTA and citric acid to the total quantity of metal ions was 1.
  • the pH of the solution was then adjusted to a value of between 6 and 8 by addition of ammonium hydroxide solution. Water was removed by evaporation at about 8O 0 C using a hot-plate. A gel formed, which was then ignited with a flame in order to combust residual organic material. The resulting powder was subsequently calcined under air for 5 hours at 900 0 C to yield the respective oxide product.
  • Membranes were prepared using the following procedures.
  • Example 1 Powders of each of the GDC and GSF compounds were mixed together in a ratio of 60wt% GDC to 40wt% GSF. They were then compressed into a disc at a pressure of 200MPa, and heated at 1400 0 C for a period between 3 and 5 hours to form the final composition (GDC60/GSF40), which could also be used as a selective oxygen-permeable membrane in subsequent experiments.
  • the disc of GDC60/GSF40 was polished to a thickness of 0.5mm, and a coating of a porous Lao. 6 Sr 0 . 4 Co0 3- s (LSC) was applied in order to improve oxygen exchange at the membrane surface. This was achieved by preparing a paste of 40wt% LSC in 60wt% terpineol-saturated methyl cellulose, the coated membrane being calcined at 900 0 C in air for one hour.
  • GSF-only and GDC-only membranes were formed by compressing a disc of GSF or GDC at 200MPa, and heating it to a temperature of 125O 0 C for 3 hours. The disc was then polished and coated with LSC in an identical way to the membrane of example 1.
  • X-ray diffraction (XRD) patterns were measured for the pure GDC 1 and GSF 2 compounds, and also for the GDC60/GSF40 membrane 3. XRD patterns were collected before any LSC coating was applied. The results are shown in Figure 1.
  • a Rigaku D/Max-RB diffractometer was used, employing Cu Ka radiation. Data were collected over a 2 ⁇ range of 20-80° in steps of 0.02°.
  • the data show that the membrane composition, after mixing and treatment at 1400 0 C, comprises a mixture of the two constituent phases; no new phase is apparent.
  • the data also show that GSF adopts a perovskite structure, and GDC adopts a fluorite structure.
  • An LSC-coated disc of GDC or GSF was loaded into a vertical high-temperature gas permeation cell.
  • a flow of a dry mixture of 80% nitrogen and 20% oxygen by volume was introduced at a rate of lOOmL/min (adjusted to standard temperature and pressure (STP), i.e. O 0 C and 1 arm pressure).
  • STP standard temperature and pressure
  • a helium (or methane) sweep gas was fed to the other side of the membrane (corresponding to the second zone of the vessel) to assist removal of permeated oxygen.
  • the separation vessel 10 comprises two zones, a first zone 11 to which air is fed through inlet 12, and a second zone 13 to which a helium sweep gas is fed through inlet 14.
  • the membrane was maintained at a temperature of 94O 0 C using heater 19. Temperature at the membrane was measured using a thermocouple 20 located within a thermowell 21 which extended to a point just above the membrane 15.. An oxygen partial pressure of 21 kPa was maintained in the first zone.
  • the initial oxygen flux was below detectable limits, i.e. less than 0.001 mL cm "2 min '1 .
  • the helium flow on the permeate side of the membrane was adjusted to give an oxygen partial pressure of 5 kPa.
  • the initial oxygen flux across the membrane was 0.26 mL cm “2 min "1 .
  • Oxygen flux through a GDC60/GSF40 membrane at temperatures of between 800 0 C and 1010 0 C was studied.
  • a flow of lOOmL/min (STP) of the oxygen-nitrogen mixture at an oxygen partial pressure of 21 kPa on one side of the membrane was used, and the helium gas flow on the other (permeate) side of the membrane was adjusted to give an oxygen partial pressure of 0.5kPa.
  • Experiment 6 The procedure was the same as Experiment 5, except that the helium gas flow on the other (permeate) side of the membrane was adjusted to give an oxygen partial pressure of 1.OkPa.
  • Experiment 7 The procedure was the same as Experiment 5 and 6, except that the helium gas flow on the other (permeate) side of the membrane was adjusted to give an oxygen partial pressure of 2.OkPa.
  • GDC60/GSF40 membrane was used, at temperatures of between 825 0 C and 94O 0 C.
  • An oxygen partial pressure on the permeate side of the membrane was maintained at a value of l.O fcPa.
  • Table 1 shows the calculated oxygen permeation activation energies for Experiments 5 through to 8.
  • Figure 7 shows the results of oxygen flux versus the log of the partial pressure differential for the 0.5mm membrane at two different temperatures, 850 and 95O 0 C.
  • the partial pressure differential is expressed as the ratio between the oxygen partial pressure in the oxygen/nitrogen mixture (PO 2 ') and the oxygen partial pressure in the oxygen/helium mixture on the permeate side of the membrane (PO 2 ")-
  • the results show that at 95O 0 C the gradient is constant, indicating bulk diffusion is the main factor limiting oxygen flux.
  • the gradient is non-linear, being larger at lower oxygen partial pressure differentials, indicating that surface exchange becomes important at this lower temperature.
  • the use of a 0.5mm GDC60/GSF40 membrane to directly separate pure oxygen from air, for feeding to a reaction for the partial oxidation of methane to carbon monoxide and hydrogen was studied.
  • the membrane was loaded into a membrane reactor, the membrane separating the reactor into two zones.
  • a LiLaNiO/ ⁇ -alumina partial oxidation catalyst which had been prepared by an impregnation method in which gamma-alumina was immersed for 24 hours in a solution comprising lithium nitrate, nickel(II) nitrate and lanthanum(III) nitrate in a 1 : 1.6:2.6 Ni:Li:La mole ratio.
  • FIG. 8 shows a reactor 100 with a first zone 101 and a second zone 102 separated by a selective oxygen-permeable membrane 103, sealed using gold rings 104. Air is fed to the first zone 101 through inlet 105. Oxygen permeating the membrane 103 enters the second zone 102 of the reactor. To the second zone of the reactor is fed a hydrocarbon, for example methane 106. The second zone also contains a partial oxidation catalyst 107. The methane combines with the permeated oxygen in the presence of the catalyst 107, and reaction occurs. An oxygen/nitrogen mixture with reduced oxygen concentration is removed from the first zone 101 of the reactor through outlet 108, while a stream comprising unreacted methane and oxygen, together with reaction products and by-products is removed from the second zone of the reactor through outlet 109.
  • Air is fed to the first zone 101 through inlet 105.
  • Oxygen permeating the membrane 103 enters the second zone 102 of the reactor.
  • a hydrocarbon for example methane 106

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une composition comprenant un constituant conducteur d'électrons et un constituant conducteur d'oxyde, caractérisée en ce que le constituant conducteur d'électrons est également un conducteur d'oxyde. Cette composition peut être utilisée dans une membrane sélectivement perméable à l'oxygène et permet de séparer l'oxygène d'un mélange gazeux renfermant de l'oxygène, tel que de l'air, la séparation étant éventuellement réalisée dans un réacteur comprenant une première et une seconde zone, un gaz contenant de l'oxygène étant acheminé vers la première zone et un réactif étant acheminé vers la seconde zone. À titre d'exemple, la réaction peut être l'oxydation partielle ou le vaporeformage d'un réactif hydrocarboné.
PCT/CN2006/003438 2006-06-21 2006-12-18 Membrane de séparation d'oxygène WO2008074181A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
PCT/CN2006/003438 WO2008074181A1 (fr) 2006-12-18 2006-12-18 Membrane de séparation d'oxygène
EP07733256A EP2040822A1 (fr) 2006-06-21 2007-06-15 Membrane de séparation de l'oxygène
PCT/GB2007/002252 WO2007148057A1 (fr) 2006-06-21 2007-06-15 Membrane de séparation de l'oxygène
EA200802401A EA200802401A1 (ru) 2006-06-21 2007-06-15 Мембрана для выделения кислорода
CNA2007800228660A CN101479021A (zh) 2006-06-21 2007-06-15 氧气分离膜
CA002654364A CA2654364A1 (fr) 2006-06-21 2007-06-15 Membrane de separation de l'oxygene
AU2007262755A AU2007262755A1 (en) 2006-06-21 2007-06-15 Oxygen separation membrane
US12/308,511 US20100234650A1 (en) 2006-06-21 2007-06-15 Oxygen separation membrane
NO20090232A NO20090232L (no) 2006-06-21 2009-01-14 Oksygenseparasjonsmembran

Applications Claiming Priority (1)

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PCT/CN2006/003438 WO2008074181A1 (fr) 2006-12-18 2006-12-18 Membrane de séparation d'oxygène

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010100432A2 (fr) 2009-03-06 2010-09-10 Institute Of Metal Research, Chinese Academy Of Sciences Technologie de scellement
CN103950895A (zh) * 2014-04-16 2014-07-30 昆明理工大学 一种化学链连续制氧方法
US8956154B2 (en) 2010-11-23 2015-02-17 Nebb Engineering As Method and system for energy efficient conversion of a carbon containing fuel to CO2 and H2O

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CN1203831A (zh) * 1998-05-06 1999-01-06 南京化工大学 一种混合导电型致密透氧膜材料
CN1795972A (zh) * 2004-12-23 2006-07-05 中国科学院大连化学物理研究所 一种钙钛矿型含铈系列混合导体透氧膜其制备及应用
CN1864830A (zh) * 2005-05-16 2006-11-22 中国科学技术大学 一种双相混合导体透氧膜及其制备方法

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CN1203831A (zh) * 1998-05-06 1999-01-06 南京化工大学 一种混合导电型致密透氧膜材料
CN1795972A (zh) * 2004-12-23 2006-07-05 中国科学院大连化学物理研究所 一种钙钛矿型含铈系列混合导体透氧膜其制备及应用
CN1864830A (zh) * 2005-05-16 2006-11-22 中国科学技术大学 一种双相混合导体透氧膜及其制备方法

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HU J. ET AL.: "Research progress in methane partial oxidation to syngas using mixed conducting oxygen-permeable membrane reactor", NATURAL GAS CHEMICAL INDUSTRY, vol. 31, no. 3, 2006, pages 61 - 66 *
HUANG W. ET AL.: "Synthesis and characterization of Ln0.6Sr0.4Fe1-xCoxO3-delta for ITSOFC", J. INORGANIC MATERIALS, vol. 17, no. 4, 2002, pages 679 - 684 *
KHARTON V.V.: "Oxygen permeability of Ce0.8Gd0.2O2-delta-La0.7Sr0.3MnO3-delta composite membranes", J. ELECTROCHEMICAL SOCIETY, vol. 147, no. 7, 2000, pages 2814 - 2821 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010100432A2 (fr) 2009-03-06 2010-09-10 Institute Of Metal Research, Chinese Academy Of Sciences Technologie de scellement
US8956154B2 (en) 2010-11-23 2015-02-17 Nebb Engineering As Method and system for energy efficient conversion of a carbon containing fuel to CO2 and H2O
CN103950895A (zh) * 2014-04-16 2014-07-30 昆明理工大学 一种化学链连续制氧方法

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