WO2021262018A1 - A membrane, a use and a method for manufacturing thereof, and a method for pressureless oxygen-enrichment of the air - Google Patents
A membrane, a use and a method for manufacturing thereof, and a method for pressureless oxygen-enrichment of the air Download PDFInfo
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- WO2021262018A1 WO2021262018A1 PCT/PL2021/050043 PL2021050043W WO2021262018A1 WO 2021262018 A1 WO2021262018 A1 WO 2021262018A1 PL 2021050043 W PL2021050043 W PL 2021050043W WO 2021262018 A1 WO2021262018 A1 WO 2021262018A1
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- Prior art keywords
- membrane
- particles
- magnetic properties
- oxygen
- magnetic
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- 239000012528 membrane Substances 0.000 title claims abstract description 84
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 51
- 239000001301 oxygen Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 44
- 239000011159 matrix material Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 230000002051 biphasic effect Effects 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
- 230000006698 induction Effects 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000006247 magnetic powder Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910020674 Co—B Inorganic materials 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005408 paramagnetism Effects 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
- B01D67/00793—Dispersing a component, e.g. as particles or powder, in another component
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/06—Flat membranes
-
- 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
- B01D69/142—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes with "carriers"
-
- 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
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
-
- 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
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- 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
- B01D2257/104—Oxygen
-
- 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
- B01D2323/218—Additive materials
- B01D2323/2181—Inorganic additives
- B01D2323/21811—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/35—Use of magnetic or electrical fields
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/46—Magnetic properties
Definitions
- the invention relates to a membrane, a use and a method for manufacturing thereof, and a method for pressureless oxygen-enrichment of the air.
- the invention relates to a field of oxygen-transporting membranes.
- a method for membrane oxygen-enrichment of the air by use of pyrolytic carbon membranes, which function on the basis of communiquémolecular sieves” i.e. larger stays, smaller passes
- this method requires use of a high pressure difference at both sides of the membrane, which involves use of additional equipment and membranes of special structures.
- a traditional, effective method for the oxygen-enrichment of the air is its liquefaction and rectification (distillation), which is yet very expensive.
- the publication JP2008018338A discloses a membrane used for oxygen-enrichment of the air, comprising particles with magnetic properties dispersed between the first and the second membrane surface generating a concentration gradient along the membrane thickness, and consequently a magnetic field gradient.
- the particle concentration gradient is uniform along the entire thickness of the membrane and can be continuous or stepwise (layered).
- a driving force of the process for oxygen-enrichment of the air employing this membrane is an air pressure difference at both sides of the membrane, which causes oxygen to diffuse in a direction of the lower pressure.
- the diffusion can be further enhanced by oxygen being attracted to the dispersed particles with magnetic properties, in a direction from the lower particle concentration to the higher particle concentration.
- An object of the present invention is providing a membrane and a method which enables oxygen-enrichment of the air, with no air pressure difference applied at both sides of the membrane.
- the invention relates to an oxygen transporting membrane comprising a matrix and particles with magnetic properties dispersed therein, wherein a concentration of particles with magnetic properties increases between one internal membrane surface and the other internal membrane surface, generating a concentration gradient along the membrane thickness, and lines of a magnetic field generated by the particles with magnetic properties extend along the membrane thickness and their direction is consistent with the direction of said concentration gradient, characterized in that the concentration gradient of the particles with magnetic properties is a discrete gradient.
- the particles with magnetic properties are, relative to the matrix, a separate phase, which adheres to one of the internal membrane surfaces.
- the matrix is a polymer matrix.
- the amount of the particles with magnetic properties dispersed in the matrix is from more than 0 to 90 % by weight.
- Preferred average grain size of the particles with magnetic properties is from 5 to 50 pm.
- the invention relates also to a use of the above-defined membrane in window panes, windows, greenhouses, films, oxygen masks, oxygen tents and oxygen chambers.
- the invention relates also to a method for pressureless oxygen-enrichment of the air, comprising contacting the external surface of the membrane as defined above, from a side with the higher concentration of particles with magnetic properties in the membrane, with the air, the air undergoing oxygen-enrichment in a direction of the lower concentration of the particles with magnetic properties in the membrane.
- the invention relates to a method for manufacturing of a biphasic, heterogenous magnetic membrane, comprising the following steps of: a) dissolving a polymer in a solvent; b) dispersing particles with magnetic properties in the mixture obtained in the step a); c) casting the dispersion obtained in the step b) on a surface of a shape corresponding to a surface of the obtained membrane; d) sedimentation of particles with magnetic properties to form a polymer phase and a magnetic phase; e) evaporating the solvent; f) exposing the obtained membrane to an external magnetic field, the lines of the external magnetic field extending along the membrane thickness and being directed towards the magnetic phase.
- the evaporation of the solvent of the step e) may be conducted during the sedimentation of the step d).
- the step f) can be also conducted simultaneously with the steps e) and d).
- step f) may be conducted during the step d) or during the step e).
- the amount of the polymer in the mixture obtained in the step a) is from 3 to 5 % by weight
- the amount of the particles with magnetic properties in the dispersion obtained in the step b) is from 1 to 11 % by weight
- the external magnetic field induction value in the step f) is from more than 0 to 40 mT.
- the polymer is preferably a low density polymer.
- the membrane of the present invention almost all particles of the material with magnetic properties adhere to one of the internal membrane surfaces.
- the particles of the material with magnetic properties generate a discrete magnetic field gradient between one internal membrane surface and the other internal membrane surface, consistent with the particle concentration gradient.
- the magnetic field at the side of the membrane with a higher concentration of the particles with magnetic properties attracts molecules of oxygen, generating the chemical potential gradient of oxygen, and then inducing diffusion of oxygen through the membrane from the side with a higher concentration of the particles with magnetic properties, in the direction of the side with a lower concentration of the particles with magnetic properties.
- the air is enriched with oxygen at the side of the membrane with a lower concentration of the particles with magnetic properties and, at the same time, is depleted in oxygen at the side with a higher concentration of the particles with magnetic properties.
- a driving force of this process is the discrete magnetic field gradient.
- no pressure difference is required, and consequently there is no need to employ additional equipment, and the membranes are not subject to damage by a high pressure, regardless of their thickness and structure.
- the invention has been shown in the following exemplary embodiment.
- the magnetic membranes with matrices from EC ethylcellulose
- HBPI a highly branched polyimide
- LPI a linear polyimide
- a suitable amount of the polymer i.e. 5 % by weight for EC, 4 % by weight for LPI and 3 % by weight for HPBI, based on a solvent, was dissolved.
- the solvent was a mixture of ethanol and toluene in the 40:60 ratio
- the solvent was N-methylpyrrolidone.
- a material with magnetic properties i.e.
- a value of 3% in the table corresponds to an increase of the oxygen level of 3% to the final level of 24% etc.
- the amount of oxygen was found to increase or decrease depending on the side of the membrane exposed outside the measuring vessel. At first, the amount of oxygen was changing rapidly, but as the time elapsed, the oxygen concentration in the vessel was changing very slowly. After 36 hours, an increase of oxygen concentration of about 8% was observed.
- the membrane of the invention allows to enrich the air in oxygen with no air pressure difference applied at both sides of the membrane.
- the invention can be applied in any place where oxygen-enrichment of the air is needed, e.g. in window panes, greenhouses, films, oxygen masks, oxygen tents and oxygen chambers. Since, in parallel to the process of oxygen-enrichment of the air, an oxygen- depletion of the air proceeds on the other side of the membrane, the invention can also be applied in any place where low level of oxygen is required, e.g. wrappings for food and drugs.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Soft Magnetic Materials (AREA)
Abstract
The invention relates to an oxygen transporting membrane, comprising a matrix and particles with magnetic properties dispersed therein, wherein concentration of the particles with magnetic properties increases between one internal membrane surface and the other internal membrane surface, generating a concentration gradient along the membrane thickness, and lines of a magnetic field generated by the particles with magnetic properties extend along the membrane thickness and their direction is consistent with the direction of said concentration gradient, characterized in that the concentration gradient of the particles with magnetic properties is a discrete gradient.
Description
A membrane, a use and a method for manufacturing thereof, and a method for pressureless oxygen-enrichment of the air
The invention relates to a membrane, a use and a method for manufacturing thereof, and a method for pressureless oxygen-enrichment of the air. The invention relates to a field of oxygen-transporting membranes.
A method for membrane oxygen-enrichment of the air by use of pyrolytic carbon membranes, which function on the basis of „molecular sieves” (i.e. larger stays, smaller passes) is known in the art. However, this method requires use of a high pressure difference at both sides of the membrane, which involves use of additional equipment and membranes of special structures. A number of layered membranes operating on the same principle, i.e. utilizing a high pressure difference and a small diffusion coefficient, were proposed, which result, however, in low enrichment effectiveness and very limited applications. A traditional, effective method for the oxygen-enrichment of the air is its liquefaction and rectification (distillation), which is yet very expensive.
To increase effectiveness of a process for oxygen-enrichment of the air, so-called magnetic membranes, comprising particles with magnetic properties dispersed in a matrix, were proposed. Working of such membranes is based on utilizing paramagnetism of oxygen and diamagnetism of nitrogen, as well as insensibility of remaining air components to a magnetic field. For instance, the publications JP59109205A, JP58112022A and JP63291621A disclose membranes used for selective transport of oxygen, comprising powdery particles with magnetic properties dispersed uniformly in a matrix. The obtained membranes were further exposed to an external magnetic field. Such membranes had better properties of oxygen selectivity compared to the traditional membranes, however they did not eliminate necessity of utilizing an air pressure difference. The attractive force of a magnetic field for oxygen was not strong enough to generate a chemical potential gradient of oxygen, and then causes its diffusion.
The publication JP2008018338A discloses a membrane used for oxygen-enrichment of the air, comprising particles with magnetic properties dispersed between the first and the second membrane surface generating a concentration gradient along the membrane thickness, and consequently a magnetic field gradient. The particle concentration gradient is uniform along the entire thickness of the membrane and can be continuous or stepwise (layered). A driving force of the process for oxygen-enrichment of the air employing this membrane is an air pressure difference at both sides of the membrane, which causes oxygen to diffuse in a direction of the lower pressure. The diffusion can be further enhanced by oxygen being
attracted to the dispersed particles with magnetic properties, in a direction from the lower particle concentration to the higher particle concentration. In spite of the observed excellent transport properties of the membrane, the need of applying the pressure difference has not been eliminated. Therefore, in case of thin membranes, the inventors consider use of additional porous supports.
In publication by P. Borys, K. Pawelek, Z. J. Grzywna, On the magnetic channels in polymer membranes, Phys. Chem. Chem. Phys., 13, 17122-17129, 2011 there are raises doubts about attracting molecules of oxygen by a magnetic field gradient generated by particles with magnetic properties in a membrane.
An object of the present invention is providing a membrane and a method which enables oxygen-enrichment of the air, with no air pressure difference applied at both sides of the membrane.
The invention relates to an oxygen transporting membrane comprising a matrix and particles with magnetic properties dispersed therein, wherein a concentration of particles with magnetic properties increases between one internal membrane surface and the other internal membrane surface, generating a concentration gradient along the membrane thickness, and lines of a magnetic field generated by the particles with magnetic properties extend along the membrane thickness and their direction is consistent with the direction of said concentration gradient, characterized in that the concentration gradient of the particles with magnetic properties is a discrete gradient.
In a preferred embodiment of the invention, the particles with magnetic properties are, relative to the matrix, a separate phase, which adheres to one of the internal membrane surfaces. Preferably, the matrix is a polymer matrix.
In another embodiment of the invention, the amount of the particles with magnetic properties dispersed in the matrix is from more than 0 to 90 % by weight.
Preferred average grain size of the particles with magnetic properties is from 5 to 50 pm.
The invention relates also to a use of the above-defined membrane in window panes, windows, greenhouses, films, oxygen masks, oxygen tents and oxygen chambers.
The invention relates also to a method for pressureless oxygen-enrichment of the air, comprising contacting the external surface of the membrane as defined above, from a side with the higher concentration of particles with magnetic properties in the membrane, with the air, the air undergoing oxygen-enrichment in a direction of the lower concentration of the particles with magnetic properties in the membrane.
Moreover, the invention relates to a method for manufacturing of a biphasic, heterogenous magnetic membrane, comprising the following steps of: a) dissolving a polymer in a solvent; b) dispersing particles with magnetic properties in the mixture obtained in the step a); c) casting the dispersion obtained in the step b) on a surface of a shape corresponding to a surface of the obtained membrane; d) sedimentation of particles with magnetic properties to form a polymer phase and a magnetic phase; e) evaporating the solvent; f) exposing the obtained membrane to an external magnetic field, the lines of the external magnetic field extending along the membrane thickness and being directed towards the magnetic phase.
Preferably, the evaporation of the solvent of the step e) may be conducted during the sedimentation of the step d).
The step f) can be also conducted simultaneously with the steps e) and d).
Moreover, the step f) may be conducted during the step d) or during the step e).
In preferred embodiments of the method, the amount of the polymer in the mixture obtained in the step a) is from 3 to 5 % by weight, the amount of the particles with magnetic properties in the dispersion obtained in the step b) is from 1 to 11 % by weight, and the external magnetic field induction value in the step f) is from more than 0 to 40 mT.
The polymer is preferably a low density polymer.
In the membrane of the present invention, almost all particles of the material with magnetic properties adhere to one of the internal membrane surfaces. As a result, the particles of the material with magnetic properties generate a discrete magnetic field gradient between one internal membrane surface and the other internal membrane surface, consistent with the particle concentration gradient. In the method of pressureless oxygen-enrichment of the air of the invention, the magnetic field at the side of the membrane with a higher concentration of the particles with magnetic properties attracts molecules of oxygen, generating the chemical potential gradient of oxygen, and then inducing diffusion of oxygen through the membrane from the side with a higher concentration of the particles with magnetic properties, in the direction of the side with a lower concentration of the particles with magnetic properties. In this way, the air is enriched with oxygen at the side of the membrane with a lower concentration of the particles with magnetic properties and, at the same time, is depleted in oxygen at the side with a higher concentration of the particles with magnetic properties. A
driving force of this process is the discrete magnetic field gradient. In contrast to membranes of the prior art, no pressure difference is required, and consequently there is no need to employ additional equipment, and the membranes are not subject to damage by a high pressure, regardless of their thickness and structure. The invention has been shown in the following exemplary embodiment.
The magnetic membranes with matrices from EC (ethylcellulose), HBPI (a highly branched polyimide) and LPI (a linear polyimide) were prepared by casting from a solution. In a solvent, a suitable amount of the polymer, i.e. 5 % by weight for EC, 4 % by weight for LPI and 3 % by weight for HPBI, based on a solvent, was dissolved. In case of EC, the solvent was a mixture of ethanol and toluene in the 40:60 ratio, and in case of HBPI and LPI, the solvent was N-methylpyrrolidone. Then a material with magnetic properties (i.e. magnetic powder) in a suitable amount (indicated in Table) was dispersed, the obtained dispersion was homogenized, and then cast into a Petri dish and the solvent was allowed to slowly (48 hours) evaporate under a filter paper cover. In the course of the solvent evaporation process, the magnetic powder sedimented to obtain the biphasic membrane (with the magnetic and polymer layers). After 2 days the membrane was collected from the Petri dish, washed and dried at 40 °C. The last step of the preparation of the magnetic membranes was their magnetization in a pulse field magnet with induction of about 2.5 T. The lines of magnetic field and their direction were consistent with a magnetic powder concentration gradient. The results for the membranes with the three different matrices and for three different thicknesses and the same amount of three different powders are reported in the following table:
* - values for the respective granulations of a given powder
- a value of 3% in the table corresponds to an increase of the oxygen level of 3% to the final level of 24% etc. ** - MQFP-B - an alloy of the composition: Nd-Fe-Co-B, MQP-14-12 - an alloy of the composition: Nd-Pr-Fe-B, NdFeB - an alloy of the composition: Nd-Fe-B; manufactured by Magnequench Company, % content of elements not disclosed by the manufacturer
In case of prototyping of a window, studies were conducted for a membrane, a polymer matrix of which comprised cellulose acetate in the amount of 18,7 % by weight, and a filling comprised neodymium in the amount of 81,3 % by weight, with the grain size of 20 pm. The studies were conducted in measuring vessels of capacities of 50 ml and 100 ml, where the hole diameters for the membrane were 4 cm and 6 cm, respectively. Vessel rims were lubricated with a silicone grease and sealed with the membrane, suitably trimmed to vessel dimensions. The entire assembly was pressed down with a ring and tightened with screws. At the bottom of the vessel an oxygen sensor with an oxygen meter was provided, which was previously calibrated on the air in the room. The studies were conducted for 36 hours, with the oxygen content checked each hour. The amount of oxygen was found to increase or decrease depending on the side of the membrane exposed outside the measuring vessel. At first, the amount of oxygen was changing rapidly, but as the time elapsed, the oxygen concentration in the vessel was changing very slowly. After 36 hours, an increase of oxygen concentration of about 8% was observed.
Based on the data above, it can be stated that the membrane of the invention allows to enrich the air in oxygen with no air pressure difference applied at both sides of the membrane.
The invention can be applied in any place where oxygen-enrichment of the air is needed, e.g. in window panes, greenhouses, films, oxygen masks, oxygen tents and oxygen chambers. Since, in parallel to the process of oxygen-enrichment of the air, an oxygen- depletion of the air proceeds on the other side of the membrane, the invention can also be applied in any place where low level of oxygen is required, e.g. wrappings for food and drugs.
Claims
1. An oxygen transporting membrane, comprising a matrix and particles with magnetic properties dispersed therein, wherein a concentration of the particles with magnetic properties increases between one internal membrane surface and the other internal membrane surface, generating a concentration gradient along the membrane thickness, and lines of a magnetic field generated by the particles with magnetic properties extend along the membrane thickness and their direction is consistent with the direction of said concentration gradient, characterized in that the concentration gradient of particles with magnetic properties is a discrete gradient.
2. The membrane according to Claim 1, characterized in that the particles with magnetic properties are, relative to the matrix, a separate phase, which adheres to one of the internal membrane surfaces.
3. The membrane according to claims 1-2, characterized in that the matrix is a polymer matrix.
4. The membrane according to claims 1-3, characterized in that the amount of the particles with magnetic properties dispersed in the matrix is from more than 0 to 90 % by weight.
5. The membrane according to claims 1-4, characterized in that an average grain size of the particles with magnetic properties is from 5 to 50 pm.
6. Use of the membrane as defined in claims 1-5 in window panes, windows, greenhouses, films, oxygen masks, oxygen tents and oxygen chambers.
7. A method for pressureless oxygen-enrichment of the air, characterized in that the method comprises contacting the external surface of the membrane as defined in claims 1-5, from a side of the higher concentration of the particles with magnetic properties in the membrane, with air, the air undergoing oxygen-enrichment in a direction of the lower concentration of particles with magnetic properties in the membrane.
8. A method for manufacturing of a biphasic, heterogenous magnetic membrane, characterized in that the method comprises the following steps of: a) dissolving a polymer in a solvent; b) dispersing particles with magnetic properties in the mixture obtained in the step a); c) casting the dispersion obtained in the step b) on a surface of a shape corresponding to a surface of the membrane to be obtained; d) sedimentation of the particles with magnetic properties to form a polymer phase and a magnetic phase; e) evaporating the solvent;
f) exposing the obtained membrane to an external magnetic field, the lines of the external magnetic field extending along the membrane thickness and being directed towards the magnetic phase.
9. The method according to claim 8, characterized in that the evaporation of the solvent of the step e) may be conducted during the sedimentation of the step d).
10. The method according to claim 9, characterized in that the step f) may be conducted simultaneously with the steps e) and d).
11. The method according to claim 8, characterized in that the step f) may be conducted during the step d) or during the step e).
12. The method according to claims 8-11, characterized in that the amount of the polymer in the mixture obtained in the step a) is from 3 to 5 % by weight.
13. The method according to claims 8-12, characterized in that the amount of the particles with magnetic properties in the dispersion obtained in the step b) is from 1 to 11 % by weight.
14. The method according to claim 8-12, characterized in that the external magnetic field induction value in the step f) is from more than 0 to 40 mT.
15. The method according to claim 8-14, characterized in that the polymer is a low density polymer.
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PL434427A PL434427A1 (en) | 2020-06-24 | 2020-06-24 | Membrane, use and method for production thereof and method for non-pressure enrichment of oxygen in air |
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WO2023102118A2 (en) | 2021-12-01 | 2023-06-08 | 10X Genomics, Inc. | Methods, compositions, and systems for improved in situ detection of analytes and spatial analysis |
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JP2008018338A (en) * | 2006-07-12 | 2008-01-31 | Equos Research Co Ltd | Oxygen-enriched membrane and its manufacturing method |
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JP2008018338A (en) * | 2006-07-12 | 2008-01-31 | Equos Research Co Ltd | Oxygen-enriched membrane and its manufacturing method |
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Cited By (1)
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WO2023102118A2 (en) | 2021-12-01 | 2023-06-08 | 10X Genomics, Inc. | Methods, compositions, and systems for improved in situ detection of analytes and spatial analysis |
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