KR20140014905A - Composite hollow fiber membrane for separation of carbon dioxide/methane in the biogas purification process, membrane module comprising the same and manufacturing method thereof - Google Patents

Abstract

The present invention provides a composite hollow fiber membrane for separating carbon dioxide and methane, which is coated with organopolysiloxane copolymers wherein repeating units including polyethylene glycol or polyethylene/propylene glycol are grafted on the surface of the hollow fiber membrane composed of glassy polymers; and a membrane module comprising the same. Also the present invention provides a method for manufacturing the composite hollow fiber membrane, comprising the steps of: acquiring a polymer solution by dissolving glassy polymers in an organic solvent; acquiring a homogeneous spinning solution by mixing the polymer solution with an additive and stirring the solution; providing a hollow fiber membrane by spinning the spinning solution via a dual spinneret; and coating an organopolysiloxane copolymer solution wherein repeating units including polyethylene glycol or polyethylene/propylene glycol are grafted on the surface of the hollow fiber membrane. The composite hollow fiber membrane manufactured according to the present invention can selectively separate and remove carbon dioxide from the mixed gas of carbon dioxide and methane in a biogas purification process and can improve the efficiency of the separation process because the trasmissivity of carbon dioxide is increased greatly.

Description

TECHNICAL FIELD [0001] The present invention relates to a hollow composite membrane for separating carbon dioxide and methane in a biogas purification process, a membrane module including the membrane composite, and a method for manufacturing the membrane composite membrane. thereof}

TECHNICAL FIELD The present invention relates to a hollow composite membrane for selectively separating carbon dioxide from a mixed gas of carbon dioxide and methane in a biogas purification process, a membrane module including the composite membrane and a method for producing the same, and more particularly, to a membrane composite module using polyethylene glycol or polyethylene / The coating of the organopolysiloxane copolymer grafted with the repeating unit containing the polymer on the surface of the hollow fiber membrane of glassy polymer greatly improves the permeability of the carbon dioxide to selectively remove and remove carbon dioxide from the mixed gas of carbon dioxide and methane in the biogas purification process And to improve the efficiency of the separation process, a membrane module including the same, and a manufacturing method thereof.

Biogas refers to a gaseous fuel including methane and carbon dioxide produced by decomposition of organic waste resources such as sludge, food waste, and livestock manure by microorganisms. In the biogas, carbon dioxide and some other gases are removed Methane gas is called biomethane, and recently it can be used as a clean fuel like natural gas, and is attracting attention as an energy source.

However, the methane contained in the biogas composition is to about 50 to 70% of calories (5,000kcal / m ³ or less) is small transporting fuel or town gas is difficult to use the methane content of the biogas to qualify a similar amount of heat and gas 95% or more. Therefore, the process of separating carbon dioxide / methane mixed gas, which accounts for most of the biogas, is applied and it can be used for power generation, boiler, factory, automobile fuel, city gas or the like.

Currently known carbon dioxide purification technologies in biogas include pressure swing adsorption, water scrubbing, methanol scrubbing, polyethylene glycol scrubbing, membrane separation, cryogenic liquefaction technology, and gas hydrate technology .

The adsorption method is a technique for selectively separating specific components of the mixed gas using the difference in the adsorption equilibrium amount caused by the pressure cycling between the adsorbent and the mixed gas. It mainly adsorbs carbon dioxide at high pressure, refines methane, and desorbs the adsorbed component at low pressure . However, since the adsorption method is an abnormal state operation, it is difficult to predict and design various operating parameters during the operation step, and there is a disadvantage that pretreatment for moisture is required depending on the adsorbent.

On the other hand, the water scrubbing process is mainly applied as the absorption method, which depends on the type of the absorbing liquid, the gas-liquid contact area, and the temperature of gas and water. However, there is a problem in that a post-treatment process in which moisture is saturated with purified methane gas is required to remove moisture.

Membrane separation is a method of selectively permeating certain components using a membrane to separate gases. Gas separation using membranes separates gases through dissolution and diffusion processes, and does not involve phase changes, resulting in low energy consumption and installation area. Because of its small size and easy maintenance, it is recently attracting attention as a gas separation and purification technology. Polymer membranes are mainly used for removing carbon dioxide in the biogas by such a membrane separation method. Commercialized carbon dioxide / methane separation membranes are mainly made of polysulfone, polyethersulfone, polycarbonate, polyimide, polyetherimide, etc. Mostly, when the gas is permeated through the dissolution and diffusion process, it is dominantly influenced by the diffusion, and the separation is performed according to the difference of the permeation rate of carbon dioxide / methane.

In addition, the separation membrane is classified into a single membrane or a composite membrane according to the material of the membrane, a symmetric membrane or an asymmetric membrane according to the structure of the membrane, and a flat membrane or hollow fiber membrane depending on the shape of the membrane, which is usually researched or developed for gas separation Asymmetric hollow fiber composite membranes are the mainstream to improve the trade-off relationship between gas permeability and selectivity.

For example, US Pat. No. 4,230,463 discloses a composite membrane in which a polydimethylsiloxane solution is coated on the surface of a porous polysulfone hollow fiber membrane. The permeability of carbon dioxide is 38 GPU and the selectivity of carbon dioxide / methane is 17. In addition, U.S. Pat. Nos. 4,871,494 and 4,880,441 disclose a method of forming an asymmetric hollow fiber membrane by forming a composite of an organic solvent additive in a polysulfone solution and solidifying it in a spin-spinning solvent, and then coating the solution with a polydimethylsiloxane solution The permeability of carbon dioxide was 65 ~ 155 GPU and the selectivity of carbon dioxide / methane was 9.5 ~ 9.8. Korean Patent Publication No. 644366 discloses a hollow fiber obtained by dissolving a polyether sulfone in a mixed solvent of NMP, DMAc or acetone using an internal coagulant having a high boiling point and a non-solvent, The permeability of carbon dioxide was 34 ~ 43 GPU and the selectivity of carbon dioxide / methane was 24 ~ 28 from the mixed gas of carbon dioxide and methane.

However, most of the asymmetric hollow fiber composite membranes, including the above mentioned literature, are coated with a solution of polydimethylsiloxane in a general hollow fiber membrane. Therefore, the coating solution has a limitation, and the permeability of carbon dioxide from the carbon dioxide / It has a problem that it is relatively low to increase the methane content by selectively separating the carbon dioxide used in the gas purification process.

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 an organic polysiloxane copolymer solution in which a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is not a conventional polydimethylsiloxane solution, A hollow composite membrane capable of selectively separating and removing carbon dioxide from the mixed gas of carbon dioxide and methane in the biogas purification process and improving the efficiency of the separation process by coating the surface of the hollow fiber membrane made of a polymer material, And a method of manufacturing the same.

In order to accomplish the above object, the present invention provides a hollow fiber membrane for carbon dioxide / methane separation coated with an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol on the surface of a hollow fiber membrane of a glass- Thereby providing a composite membrane.

Wherein the glassy polymer is any one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile, and cellulose acetate.

The organopolysiloxane copolymer in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is grafted is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) , Poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane- (Ethylene / propylene glycol), poly [dimethylsiloxane-co-methyl (3-hydroxy-3-hydroxypropyl) siloxane] graft-poly (ethylene glycol) (Ethyleneglycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] - graft- Trimethylammonio) propyl chloride. Lauryl group, or a mixture thereof.

The present invention also provides a membrane module comprising the hollow composite membrane as shown in FIG.

Wherein 1,000 to 150,000 hollow fiber bundles are inserted into the housing of the membrane module and both ends of the membrane module are blocked by a potting agent.

The housing of the membrane module is made of any one material selected from the group consisting of aluminum, carbon steel, and stainless steel.

The present invention also provides a process for producing a hollow fiber composite membrane for carbon dioxide / methane separation comprising the steps of:

i) dissolving the glassy polymer in an organic solvent to obtain a polymer solution; ii) mixing an additive to the polymer solution obtained in step i) and stirring to obtain a uniform spinning solution; iii) providing a hollow fiber membrane by spinning the spinning solution obtained in the step ii) through a double spinneret; And iv) coating a solution of an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol on the surface of the hollow fiber membrane in step iii).

The glassy polymer in step i) is any one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile, and cellulose acetate.

The organic solvent in step i) is any one selected from the group consisting of N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), and dimethylformamide (DMF).

And the polymer solution in step i) is 20 to 40% by weight.

The additive in step ii) may be any one selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, ethyl acetate, trichloroethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethyl ether, , And any one selected from the group consisting of methanol, ethanol, 2-propanol, 2-pentanol, methoxyethanol, butoxyethanol, perlyl alcohol and tertiary amyl alcohol is mixed and added.

The additive of step ii) is characterized in that for adding 10 to 30 parts by weight based on 100 parts by weight of the spinning solution.

The double spinneret of step iii) is water, isopropanol, butanol, ethylene glycol, polyethylene glycol, glycerol, dimethoxyethanol, diethoxyethanol, butoxymethanol, dimethoxybutylene oxide or diglycidyl dimethyl ether It is characterized in that to use any one selected from the internal coagulation solution.

The organopolysiloxane copolymer in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol in step iv) above is grafted is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft- Methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane-co- Poly (dimethylsiloxane-co-methyl) siloxane] - graft-poly (ethylene / propylene glycol), poly [dimethylsiloxane-co-methyl (Ethyleneglycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft- poly (ethylene glycol) [3- (trimethylammonio) propyl cro Jethro is characterized in that in any one or a mixture thereof selected from the group consisting of.

The organopolysiloxane copolymer solution in which the repeating unit containing polyethylene glycol or polyethylene / propylene glycol in the step iv) is grafted may be prepared by reacting an aliphatic alcohol having 1 to 5 carbon atoms, an aliphatic or alicyclic alkane having 5 to 10 carbon atoms, Alkyl ether or a mixture thereof is used as a solvent.

The organopolysiloxane copolymer solution in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol in the step iv) is grafted is characterized by a concentration of 1 to 5% by weight.

In the present invention, the permeability of carbon dioxide is greatly improved by coating a solution of an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol on the surface of a glassy polymer hollow fiber membrane, and thus the carbon dioxide / methane It is possible to provide a hollow fiber composite membrane capable of selectively separating and removing carbon dioxide from the mixed gas of the gas mixture and improving the efficiency of the separation process.

1 is a hollow fiber membrane manufacturing apparatus.
Figure 2 is a membrane module comprising a hollow fiber composite membrane according to the present invention.
3 is an electron scanning micrograph of the hollow fiber composite membrane surface layer according to the present invention.
Figure 4 is a gas permeability measuring device of the hollow fiber composite membrane according to the present invention.

Hereinafter, the permeability of carbon dioxide is greatly improved by coating the surface of the hollow fiber membrane of the glass-like polymer material with the organopolysiloxane copolymer solution in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol according to the present invention is grafted, A hollow fiber composite membrane capable of selectively separating and removing carbon dioxide from a mixed gas of carbon dioxide and methane and improving the efficiency of the separation process will now be described in detail.

First, the hollow fiber composite membrane of the present invention uses glass-like polymer as the porous support, and the hollow fiber composite membrane is prepared from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile or cellulose acetate Any one selected may be used, and polysulfone or polyetherimide is more preferable. In general, when gas is separated, a glassy polymer having high attractive force between polymer chains is used as a substrate in view of low permeability but relatively high selectivity.

In addition, the hollow composite membrane according to the present invention is coated on the surface of the hollow fiber membrane with an organopolysiloxane copolymer in which a repeating unit including polyethylene glycol or polyethylene / propylene glycol is grafted. The polyethylene glycol or polyethylene / propylene glycol (Ethylene glycol) methyl ether, poly [dimethylsiloxane-co-methyl (dimethylsiloxane) -cyclohexane (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane- Poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol), poly [dimethylsiloxane- (Ethyleneglycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] - graft-poly (ethylene glycol) ) Propyl chloride, or a mixture thereof. Unlike conventional hollow fiber composite membranes coated with only polydimethylsiloxane on the surface of the hollow fiber membrane according to the present invention, a variety of coating agents, such as polyethylene glycol or polyethylene / propylene glycol-grafted repeating units, By coating the copolymer, the solubility of carbon dioxide is greatly increased and the permeability of carbon dioxide from the mixed gas of carbon dioxide / methane is remarkably improved.

The present invention also provides a membrane module including the hollow composite membrane as shown in FIG. 2, wherein a hollow fiber bundle of 1,000 to 150,000 fibers is inserted into the housing of the membrane module, Lt; / RTI > The housing of the membrane module is made of any one material selected from the group consisting of aluminum, carbon steel, and stainless steel.

Hereinafter, a method of manufacturing the hollow fiber composite membrane according to the present invention will be described in detail. As a first step to obtain a hollow fiber composite membrane, the glassy polymers are dissolved in an organic solvent to obtain a polymer solution. It is preferable to use a good solvent having a relatively high boiling point as the organic solvent. If the boiling point is low, defects may occur in the selective layer of the hollow fiber due to the rapid evaporation of the organic solvent in the high-temperature hollow fiber spinning process. If the boiling point is too high, the organic solvent does not evaporate while the spinning solution passes through the air, so the selection is smooth. No floor can be obtained. Therefore, as the organic solvent, any one selected from the group consisting of N-methylpyrrolidone (NMP), dimethylacetamide (DMAc) or dimethylformamide (DMF) can be used, and N-methylpyrrolidone (NMP) This is more preferable.

In addition, the polymer solution is adjusted to a concentration of 20 to 40% by weight, if the concentration is less than 20% by weight, the mechanical strength of the hollow fiber is weak to serve as a porous support, when the concentration exceeds 40% by weight gas permeability Since it can be very low, it is desirable to maintain the concentration in the above range.

Next, a uniform spinning solution is obtained by mixing and stirring an additive in the polymer solution. Examples of the additives include tetrahydrofuran, methyl ethyl ketone, ethyl acetate, trichloroethane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, which function to reduce the viscosity of the polymer solution to some extent and maintain the state of the polymer solution uniformly , Dimethyl ether or diethyl ether and one or more selected from the group consisting of methanol, ethanol, 2-propanol, 2-pentanol, methoxy ethanol, butoxy ethanol, peryl alcohol or tertiary amyl alcohol It is preferable that any one selected is mixed and added, and it is more preferable to mix tetrahydrofuran and ethanol.

When the content of the additive is less than 10 parts by weight, it is difficult to obtain a homogeneous spinning solution while decreasing the viscosity of the polymer solution. When the content of the additive exceeds 30 parts by weight Since the concentration of the spinning solution is too low, the mechanical strength of the hollow fiber decreases. Therefore, it is preferable to maintain the content of the additive within the above range.

The hollow fiber membrane is obtained by spinning the spinning solution through the double spinneret using the hollow fiber membrane production apparatus shown in FIG. 1. First, the spinning solution removes air bubbles, removes foreign substances using a filter, and then sends the double spinning spinneret while maintaining a 60 to 80 ° C. and an air gap of 10 to 30 cm through a gear pump. Subsequently, the spinning solution comes out through the outer nozzle of the double spinneret, and the inside of the double spinneret discharges the internal coagulating solution to spin the hollow fiber. At this time, the internal coagulating solution is water, isopropanol, butanol, ethylene glycol, polyethylene glycol, glycerol, dimethoxyethanol, diethoxyethanol, butoxymethanol, dimethoxybutylene oxide or diglycidyl dimethyl ether Any one selected may be used, more preferably water. The external coagulation bath containing the external coagulating solution is maintained at 15 to 20 ° C, and the hollow fiber is wound through the phase transition process. The residual coagulating bath is washed with flowing water for 2 to 3 days to remove the residual solvent and additives, And then immersed in n-hexane for 3 to 5 hours to replace the methanol with n-hexane and then dried in a vacuum oven at 70 to 80 ° C for 3 hours or more to obtain a hollow fiber membrane.

In the present invention, a hollow composite membrane is prepared by coating a solution of an organopolysiloxane copolymer having a repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol on the surface of the hollow fiber membrane.

The organopolysiloxane copolymer in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is grafted is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) , Poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane- (Ethylene / propylene glycol), poly [dimethylsiloxane-co-methyl (3-hydroxy-3-hydroxypropyl) siloxane] graft-poly (ethylene glycol) (Ethyleneglycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] - graft- Trimethylammonio) propyl chloride. Lauryl group, or a mixture thereof.

The organic polysiloxane copolymer in which a repeating unit including polyethylene glycol or polyethylene / propylene glycol is grafted on the surface of the hollow fiber membrane is coated to increase the solubility of carbon dioxide to selectively remove carbon dioxide from the carbon dioxide / methane mixture gas in the biogas purification process Separation and removal and improve the efficiency of the separation process.

In addition, the organopolysiloxane copolymer solution in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol is grafted can be obtained by reacting an aliphatic alcohol having 1 to 5 carbon atoms, an aliphatic or alicyclic alkane having 5 to 10 carbon atoms, a halogenated alkane, Or a mixture thereof is used as a solvent. When the concentration of the coating solution is less than 1 wt%, the coating solution is too low to coat the defects on the outer surface of the hollow fiber, so that the coating solution is not properly applied. The selectivity of the membrane is decreased. If the concentration exceeds 5 wt%, a new coating layer is formed on the outer surface of the hollow fiber to decrease the permeability. Therefore, it is preferable to adjust the concentration of the coating solution within the above range.

Hereinafter, specific embodiments will be described in detail.

( Example  One)

500 g of N-methylpyrrolidone was added to a 2 L reactor equipped with a stirrer, and 300 g of polyetherimide was slowly added to obtain a polymer solution. 5 g of tetrahydrofuran and 15 g of ethanol were added as an additive to the polymer solution and mixed to obtain a homogeneous spinning solution. The spinning solution was used to remove air bubbles and remove foreign matter using a 60-μm filter. Then, it was sent through the gear pump to the double spinneret while maintaining the radiation temperature of 60 ° C and the air gap of 10 cm. At this time, room temperature water was used as the internal coagulating solution of double spinneret. The external coagulation bath containing water was cooled to 15 ° C, and the hollow fiber was wound around the tube. The remaining solvent and additives were removed by washing with running water for 2 days. Subsequently, it was immersed in methanol for 3 hours, immersed again in n-hexane for 3 hours, the methanol was replaced with hexane, and dried in a vacuum oven at 70 캜 for 4 hours to obtain a hollow fiber membrane. The resultant hollow fiber membrane was dip-coated on a coating solution prepared by dissolving 5 wt% of poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) methyl ether in ethanol, Lt; 0 > C for 12 hours to prepare a hollow fiber composite membrane. The surface structure of the hollow composite membrane finally produced from Example 1 was analyzed by an electron scanning microscope. The results are shown in FIG. 3, and it was confirmed that a coating layer was formed on the surface of the hollow fiber membrane as the porous support.

( Example  2)

500 g of N-methylpyrrolidone was added to a 2 L reactor equipped with a stirrer, and 300 g of polysulfone was slowly added to obtain a polymer solution. 10 g of tetrahydrofuran and 10 g of ethanol were added as an additive to the polymer solution and mixed to obtain a homogeneous spinning solution. The remaining steps were performed in the same manner as in Example 1 to prepare hollow composite membranes.

( Comparative Example  One)

A hollow fiber membrane was obtained in the same manner as in Example 1, and the coating step was not carried out.

( Comparative Example  2)

A hollow fiber membrane was obtained in the same manner as in Example 2, and the coating step was not carried out.

( Test Example Measurement of Gas Permeability of Hollow Fiber Membrane

The gas permeabilities of the hollow composite membranes prepared in Examples 1 and 2 and the hollow fiber membranes prepared in Comparative Examples 1 and 2 were measured using the gas permeability measurement apparatus shown in FIG. The average permeability and selectivity of carbon dioxide and methane were measured by preparing 5 identical hollow fiber membrane modules under 5 atmospheres, using 99.99% carbon dioxide and methane as the mixer, respectively. The gas permeability was measured using a flow meter, and the gas permeation unit was GPU (Gas Permeation Unit, 10 ^-6 × cm ³ / cm ² sec · cmHg). The results are shown in Table 1 below.

Measurement example Carbon dioxide permeability
(P _CO2 , GPU) Methane permeability
(P _CH4 , GPU) Carbon dioxide / methane selectivity
(P _CO2 / P _CH4 ) Example 1 113.8 2.4 47.4 Comparative Example 1 91.3 2.5 36.5 Example 2 222 7.6 29.2 Comparative Example 2 171.2 7.5 22.8

As shown in Table 1, the hollow fibers coated with poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) methyl ether prepared in Examples 1 and 2 of the present invention The permeability of carbon dioxide was greatly increased in the composite membranes compared to the uncoated hollow fiber membranes of Comparative Examples 1 and 2, but the permeability of methane remained unchanged, thereby selectively separating carbon dioxide from the mixed gas of carbon dioxide and methane in the biogas purification process The performance can be greatly improved.

Claims (16)

A hollow fiber composite membrane for separating carbon dioxide / methane coated with an organic polysiloxane copolymer grafted with repeating units containing polyethylene glycol or polyethylene / propylene glycol on the surface of a hollow fiber membrane made of glassy polymer material. The method according to claim 1, wherein the glassy polymer is any one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile or cellulose acetate. Hollow Fiber Composite Membrane for Separation of Methane. The method of claim 1, wherein the organopolysiloxane copolymer grafted repeating units comprising polyethylene glycol or polyethylene / propylene glycol is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane]-graft-poly (Ethylene glycol) methyl ether, poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane-co-methyl (3-hydrate Roxypropyl) siloxane] -graft-poly (ethylene glycol), poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol), poly [dimethylsiloxane-co -Methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene Glycol) [3- (trimethylammonio) propyl Hollow fiber composite membrane for carbon dioxide / methane separation, characterized in that any one or a mixture thereof selected from the group consisting of chloride. Membrane module comprising a hollow fiber composite membrane for separating carbon dioxide / methane of any one of claims 1 to 3. 5. The membrane module of claim 4, wherein the membrane module is inserted into the housing by 1,000 to 150,000 strands of hollow fibers and both ends of the membrane module are blocked by a potting agent. The membrane module according to claim 5, wherein the housing is made of any one material selected from the group consisting of aluminum, carbon steel, and stainless steel. Method for producing a hollow fiber composite membrane for carbon dioxide / methane separation comprising the following steps.
i) dissolving the glassy polymer in an organic solvent to obtain a polymer solution;
ii) mixing an additive to the polymer solution obtained in step i) and stirring to obtain a uniform spinning solution;
iii) providing a hollow fiber membrane by spinning the spinning solution obtained in the step ii) through a double spinneret; And
iv) coating an organopolysiloxane copolymer solution grafted with repeating units comprising polyethylene glycol or polyethylene / propylene glycol on the surface of the hollow fiber membrane of step iii). 8. The method of claim 7, wherein the glassy polymer is any one selected from the group consisting of polysulfone, polyethersulfone, polyimide, polyetherimide, polyamide, polycarbonate, polyacrylonitrile or cellulose acetate. / METHOD FOR MANUFACTURING HYBRID COMPOSITE FILM FOR DETECTING. The method of claim 7, wherein the organic solvent in step i) is any one selected from the group consisting of N-methylpyrrolidone (NMP), dimethylacetamide (DMAc), and dimethylformamide (DMF) / METHOD FOR MANUFACTURING HYBRID COMPOSITE FILM FOR DETECTING. [8] The method of claim 7, wherein the polymer solution in step i) is 20 to 40% by weight. The method according to claim 7, wherein the additive in step ii) is selected from the group consisting of tetrahydrofuran, methyl ethyl ketone, ethyl acetate, trichloroethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dimethyl ether or diethyl ether , And any one selected from the group consisting of methanol, ethanol, 2-propanol, 2-pentanol, methoxyethanol, butoxyethanol, perlyl alcohol and tertiary amyl alcohol is mixed and added Wherein the hollow fiber composite membrane comprises a hollow fiber composite membrane. The method according to claim 7 or 11, wherein the additive in step ii) is added in an amount of 10 to 30 parts by weight based on 100 parts by weight of the spinning solution. 8. The method of claim 7, wherein the dual spinneret in step iii) is selected from the group consisting of water, isopropanol, butanol, ethylene glycol, polyethylene glycol, glycerol, dimethoxyethanol, diethoxyethanol, butoxymethanol, dimethoxybutylene oxide, And a second step of preparing a hollow composite membrane for carbon dioxide / methane separation. The method according to claim 7, wherein the organic polysiloxane copolymer grafted repeating units comprising polyethylene glycol or polyethylene / propylene glycol of step iv) is poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane]- Graft-poly (ethylene glycol) methyl ether, poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol) methyl ether, poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol), poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene / propylene glycol), poly [ Dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft-poly (ethylene glycol) 3-aminopropyl ether or poly [dimethylsiloxane-co-methyl (3-hydroxypropyl) siloxane] -graft -Poly (ethylene glycol) [3- (trimethylammonium 5) Method for producing a hollow fiber composite membrane for carbon dioxide / methane separation, characterized in that any one or a mixture thereof selected from the group consisting of propyl chloride. [Claim 8] The method according to claim 7, wherein the organopolysiloxane copolymer solution in which the repeating unit containing polyethylene glycol or polyethylene / propylene glycol in step iv) is grafted comprises an aliphatic alcohol having 1 to 5 carbon atoms, an aliphatic or alicyclic Alkane, halogenated alkane, dialkyl ether, or a mixture thereof as a solvent. 2. A method for producing a hollow fiber composite membrane for carbon dioxide / methane separation according to claim 1, The method of claim 7 or 15, wherein the organopolysiloxane copolymer solution in which the repeating unit grafted with polyethylene glycol or polyethylene / propylene glycol in step iv) is grafted is in a concentration of 1 to 5% by weight. A method for producing a hollow composite membrane for methane separation.

Images