EP3445476A1 - Dispositif et procédé pour le transport contrôlé de gaz sur des membranes à structure métallo-organique - Google Patents
Dispositif et procédé pour le transport contrôlé de gaz sur des membranes à structure métallo-organiqueInfo
- Publication number
- EP3445476A1 EP3445476A1 EP17739209.9A EP17739209A EP3445476A1 EP 3445476 A1 EP3445476 A1 EP 3445476A1 EP 17739209 A EP17739209 A EP 17739209A EP 3445476 A1 EP3445476 A1 EP 3445476A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mof material
- electric field
- mof
- gaseous compound
- process according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
- 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
- B01D53/02—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 adsorption, e.g. preparative gas chromatography
- B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0454—Controlling adsorption
-
- 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
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
-
- 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
- B01D71/028—Molecular sieves
- B01D71/0281—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/10—Single element gases other than halogens
- B01D2257/108—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/40—Further details for adsorption processes and devices
- B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- 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
- B01D53/32—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 electrical effects other than those provided for in group B01D61/00
- B01D53/323—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 electrical effects other than those provided for in group B01D61/00 by electrostatic effects or by high-voltage electric fields
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C—MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03C9/00—Electrostatic separation not provided for in any single one of the other main groups of this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Definitions
- the present invention relates to a device and a process for controlled transport of a gaseous compound into and/or out of a metal-organic framework (MOF) material, which preferably is in the form of a MOF membrane, and to the use of the device as a separation device for a gaseous compound from a gas composition.
- MOF metal-organic framework
- the device and the process allow to control the flux and/or the composition of a gaseous compound, which can be a component of a gas composition, into the MOF material and out of the MOF material, e.g. a gas separation process in which a gaseous component contained in a gas composition is transported through the MOF material.
- a gas separation process in which a gaseous component contained in a gas composition is transported through the MOF material.
- the device and process of the invention allow to control the flux and/or selectivity of the gaseous compound contained in the gas composition, wherein the gaseous compound permeates across a MOF membrane.
- the device and process of the invention allow control of the rate and/or selectivity of the absorption and/or desorption, and of the permeation of the gaseous compound, respectively.
- the gas gaseous compound can comprise or consist of one or more molecule species.
- WO 2013/177199A1 describes the production of metal-organic framework (MOF) membranes by dip-coating a porous polymer, e.g. in the form of hollow tubes, into a suspension of MOF nanocrystals as a seed, followed by drying and growing larger MOF crystals on the porous polymer from a MOF precursor solution at temperatures as low as 65°C.
- MOF metal-organic framework
- WO2014/115177 A2 describes an in situ production process for a MOF-polymer composite, e.g. a zinc imidazolate framework on polysulfone without pre-seeding of MOF or polymer modification.
- the MOF layer can substantially cover the porosity of the membrane.
- US 7,637,983 Bl describes membranes of polymers forming a continuous phase that contains dispersed MOF particles having highly crystalline zeolite-like structures.
- the polymer is a glassy polymer, e.g. polyimide, polyetherimide, cellulose acetate, polysulfone or polyethersulfone.
- the MOF particles are mixed with the polymer in a solvent and formed by solution casting of the slurry of the MOF particles in the polymer in solvent.
- WO 2012/164395 Al and US 9248400 B2 describe the production of a zeolitic imidazole framework (ZIF) membrane by deposition of ZIF seed particles on an a-alumina, glass, polymer or stainless steel support, and growing ZIF crystals from solution.
- ZIF zeolitic imidazole framework
- these known processes using MOF in the form of pure or composite membranes have the disadvantage that they show a permanent gas flux through the membrane, and that the composition of a permeate is constant for a given original gas composition.
- a further disadvantage can be that molecules which are larger than expected from the pore size can pass the membrane, e.g. due to lattice vibrations and/or linker flip-flop rotational motions.
- US2010/0319534 Al describes that the batch- wise adsorption of a gaseous compound onto the surface of a porous dielectric material, e.g. a MOF, can be enhanced by application of an electric field to the porous dielectric.
- the adsorption which is believed to be caused by increased electrostatic binding forces generated between the porous dielectric and the gas, can be used for gas storage and for electric field swing adsorption in analogy to pressure swing adsorption.
- US 2015/0073164 Al describes the adsorption of C0 2 onto a MOF material containing a metal ion having an unpaired electron, the metal atom being bound by coordination with an organic compound.
- the application of an electric field, which preferably is an alternating field, or of an electromagnetic field increases the amount of adsorbed CO2.
- the adsorptive processes using application of an electric field during contact of the gas and the porous material are based on charge shifting or polarizing the surface of the porous material, resulting in increased interaction with polarizable gas molecules.
- the invention provides a device and process for controlling the flux and/or the composition of a gaseous compound permeating through a metal-organic framework membrane.
- the invention achieves the object by the features of the claims, especially by a device and a process as well as by the use of the device as a separation device for a gaseous compound by contacting a gaseous compound with a MOF material, wherein optionally the gaseous compound is contained in a gas composition.
- the invention is characterized by the application of an electric field to the MOF material during permeation of the gaseous compound. It has been found that the application of an electric field to the MOF material changes permeation of the gaseous compound. In detail, it has been found that e.g.
- the application of an electric field changes the flux and composition of the permeating gaseous compound from a gas composition, and that the application of an electric field changes the desorption of a gaseous compound.
- the electric field can be applied to the MOF material by generating an electric field between a pair of electrodes, the electric field encompassing the MOF material.
- the electrodes are arranged at opposite sides of the MOF material, e.g. the electrodes can form a capacitor containing the MOF material between its electrodes.
- the electrodes can be arranged with a spacing from the MOF material, or the electrodes can be arranged adjacent the MOF material, e.g. in direct electric contact with the MOF material.
- both the electrodes extend over the cross-section of the MOF material that is parallel to the electrodes.
- At least one of the electrodes can have a closed surface or can have openings allowing the passage of gas across the electrode, e.g. at least one electrode, e.g. both electrodes, can be formed as a grid of a conductive material.
- the electrodes are electrically connected with opposite polarities of a voltage source.
- the voltage source can be disposed to provide the electrodes with constant voltage (DC) or with alternating voltage (AC).
- DC constant voltage
- AC alternating voltage
- the voltage source is disposed to provide the electrodes with alternating voltage.
- voltage source is disposed to provide the electrodes with constant voltage.
- the voltage source can be disposed to provide pulsed voltage, e.g. at a frequency of at least 0.01 per min, preferably at least 0.1 per min, e.g. up to 50 Hz, e.g. up to 10 or up to 2 Hz.
- the MOF material can be in the form of a membrane, e.g. one or at least two MOF membranes arranged with a spacing in parallel or in a spiral shape.
- the MOF material can e.g. be in the form of MOF material particles dispersed in a polymer forming a membrane, in the form of a layer arranged on a carrier, optionally forming a membrane.
- the polymer preferably is permeable for the gaseous compound, e.g. porous, and the polymer can e.g. be one of polyimide, polyetherimide, cellulose acetate, polysulfone and polyethersulfone, as known in the art.
- the carrier is permeable for the gaseous compound and can e.g.
- the MOF material can consist of MOF material, e.g. in the form of a membrane or in particulate form, preferably connected by a polymer, which is gas-permeable or gas-impermeable.
- the MOF material is in the form of a membrane which is arranged in a housing, the MOF membrane separating a first inlet port and a first outlet port on one side of the MOF membrane from a second outlet port arranged on the opposite side of the MOF membrane.
- the MOF material is flexible and/or shows shear deformation and/or soft- mode phase changes when exposed to the electric field, optionally depending on the field strength.
- the soft-mode phase changes are e.g. changes from a cubic to a monoclinic or triclinic morphology, preferably as detected by X-ray diffraction (XRD) analysis.
- XRD X-ray diffraction
- the phase changes are detected as a lattice deformation of the starting MOF framework as a result of the ionic and dipolar interaction of the MOF ions and dipolar linker with an electric field.
- the property of the MOF material being flexible is e.g. determined as a MOF with dipolar linker molecules which allow rotatory motions and with a crystal lattice which allows soft mode motions as a result of the interactions of the dipolar linker molecules and the ions with an external electric field.
- the property of the MOF material showing soft mode deformation is e.g. determined as a material which is stiffened in interaction with and electric field and which changes its pore diameter in interaction with the electric field.
- the change of gas transport characteristics can be reversible, e.g. within a time of less than 1 s or up to 90 min after termination of the electric field, Therefore, the electric field can be applied intermittently, e.g. for a pulse duration in the range from 0.1s to .. s, with no field between pulses for a time in the range from 1 to 90 min, e.g. 5 to 30 min.
- the present invention also relates to a process for producing a MOF material by a step of exposing the MOF material to an electric field, which step can permanently change the permeation properties.
- the field strength can e.g. be in the range from 100 to 1000 V/mm, e.g. from 300 to 700 V/mm, e.g. 500 V/mm, constant or alternating polarity.
- the electric field is in perpendicular to the main plane of the MOF material.
- the MOF material preferably is a zeolitic imidazole framework (ZIF) material, e.g. ZIF-90, ZIF-8, MIL-96, or a mixture of at least two of these.
- ZIF zeolitic imidazole framework
- the gaseous compound can e.g. be H 2 , C0 2 , NOx, hydrocarbons, or a mixture of at least two of these.
- Fig. 1 a device and process according to the invention
- Fig. 2 a graph for the permeance of a MOF material in presence and absence of an electric field.
- Figure 1 depicts a MOF material 1 arranged as a layer on a carrier 2 which is permeable for a gaseous compound.
- a pair of electrodes 3, 4 is arranged with a spacing on both sides of the MOF material 1. As preferred, the electrodes 3, 4 are parallel to the MOF material 1 layer.
- the electrodes extend over the MOF material 1 in order to generate an electric field 5 encompassing the entire MOF material 1.
- the electrodes are electrically connected to opposite polarity contacts of a voltage source 6.
- the MOF material 1 is arranged in a housing 7 and separates a first inlet port 8 and a first outlet port 9 from a second outlet port 10.
- the voltage source provides voltage to the electrodes 3, 4 during absorption of a gaseous compound 11 into the MOF material 1 and/or during desorption of a gaseous compound 11 from the MOF material 1.
- the gaseous compound 11 is contacted with the MOF material 1, e.g. introduced into the housing 7 via first inlet port 8.
- the gaseous compound can exit from the housing via first outlet port 9 and/or in case the carrier 2 is permeable, the gaseous compound can exit from the housing via second outlet port 10.
- the gaseous compound 11 is contained in a gas composition that is fed into the first inlet port 8, a retentate gas fraction can exit via first outlet port 9, which retentate gas is depleted for the gaseous compound 11 permeating through the MOF material 1 and carrier 2.
- the permeated gaseous compound 12 can exit the housing via second outlet port 10.
- the electrodes 3, 4 are provided with voltage generating an electric field 5 encompassing the MOF material 1 in order to change the permeating flux and/or the constituents of the permeated gaseous compound 8.
- a MOF membrane of a ZIF-8 layer supported by a carrier was arranged in a device as generally shown in Fig. 1.
- CO2 was introduced into the housing via first inlet port 8 and allowed to exit via first outlet port 9 and via second outlet port 10, which was separated by the MOF material.
- the MOF material ZIF-8 was grown on a carrier formed by a ceramic disc comprising (X-AI2O3 having an asymmetric structure and a mean pore diameter of 70 nm (obtained from Inocermic, Hermsdorf, Germany).
- the electrodes 3, 4 were formed by metal meshes.
- Fig. 2 depicts the permeation rate of C0 2 across the MOF membrane, showing that after switching on the electric field, after an equilibration or switching period about 8 min the permeation rate is drastically reduced by a factor of about 3.
- Example 2 Separation of hydrogen from a mixture of hydrogen and CQ 2
- MOF-90 As a MOF material, ZIF-90 was grown on a carrier formed by a ceramic disc comprising a- AI2O3 having an asymmetric structure and a mean pore diameter of 70 nm (obtained from Inocermic, Hermsdorf, Germany) to form a MOF membrane.
- the MOF membrane was arranged in a device according to Fig. 1, using electrodes 3, 4 formed by metal meshes.
- a gas composition of equimolar contents of H 2 and C0 2 was introduced into the housing via first inlet port 8.
- the permeated gaseous compound was 70% H 2 and 30% C0 2 .
- the permeated gaseous compound When applying voltage to generate a constant electric field of 500 V/mm, after 8 min the permeated gaseous compound is 85% H 2 and 15% C0 2 . This demonstrates that the electric field influences the selectivity of the MOF material for a gaseous compound.
- Example 3 Separation of hydrogen from a mixture of hydrogen and C0 2
- MIL-96 was grown on a carrier formed by a ceramic disc comprising a- AI2O3 having an asymmetric structure and a mean pore diameter of 70 nm (obtained from Inocermic, Hermsdorf, Germany) to form a MOF membrane.
- the MOF membrane was arranged in a device according to Fig. 1, using electrodes 3, 4 formed by metal meshes.
- a gas composition of equimolar contents of H 2 and C0 2 was introduced into the housing via first inlet port 8. In the absence of an electric field, the permeated gaseous compound was 70% H 2 and 30% C0 2 .
- the permeated gaseous compound When applying alternating voltage to generate an electric field of 500 V/mm alternating at a frequency of 0.1 per min, the permeated gaseous compound is 90% H 2 and 10%) C0 2 at full field strength, the composition of the permeated gaseous compound alternating with the same frequency of 0.1 per min as the voltage. This demonstrates that the electric field influences the selectivity of the MOF material for a gaseous compound.
- Example 4 Separation of hydrogen from a mixture of hydrogen and CQ 2
- MOF material 10 vol.-% MIL- 125, crystal size 2 - 4 ⁇ , was dispersed in 90 vol.-% polyimide (Matrimid) to form a MOF material containing membrane.
- the MOF membrane was arranged in a device according to Fig. 1, using electrodes 3, 4 formed by metal meshes.
- a gas composition of equimolar contents of H 2 and C0 2 was introduced into the housing via first inlet port 8.
- the permeated gaseous compound is 75% H 2 and 25% C0 2 .
- the permeated gaseous compound is 95% H 2 and 5% C0 2 . This demonstrates that the electric field influences the selectivity of the MOF material for a gaseous compound.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16179033.2A EP3269441A1 (fr) | 2016-07-12 | 2016-07-12 | Dispositif et procédé de transport de gaz contrôlé sur des membranes à structure métal-organique |
| PCT/EP2017/065851 WO2018010951A1 (fr) | 2016-07-12 | 2017-06-27 | Dispositif et procédé pour le transport contrôlé de gaz sur des membranes à structure métallo-organique |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3445476A1 true EP3445476A1 (fr) | 2019-02-27 |
Family
ID=56413490
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP16179033.2A Withdrawn EP3269441A1 (fr) | 2016-07-12 | 2016-07-12 | Dispositif et procédé de transport de gaz contrôlé sur des membranes à structure métal-organique |
| EP17739209.9A Withdrawn EP3445476A1 (fr) | 2016-07-12 | 2017-06-27 | Dispositif et procédé pour le transport contrôlé de gaz sur des membranes à structure métallo-organique |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP16179033.2A Withdrawn EP3269441A1 (fr) | 2016-07-12 | 2016-07-12 | Dispositif et procédé de transport de gaz contrôlé sur des membranes à structure métal-organique |
Country Status (2)
| Country | Link |
|---|---|
| EP (2) | EP3269441A1 (fr) |
| WO (1) | WO2018010951A1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023069826A (ja) * | 2021-11-08 | 2023-05-18 | Eneos株式会社 | 複合体、二酸化炭素捕捉剤、及び複合体の製造方法 |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7637983B1 (en) | 2006-06-30 | 2009-12-29 | Uop Llc | Metal organic framework—polymer mixed matrix membranes |
| US8449650B2 (en) * | 2009-06-17 | 2013-05-28 | Los Alamos National Security, Llc | Gas storage and separation by electric field swing adsorption |
| US8197579B2 (en) * | 2009-06-19 | 2012-06-12 | Empire Technology Development Llc | Gas storage and release using piezoelectric materials |
| CN103702741B (zh) | 2011-05-31 | 2018-01-26 | 阿卜杜拉国王科技大学 | 用于分离c2‑和c3+混合物的膜 |
| US9375678B2 (en) | 2012-05-25 | 2016-06-28 | Georgia Tech Research Corporation | Metal-organic framework supported on porous polymer |
| WO2014115177A2 (fr) | 2013-01-28 | 2014-07-31 | Council Of Scientific & Industrial Research | Procédé pour la préparation de composites de membrane polymère poreuse aux mof |
| JP2015077594A (ja) * | 2013-09-12 | 2015-04-23 | パナソニックIpマネジメント株式会社 | 多孔性金属有機骨格材料に二酸化炭素を吸着させる方法、多孔性金属有機骨格材料を冷却する方法、多孔性金属有機骨格材料を用いてアルデヒドを得る方法、および多孔性金属有機骨格材料を加温する方法 |
-
2016
- 2016-07-12 EP EP16179033.2A patent/EP3269441A1/fr not_active Withdrawn
-
2017
- 2017-06-27 WO PCT/EP2017/065851 patent/WO2018010951A1/fr not_active Ceased
- 2017-06-27 EP EP17739209.9A patent/EP3445476A1/fr not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018010951A1 (fr) | 2018-01-18 |
| EP3269441A1 (fr) | 2018-01-17 |
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