KR101791422B1 - Hollow Fiber Membrane comprising Derivatives of Transition Metal-Salen for Separating Oxygen and Manufacturing Method thereof - Google Patents
Hollow Fiber Membrane comprising Derivatives of Transition Metal-Salen for Separating Oxygen and Manufacturing Method thereof Download PDFInfo
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- KR101791422B1 KR101791422B1 KR1020150151806A KR20150151806A KR101791422B1 KR 101791422 B1 KR101791422 B1 KR 101791422B1 KR 1020150151806 A KR1020150151806 A KR 1020150151806A KR 20150151806 A KR20150151806 A KR 20150151806A KR 101791422 B1 KR101791422 B1 KR 101791422B1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- 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
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- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow fiber membrane for oxygen separation, and more particularly to a hollow fiber membrane for oxygen separation in which a coating layer containing a transition metal-salen derivative is formed on the inner surface. The hollow fiber membrane for oxygen separation according to the present invention is characterized in that the coating solution containing the transition metal-salen derivative is coated on the inner surface of the porous tubular polymer membrane so that the selectivity and permeability of oxygen gas are excellent even at low pressure, Efficiency can be shown.
Description
The present invention relates to a hollow fiber membrane for oxygen separation, and more particularly, to a hollow fiber membrane for oxygen separation in which a coating layer containing a transition metal-salen derivative is formed on a hollow inner surface.
Recently, interest in the environment and energy has been increasing, and researches on oxygen membranes have been actively carried out. Oxygen separation membrane extracts only pure oxygen from the air and is widely used in the field of ammonia synthesis and other synthetic chemical industries, metallurgy, metal welding, and cutting. It is also used in the post-combustion capture process, which is a technique for capturing the carbon dioxide contained in the post-combustion flue gas in relation to the carbon dioxide capture technique. The most important design factor in the separation process using the wet sorbent which is most widely used during the post-combustion capture process is the efficiency and rate of carbon dioxide removal of the sorbent. In this case, when oxygen is present in the flue gas, The carbon dioxide absorbing ability is lowered due to the oxidative degradation.
Examples of the oxygen separation method include a cryogenic method, a pressure swing adsorption method, and a membrane separation method. Although PSA and PSA are commercialized in this process, there is a disadvantage in that a large amount of oxygen separation process requires a large amount of investment and energy due to the characteristics of the equipment. On the other hand, the oxygen separation process using membranes, which has been actively researched recently, is expected to replace the existing processes with high efficiency and low process cost as compared with the existing gas separation technology.
The oxygen separation method using a separation membrane is a separation method using a ceramic separation membrane or a polymer separation membrane. Oxygen separation using a ceramic membrane separates oxygen and electrons from oxygen in various components of the air. The separated oxygen ions and electrons are respectively transmitted through the oxygen separation membrane, and the transferred oxygen ions and electrons are recombined to allow oxygen molecules to escape to the outside of the oxygen separation membrane, thereby separating pure oxygen. However, the ceramic separator is driven at a high temperature, requires a catalyst containing a noble metal, and is expensive to manufacture. The oxygen separation method using the polymer membrane uses the principle of molecular sieve to separate oxygen according to the size of the gas molecules. The oxygen separation method using the conventional polymer membrane has a problem in that the selectivity and the permeability are inversely proportional to each other. Therefore, compounds for fixing oxygen molecules can be used to improve oxygen selectivity. In order to apply such a compound to a polymer membrane, a coating method for sufficiently exhibiting a selective oxygen fixation and release function, that is, an oxygen permeation function of a polymer membrane, is needed.
Korean Unexamined Patent Application Publication No. 2005-0039433 discloses a hollow fiber membrane manufacturing method for gas separation, and discloses a hollow fiber membrane production method using a spinning method by adding a transition metal containing cobalt to a polymer solution. However, this is a method of merely mixing a transition metal with a polymer material, resulting in inefficiency of gas selectivity and permeability.
US Patent Publication No. 2014-0102884 relates to a gas separation membrane, and discloses a plate separation membrane including nanoparticles such as nonvolatile liquid and silica. However, this is a separation membrane used in an electrochemical system, which requires additional energy and a complicated manufacturing method.
Therefore, it is necessary to develop an oxygen separation membrane having high selectivity and permeability and exhibiting high efficiency even at low pressure.
SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a hollow fiber membrane for oxygen separation in which a coating layer containing a transition metal-salen derivative is formed on a hollow inner surface.
The present inventors have succeeded in separating the oxygen in the flue gas by using the hollow fiber membrane for oxygen separation in the post-combustion collecting process of collecting the carbon dioxide contained in the post-combustion flue gas and injecting the oxygen-depleted flue gas into the absorption tower, The present invention has been accomplished by finding a hollow fiber membrane for oxygen separation for maximizing the absorption capacity.
The present invention relates to a porous tubular polymer membrane; And a porous coating layer formed on the inner surface of the tubular polymer membrane, wherein the coating layer comprises a transition metal-salen derivative and a polymer compound in a weight ratio of 1: 100 to 50: 100, and the transition metal- Wherein the derivative compound is a compound represented by the following formula:
[Chemical Formula 1]
Wherein the transition metal is selected from the group consisting of Co, Cu, Fe, Ni, Mn, Ru and Rh, Pt, Mg, (Pb), palladium (Pd), zinc (Zn), titanium (Ti), vanadium (V), chromium (Cr), silver (Ag), gold (Au) , Tin (Sn) and zirconium (Zr), wherein R1 and R2 are the same or different and each independently represent hydrogen, halogen, alkyl of 1 to 10 carbon atoms, alkenyl of 1 to 10 carbon atoms , Alkynyl having 1 to 10 carbon atoms, aryl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkylcarbonyl having 1 to 10 carbon atoms, or
The polymer membrane and the polymer compound may be made of the same or different polymer materials, and the polymer material may be a cellulose polymer, a polyethylene polymer, a polyethylene glycol polymer, a silicone polymer, a melamine resin polymer, a polyolefin polymer, a polystyrene polymer, Which is at least one selected from the group consisting of a carbonate polymer, a polysulfone polymer, a polyamide polymer, a polyimide polymer, a polymethacrylate polymer, a polyester polymer, a polybenzimidazole polymer, and a polyacetal polymer, -Salen derivatives of the present invention.
The present invention also provides a hollow fiber membrane for oxygen separation comprising a transition metal-salen derivative, wherein said coating layer is 1 nm to 400 nm thick.
The present invention also relates to a method for producing a hollow fiber membrane for oxygen separation wherein a transition metal-salen derivative is coated on the inner surface, comprising the steps of: preparing a spinning solution containing a polymer; Preparing a porous tubular polymer membrane through the nozzle with the spinning solution; Preparing a coating solution coated on the inner surface of the porous tubular polymer membrane; And coating the coating solution on the inner surface of the porous tubular polymer, wherein the step of preparing the coating solution comprises mixing the transition metal-salen derivative and the polymer compound in a weight ratio of 1: 100 to 50: 100 And a transition metal-salen derivative, wherein the organic solvent is mixed with an organic solvent.
The present invention also
Wherein the transition metal-salen derivative compound is a compound represented by the following formula:
[Chemical Formula 1]
Wherein the transition metal is selected from the group consisting of Co, Cu, Fe, Ni, Mn, Ru and Rh, Pt, Mg, (Pb), palladium (Pd), zinc (Zn), titanium (Ti), vanadium (V), chromium (Cr), silver (Ag), gold (Au) , Tin (Sn) and zirconium (Zr), wherein R1 and R2 are the same or different and each independently represent hydrogen, halogen, alkyl of 1 to 10 carbon atoms, alkenyl of 1 to 10 carbon atoms , Alkynyl having 1 to 10 carbon atoms, aryl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, alkylcarbonyl having 1 to 10 carbon atoms, or
The present invention also relates to a method for producing a spinning solution, wherein the spinning solution is selected from the group consisting of cellulose polymer, polyethylene polymer, polyethylene glycol polymer, melamine resin polymer, polyolefin polymer, polystyrene polymer, polycarbonate polymer, polysulfone polymer, polyamide polymer, A mixture of at least one member selected from the group consisting of a methacrylate-based polymer, a polyester-based polymer, a polybenzimidazole polymer, or a polyacetal polymer; N-dimethlaniline, N-methylpyrrolidone, tetrahydrofurane; And a transition metal-salen derivative which is a mixture of lithium chloride and lithium chloride. The present invention also provides a method for producing a hollow fiber membrane for oxygen separation.
The present invention also relates to the above-mentioned polymer compound, wherein the polymer compound is at least one selected from the group consisting of silicone polymers, cellulose polymers, polyethylene polymers, polyethylene glycol polymers, melamine resin polymers, polyolefin polymers, polystyrene polymers, polycarbonate polymers, polysulfone polymers, Preparation of a hollow fiber membrane for oxygen separation comprising at least one transition metal-salen derivative selected from the group consisting of a polymer, a polymethacrylate-based polymer, a polyester-based polymer, a polybenzimidazole polymer, and a polyacetal polymer ≪ / RTI >
The coating process may further include coating the inner surface of the porous tubular polymer membrane, removing the coating solution at the center of the porous tubular polymer membrane after the coating solution is injected into the porous tubular polymer membrane for 10 seconds to 60 seconds, Wherein the drying is carried out at a temperature of from room temperature to room temperature, and the transition metal-salen derivative compound is dried at a temperature of from room temperature to room temperature.
The hollow fiber membrane for oxygen separation according to the present invention is characterized in that a coating solution containing a transition metal-salen derivative is coated on the inner surface of a porous tubular polymer membrane to exhibit high selectivity and permeability of oxygen gas even at low pressure, It is possible to exhibit excellent efficiency in separation.
1 is a schematic view illustrating a method of manufacturing a porous tubular polymer membrane according to an embodiment of the present invention.
2 is a schematic view illustrating a method of forming a coating layer on the outer side of a multistage tubular polymer membrane according to an embodiment of the present invention.
3 illustrates a gas permeability measurement system according to an embodiment of the present invention.
FIG. 4 is a graph showing gas permeability and selectivity for oxygen and nitrogen gas in a hollow fiber membrane coated with 10% t-Bu-Co (Salen) -PDMS according to an embodiment of the present invention.
FIG. 5 is a graph showing gas permeability and selectivity for oxygen and nitrogen gas in a hollow fiber membrane coated with 25% t-Bu-Co (Salen) -PDMS according to one embodiment of the present invention.
FIG. 6 is a graph showing gas permeability and selectivity for oxygen and carbon dioxide gas in a hollow fiber membrane coated with 25% t-Bu-Co (Salen) -PDMS according to an embodiment of the present invention.
FIG. 7 is a graph comparing the oxygen permeability of a hollow fiber membrane coated with 25% t-Bu-Co (Salen) -PDMS according to an embodiment of the present invention with a conventional commercialized membrane.
Prior to the detailed description of the present invention, terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms. Therefore, the embodiments described in this specification and the configurations shown in the drawings are merely the most preferred embodiments of the present invention and do not represent all the technical ideas of the present invention. Therefore, It is to be understood that equivalents and modifications are possible.
In one aspect, the present invention provides a porous tubular polymer membrane; And a porous coating layer formed on the inner surface of the tubular polymer membrane, wherein the coating layer comprises a transition metal-salen derivative and a polymer compound in a weight ratio of 1: 100 to 20: 100 . The separation membrane can be defined as an interface (material) having a function of selectively restricting the movement of a substance between two phases. Gas separation using membranes proceeds by selective gas permeation principle for membranes. That is, when the gas mixture contacts the surface of the membrane, the gas component dissolves and diffuses into the membrane, where the solubility and permeability of the respective gas components are different for the membrane material. The propulsive force for gas separation is the partial pressure difference for the particular gas component applied across the membrane. In particular, the membrane separation process using a separation membrane has been widely used in various fields because it has no phase change and energy consumption is low. The present invention provides a hollow fiber membrane for oxygen separation which separates oxygen from a post-combustion exhaust gas supplied to carbon dioxide capture.
The hollow fiber membrane for oxygen separation of the present invention is a two-layer structure in which a porous tubular polymer membrane is used as a support and a coating layer is formed thereon. In one embodiment, the material of the tubular polymer membrane is selected from the group consisting of cellulose polymer, polyethylene polymer, polyethylene glycol polymer, melamine resin polymer, polyolefin polymer, polystyrene polymer, polycarbonate polymer, polysulfone polymer, polyamide polymer, At least one polymer selected from the group consisting of polyacrylates, polymethacrylates, polyester polymers, polybenzimidazole polymers, and polyacetal polymers, and preferably at least one selected from the group consisting of polysulfone, polyethersulfone , Sulfonated polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyimide, polyetherimide, polyester, polybenzimidazole, and polyamide. The tubular polymer membrane has a diameter of 100 탆 to 1,500 탆, preferably 400 탆 to 1,000 탆. When the diameter is more than 100 탆, the gas can not pass smoothly due to the pressure when the gas is injected into the tubular polymer membrane. When the diameter is more than 1500 탆, the gas passage efficiency of the membrane is decreased because the probability of contact of the gas with the polymer membrane wall is low. The surface of the tubular polymer membrane may be a porous membrane permeable to gas, and the porous membrane may have a pore size ranging from 10 nm to 400 nm.
The coating layer coated on the inner surface of the tubular polymer membrane of the present invention is a transition metal-salen derivative represented by the following formula (1), including a transition metal compound of the N2O2 type for transferring a transition metal to a ligand of the N2O2 type. In one embodiment, the transition metal is selected from the group consisting of Co, Cu, Fe, Ni, Mn, Ru and Rh, Pt, Mg, Pb, Pd, Zn, Ti, V, Cr, Ag, Au and Al, (Sb), tin (Sn), and zirconium (Zr). Wherein R 1 and R 2 are the same or different and each is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, alkenyl of 1 to 10 carbon atoms, alkynyl of 1 to 10 carbon atoms, aryl of 1 to 10 carbon atoms, Alkoxy of 1 to 10 carbon atoms, cycloalkyl containing R 1 and R 2 , and R 3 to R 6 are the same or different and each is hydrogen, halogen, alkyl of 1 to 10 carbon atoms, Alkenyl having 1 to 10 carbon atoms, alkynyl having 1 to 10 carbon atoms, aryl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, or alkylcarbonyl having 1 to 10 carbon atoms. The transition metal-salen derivatives of the present invention are preferably (1S, 2S) - (+) - 1,2-Cyclohexanediamino-N, N'- bis (3,5- di- t- butylsalicylidene) cobalt ), Which is a compound having an oxygen-activating function and reversibly plays an oxygen-fixing role due to the specific molecular form of the salen ligand. In addition, since it has an affinity for oxygen more than carbon dioxide, it shows excellent efficiency in oxygen separation in combustion exhaust gas. The transition metal-salen derivative of the present invention can be obtained at a high yield of 80% to 90% using salicylaldehyde and ethylenediamine, so that the manufacturing cost can be reduced as compared with the conventional oxygen separator.
[Chemical Formula 1]
Porphyrin compounds such as cobalt-porphyrin, which is conventionally used as an oxygen fixing compound, have a solubility of 4.5 g / L in toluene, which is not high in solubility in a solvent, which makes it difficult to prepare a coating solution. In addition, the porphyrin compound is an N4 type ligand in the molecular structure, and the electron density of the metal at the center of the molecule is relatively low due to high conjugation state due to delocalized electron, However, since the solubility of the transition metal-salen derivative such as cobalt-salen is higher than that of the porphyrin compound at 40 g / L in toluene, it is easy to prepare the coating solution, and the metal coordinated to the N2O2- The oxygen affinity is very high. That is, the transition metal-salen compound shows better efficiency in oxygen separation than the porphyrin compound.
When an oxygen-containing mixed gas, for example, a combustion gas, is injected into the hollow fiber membrane for oxygen separation, it is diffused into the separation membrane to be brought into contact with the transition metal-salen derivative coated on the tubular polymer membrane and oxygen is converted into a transition metal- So that oxygen can be separated from the mixed gas. In one embodiment of the present invention, the derivative is coated on the inner surface of the hollow fiber membrane using the property that oxygen easily adsorbs to the transition metal-salen derivative, and a flue gas for separating oxygen is injected into the hollow fiber membrane, .
In one embodiment, the transition metal-salen derivative is mixed with a polymer compound in a solvent to prepare a coating solution in a liquid state, and the coating solution is coated on the tubular polymer membrane. The polymer compound included in the coating solution is to facilitate the formation of a coating layer containing a transition metal-salen derivative compound in the porous tubular polymer membrane. It is desirable to improve the adhesion between the coating layer and the tubular polymer membrane during formation of the coating layer, It can be evenly distributed on the coating layer and makes the coating layer firm. The coating layer contains a transition metal-salen derivative and a polymer compound in a weight ratio of 1: 100 to 50: 100. When the transition metal-salen derivative is less than 1 per 100 weight parts of the polymer compound, the oxygen active site is decreased and the oxygen selectivity is lowered. If the transition metal-salen derivative is 50 or more per 100 weight parts of the polymer compound, And thus it is not easy to coat the tubular polymer membrane. In one embodiment, the polymer membrane and the polymer compound are composed of the same or different polymer materials, and the polymer material is selected from the group consisting of a cellulose polymer, a polyethylene polymer, a polyethylene glycol polymer, a silicone polymer, a melamine resin polymer, a polyolefin polymer, a polystyrene polymer, At least one selected from the group consisting of a carbonate polymer, a polysulfone polymer, a polyamide polymer, a polyimide polymer, a polymethacrylate polymer, a polyester polymer, a polybenzimidazole polymer, and a polyacetal polymer. Preferably a polymeric material selected from the group consisting of polysulfone, polyethersulfone, sulfonated polysulfone, polyvinylidene fluoride, polyacrylonitrile, polyimide, polyetherimide, polyester, polybenzimidazole, polyamide and polydimethylsiloxane , More preferably the tubular porous polymer membrane is made of polyethersulfone, and the polymer to be mixed in the coating solution is PDMS (polydimethylsiloxane). The coating layer comprising the transition metal-salen derivative and the polymer compound is coated on at least one side of the porous tubular polymer membrane with a thickness of 0.5 nm to 400 nm, preferably 50 nm to 400 nm. The coating layer having a thickness of 0.5 nm or less has poor oxygen selectivity, and the coating layer having a thickness of 400 nm or more has a low transmittance.
The hollow fiber membrane for oxygen separation of the present invention can be used to separate the oxygen in the combustion exhaust gas before feeding it to the carbon dioxide capture device in supplying oxygen-containing combustion exhaust to the carbon dioxide capture device. Conventional oxygen separation or deoxygenation apparatuses require oxygen at a high pressure or a high temperature driving environment in the case of a ceramic separation membrane. However, the hollow fiber membranes for oxygen separation according to the present invention can perform oxygen separation with high efficiency under relatively mild conditions of low pressure and low temperature by coating a transition metal-salen derivative, which is a reversible oxygen adsorption compound, on the porous tubular polymer membrane. Particularly, the above-mentioned derivative is coated on the inner surface of the hollow fiber membrane and the exhaust gas is injected into the hollow fiber membrane to optimize the separation efficiency by taking advantage of the characteristics of the above-mentioned derivative.
In another aspect, the present invention provides a method for producing a hollow fiber membrane for oxygen separation comprising the above-described transition metal-salen derivative, comprising the steps of: preparing a spinning solution containing a polymer; Preparing a porous tubular polymer membrane through the nozzle with the spinning solution; Preparing a coating solution coated on the inner surface of the porous tubular polymer membrane; And coating the coating solution on the inner surface of the porous tubular polymer membrane, wherein the step of preparing the coating solution comprises mixing the transition metal-salen derivative and the polymer compound at a weight ratio of 1: 100 to 50: 100 And a transition metal-salen derivative, wherein the mixture is mixed with an organic solvent.
The porous tubular polymer membrane can be produced by, for example, a dry-wet phase inversion method. A spinning solution is prepared, which is made into a tubular polymer membrane through a nozzle. In one embodiment, the spinning solution is selected from the group consisting of cellulose polymer, polyethylene polymer, polyethylene glycol polymer, melamine resin polymer, polyolefin polymer, polystyrene polymer, polycarbonate polymer, polysulfone polymer, polyamide polymer, polyimide polymer, poly A mixture of one or more selected from the group consisting of a methacrylate-based polymer, a polyester-based polymer, a polybenzimidazole polymer, or a polyacetal polymer; N-dimethlaniline, N-methylpyrrolidone, tetrahydrofurane; And lithium chloride. 1 is a schematic view illustrating a method of manufacturing a porous tubular polymer membrane according to an embodiment of the present invention. The spinning solution (a) and the internal coagulating agent (b) are supplied to the gear pump (c) and the HPLC pump (d) under a nitrogen atmosphere, and the water bath (e) and the cooler (k) f. The polymer membrane emitted from the radiator f is wound on the take-up device j after the tension test i through the first coagulation bath g and the second coagulation bath h.
The coating layer coated on at least one side of the porous tubular polymer membrane is formed using a coating solution in which a transition metal-salen derivative compound, a polymer compound and a solvent are mixed. In one embodiment, the coating may be coated on the outside of the porous tubular polymer membrane using a coating apparatus. 2, the coating apparatus includes a
Hereinafter, embodiments are provided to facilitate understanding of the present invention. However, the following examples are provided only for the purpose of easier understanding of the present invention, and the present invention is not limited to the following examples.
Example 1 Preparation of Porous Tubular Polymer Membranes
(PES, Ultrason® E6020P, BASF, Germany), which exhibits thermal stability and high chain strength, to produce a porous tubular polymer membrane that serves as a support for oxygen-separated hollow fiber membranes. 18.0 wt% of PES solution was dried at 80 ° C for 3 days, and 5 wt% of N-methylpyrrolidone (NMP, Merck) and lithium chloride (LiCl, Sigma Aldrich, USA) The composition ratios were mixed as shown in Table 1.
[Table 1]
The prepared spinning solution was spun while maintaining distilled water as an internal coagulating agent and air gap of 0-20 cm in a dual tube spinning nozzle having an inner opposite diameter of 0.12 / 0.6 mm to prepare a porous tubular polymer membrane. After spinning, the solvent with which the fibers remained was washed for 6 days in flowing water at a flow rate of 313 K of 50 cm 3 / min. The washed porous tubular polymer membrane was treated with methanol for 2 hours and dried for 6 days.
Example 2 for oxygen separation Hollow fiber Fabrication of membranes
(1S, 2S) - (+) - 1,2-Cyclohexanediamino-N, N'-bis (3,5-di -t-butylsalicylidene) cobalt (II) (t-Bu-Co (salen)). The coating solution was prepared by mixing PDMS (Polydimethylsiloxane), t-Bu-Co (salen) and Bim (Benzoimidazole) in 40 mL of toluene in the same mass as shown in Table 2 and further adding toluene a t-Bu-Co (salen) -
[Table 2]
● Bim: Benzoimidazole (benzoimidazole)
Example 3 Oxygen separation function measurement of hollow fiber membranes for oxygen separation
The oxygen and nitrogen (99.99%, SAFETY GAS, Korea) permeability of the hollow fiber membranes corresponding to Experimental Examples 1 and 2 were measured in order to measure the oxygen separation function of the hollow fiber membrane for oxygen separation prepared according to Examples 1 and 2 Respectively. Fig. 3 schematically shows a method of measuring gas permeability. The gases were injected into the hollow fiber membrane to directly contact the coating layer, thereby maximizing the oxygen transmission efficiency. The hollow fiber membranes according to Experimental Example 1 (t-Bu-Co (salen) -
[Table 3]
The gas was injected at 0.15 to 0.5 bar, and the permeation side of the separation membrane was maintained at atmospheric pressure. The operating temperature was kept constant at 25 占 폚 using the air circulation of the oven (30) in order to balance the feed gas flow with the oxygen separation membrane module. The gas flow rate through the module was measured with a bubble flow meter (40). Gas permeability was calculated using the following equation (1): < RTI ID = 0.0 >
Q p is the permeation flux through the membrane, ΔP is the pressure of the gas passing through the membrane, and A is the membrane area. The unit of P is GPU (1 GPU = 1 x 10 -6 cm 3 (STP) / cm 2 · cmHg · sec).
The gas permeability and selectivity of the hollow fiber membrane module according to Experimental Example 1 were measured and the results are shown in FIG. In the case of oxygen permeability, the permeability tended to decrease with increasing pressure over the entire pressure range, and the permeability was remarkably high at the lowest pressure of 0.15 bar. It is considered that as the pressure increases, the oxygen vacancy is saturated in t-Bu-Co (salen), and the permeability decreases at high pressure. On the other hand, the nitrogen permeability showed a relatively constant permeability over the entire pressure range. It is considered that nitrogen is not influenced by t-Bu-Co (salen).
The gas selectivity was calculated using the following equation (2): < RTI ID = 0.0 >
a represents the pressure ratio of the two gases i and j, and the pressure ratio is the permeability of each gas, and the ratio thereof represents gas selectivity. 0.15 bar The highest oxygen selectivity was 1.94.
The hollow fiber membranes according to Experimental Example 2 (t-Bu-Co (salen) -
[Table 4]
The permeability of each gas of nitrogen and oxygen was measured in the same manner as in FIG. 3, and the permeability was calculated using Equation (1). In the case of selectivity, the permeability was calculated using the equation (2) Respectively. The gas permeability and selectivity of the hollow fiber membrane module according to Experimental Example 2 (t-Bu-Co (salen) -
6 is a graph showing the transmittance and selectivity of 25% t-Bu-Co (salen) -PDMS according to Experimental Example 2 for carbon dioxide and oxygen. Oxygen and carbon dioxide were measured for permeability under the same conditions as shown in Table 5.
[Table 5]
The permeability of each gas of nitrogen and carbon dioxide was measured in the same manner as in FIG. 3 and the permeability was calculated using Equation (1). In the case of selectivity, the permeability was calculated using the equation (2) Respectively. As a result, the permeability of carbon dioxide remained relatively constant throughout the experimental pressure. Since the molecular size of carbon dioxide is smaller than that of oxygen molecule, it moves relatively faster than oxygen gas, and the probability of passing through the membrane is high. However, the oxygen selectivity of the t-Bu-Co (salen) -
(Nitrogen) / oxygen (O2) of the hollow fiber membranes for oxygen separation of 25% of the t-Bu-Co (salen) -PDMS of the present invention of the present invention and the conventional commercial separator (Yong et al., J. Membr. Sci. As a result of comparing the selectivities, the selectivity of oxygen was much higher than that of the conventional membrane at low pressure as shown in FIG. Therefore, it is considered that the hollow fiber membrane for oxygen separation formed with the coating layer containing t-Bu-Co (salen) of the present invention exhibits better oxygen separation effect at low pressure.
While the present invention has been described in connection with what is presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, .
All technical terms used in the present invention are used in the sense that they are generally understood by those of ordinary skill in the relevant field of the present invention unless otherwise defined. The contents of all publications referred to herein are incorporated herein by reference.
100. Bobbin
110. Coating section
120. Drying section
130. Coated tubular polymer membrane
140. Winder
Claims (8)
And a porous coating layer formed on the inner surface of the tubular polymer membrane,
The coating layer may be formed by coating a mixture of (1S, 2S) - (+) - 1,2-Cyclohexanediamino-N, N'- bis (3,5- di- t- butylsalicylidene) cobalt (II) and PDMS (polydimethylsiloxane) 50: 100 by weight,
Wherein the coating layer has a thickness of 1 nm to 400 nm,
A hollow fiber membrane for oxygen separation comprising a transition metal-salen derivative.
The material of the polymer membrane may be selected from the group consisting of cellulose polymer, polyethylene polymer, polyethylene glycol polymer, silicone polymer, melamine resin polymer, polyolefin polymer, polystyrene polymer, polycarbonate polymer, polysulfone polymer, polyamide polymer, polyimide polymer, Which is at least one member selected from the group consisting of a methacrylate-based polymer, a polyester-based polymer, a polybenzimidazole polymer, and a polyacetal polymer,
A hollow fiber membrane for oxygen separation comprising a transition metal-salen derivative.
The method comprises the steps of: preparing a spinning solution containing a polymer;
Preparing a porous tubular polymer membrane through the nozzle with the spinning solution;
Preparing a coating solution coated on the inner surface of the porous tubular polymer membrane; And
And coating the coating solution on the porous tubular polymer membrane,
The step of preparing the coating solution is a step of mixing an organic solvent with a mixture of a transition metal-salen derivative and a polymer compound in a weight ratio of 1: 100 to 50: 100,
The coating is coated to a thickness of 1 nm to 400 nm,
The transition metal-salen derivative compound is (1S, 2S) - (+) - 1,2-Cyclohexanediamino-N, N'-bis (3,5-
The polymer compound may be PDMS (polydimethylsiloxane)
A method for producing a hollow fiber membrane for oxygen separation comprising a transition metal-salen derivative.
The coating step is to coat the inner surface of the porous tubular polymer membrane,
The coating solution is injected into the porous tubular polymer membrane and maintained for 10 seconds to 60 seconds. Then, the coating solution at the center of the porous tubular polymer membrane is removed and dried at 50 ° C to 100 ° C.
A method for producing a hollow fiber membrane for oxygen separation comprising a transition metal-salen derivative.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150151806A KR101791422B1 (en) | 2015-10-30 | 2015-10-30 | Hollow Fiber Membrane comprising Derivatives of Transition Metal-Salen for Separating Oxygen and Manufacturing Method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020150151806A KR101791422B1 (en) | 2015-10-30 | 2015-10-30 | Hollow Fiber Membrane comprising Derivatives of Transition Metal-Salen for Separating Oxygen and Manufacturing Method thereof |
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| KR101791422B1 true KR101791422B1 (en) | 2017-10-31 |
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| WO2019116075A1 (en) * | 2017-12-11 | 2019-06-20 | Poorkhalil Ali | Method and system for coating hollow fiber membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302412A (en) * | 1999-04-22 | 2000-10-31 | Agency Of Ind Science & Technol | Concentration of oxygen and apparatus therefor |
| JP2003053125A (en) * | 2001-08-22 | 2003-02-25 | Univ Waseda | Oxygen permeable polymer membrane |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000302412A (en) * | 1999-04-22 | 2000-10-31 | Agency Of Ind Science & Technol | Concentration of oxygen and apparatus therefor |
| JP2003053125A (en) * | 2001-08-22 | 2003-02-25 | Univ Waseda | Oxygen permeable polymer membrane |
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