KR101868049B1 - MFI zeolite membrane for separating nitrogen and sulfur hexafluoride and preparation method of the same - Google Patents
MFI zeolite membrane for separating nitrogen and sulfur hexafluoride and preparation method of the same Download PDFInfo
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Abstract
The present invention relates to an MFI zeolite layer; And the nitrogen permeability coating in the MFI zeolite layer surface 50 barrer or more polymers; provides a nitrogen (N 2) and sulfur hexafluoride (SF 6) separating the zeolite separation membrane for containing the membrane during heat treatment of conventional MFI membrane SF 6 can be effectively separated from the waste gas containing N 2 and SF 6 by compensating for the thermal defects that are generated, and it has an effect of preventing moisture adsorption due to surface hydrophobicity.
Description
The present invention relates to an MFI zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ), and an MFI zeolite separation membrane for separating N 2 and SF 6 produced therefrom.
Sulfur hexafluoride (SF 6 ) is a global warming gas that is regulated by the Kyoto Protocol. Currently, it is mainly used as a semiconductor process and heavy equipment insulator, and the waste gas hexafluoride gas is decomposed and removed through heat and plasma, and energy efficiency is low and resource circulation is not achieved.
In recent years, studies have been made to separate sulfur hexafluoride gas through a membrane-based process with high energy efficiency and resource recycling. The polysulfone membrane, which is a polymer membrane for this purpose, exhibits excellent performance with a nitrogen permeability of 7 gpu and a selectivity of N 2 / SF 6 of about 30, but the permeability (nitrogen permeability 7 gup) A very large membrane area is required. In the case of the polymer membrane, there is almost no micropore structure, and gas permeation is caused by a change in the free volume of the polymer chain, so that the improvement of the permeability is limited.
On the other hand, in the case of the inorganic separator, since the micropores are present and the micropores are separated by the size difference, high gas permeability and high N 2 / SF 6 selectivity can be obtained.
Especially, in case of MFI (mobile five) zeolite, the pore size is 0.55 nm, which is larger than nitrogen gas molecules (0.365 nm) and similar to hexafluorosulfur gas molecules (0.55 nm) have. The zeolite separation membrane is made by a seed growth technique and is completed through heat treatment after seed growth (Korean Patent Laid-Open No. 10-2015-0142465). The heat treatment process is an essential process for removing the organic substances contained in the zeolite pores and opening the pores. However, at this time, stress is applied due to the difference in thermal expansion coefficient between the zeolite membrane and the support, thermal cracks are generated, and large gases which can not pass through the zeolite membrane are permeated, thereby deteriorating the membrane performance. In order to prevent the generation of such defects, preparation of zeolite having a deflecting direction (Korean Patent Laid-Open No. 10-2005-0015373), alteration of heat treatment method, thickness control of separator film, and the like have been conducted. Therefore, there is a problem that the performance is always accompanied with deterioration in performance when the membrane is made to have a basic performance higher than that of the zeolite.
An object of the present invention is to provide a MFI zeolite membrane for nitrogen (N 2) / sulfur hexafluoride (SF 6) selectivity is enhanced nitrogen (N 2) and sulfur hexafluoride (SF 6) separated.
The present invention
MFI zeolite layer; And
And a polymer having a nitrogen permeability of 50 barrer or more coated on the surface of the MFI zeolite layer to provide an MFI zeolite separation membrane for separation of nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ).
In addition,
Preparing zeolite particles having a particle size of 40 nm to 70 nm and coating the zeolite particles on a porous support to form a zeolite nano seed (step 1);
Preparing a zeolite synthesis solution, immersing the porous support in which the zeolite nano seeds are formed in the zeolite synthesis solution in the step 1, synthesizing an MFI zeolite precursor, drying and firing to form an MFI zeolite layer (step 2); And
(N 2 ) and sulfur hexafluoride (SF 6 ) separating the solution containing the polymer having a nitrogen permeability of 50 barrer or more onto the surface of the MFI zeolite layer formed in the step 2 A method for producing a separation membrane is provided.
Further,
A method for separating SF 6 from a waste gas containing nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) using the above separation membrane is provided.
The MFI zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention has an advantage that SF 6 can be effectively separated from a waste gas containing N 2 and SF 6 , There is an effect of preventing moisture adsorption.
In addition, the nitrogen in accordance with the present invention (N 2) and sulfur hexafluoride (SF 6) of the separation MFI zeolite separation membrane production method and compensate for thermal defects occurring during heat treatment of conventional MFI membrane, MFI zeolite membrane for N 2 and SF 6 And the separation performance is improved.
1 is a schematic view showing an example of a method for producing an MFI zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention.
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings. However, the embodiments of the present invention can be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below. Further, the embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art. Accordingly, the shapes and sizes of the elements in the drawings may be exaggerated for clarity of description, and the elements denoted by the same reference numerals in the drawings are the same elements. In addition, "including" an element throughout the specification does not exclude other elements unless specifically stated to the contrary.
The present invention
MFI zeolite layer; And
The present invention provides a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) containing a polymer having a nitrogen permeability of 50 barrer or more coated on the surface of the MFI zeolite layer.
Hereinafter, the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention will be described in detail.
Conventional MFI zeolites have a pore size of 0.55 nm which is larger than nitrogen gas molecules (0.365 nm) and similar to hexafluorosulfur gas molecules (0.55 nm), so that high gas permeation and separation performance can be expected However, the zeolite separation membrane is made by a seed growth technique, thermal cracks are generated through a heat treatment process after seed growth, large gases which can not permeate the zeolite membrane are permeated, It becomes a tree.
In the present invention, an MFI zeolite layer; And a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) containing a polymer having a nitrogen permeability of 50 barrer or more coated on the surface of the MFI zeolite layer to compensate thermal defects of zeolite generated by heat treatment And to exhibit excellent nitrogen and hexafluoride separation performance.
In the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention, the MFI zeolite layer may be formed by growing from a porous support. At this time, the porous support easily permeates the waste gas such as N 2 and SF 6 , and supports the MFI zeolite layer.
Specifically, the porous support may be alumina, zirconia, silica, or stainless steel. However, the porous support may be any material capable of permeating a waste gas containing nitrogen and hexafluoride as a base on which MFI zeolite can be grown It is not.
Original MFI type internal pores of the zeolite may have a size of about 0.50 nm to 0.60 nm, larger than the size of 0.365 nm in the N 2 gas molecules, to closer to the size of 0.55 nm of the SF 6 gas molecules, N 2 and SF 6 Gas separation performance is expected. Generally, when MFI zeolite membrane is formed, a crack due to a difference in thermal expansion coefficient is generated during a heat treatment process, thereby reducing gas separation ability. Accordingly, in the present invention, high N 2 / SF 6 selectivity can be obtained by coating a polymer having a nitrogen permeability of 50 barrer or more, which can compensate cracks of the MFI zeolite membrane.
In the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention, the polymer having a nitrogen permeability of 50 barrer or more coated on the surface of the MFI zeolite layer may be poly [4,5-difluoro- (PTFE), poly (1-trimethylsilyl-1-propyne) (PTMSP), poly (dimethylsiloxane) (PDMS), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polyethylene chlorotrifluoroethylene (ECTFE), and preferably polytetrafluoroethylene (PTFE AF), but the nitrogen permeability which can effectively separate N 2 and SF 6 gas is lower than that of poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole-co-tetrafluoroethylene] If the polymer is more than 50 barrer, The.
The nitrogen permeability of the polymer having a nitrogen permeability of 50 barrer or more may have a nitrogen permeability of 50 barrer to 10,000 barrer, and may be 50 barrer to 5,000 barrer.
The nitrogen (N 2) and sulfur hexafluoride (SF 6) permeability of the sulfur hexafluoride (SF 6) separating the zeolite separation membrane for may be a 7 gpu to 63 gpu, can be a 9 gpu to 60 gpu, 11 gpu to 57 gpu.
The nitrogen (N 2 ) permeability of the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) may be from 700 gpu to 900 gpu, from 710 gpu to 890 gpu, from 720 gpu to 880 gpu gpu.
The permeation unit gpu (gas permeation unit) is 10 -6 cm 3 / cm 2 · s · cmHg, and represents a unit area, a unit pressure difference, and a gas volume permeated per hour.
Also, the permeability unit barrer is 10 -10 cm 3 · cm / cm 2 · s · cmHg, and represents the gas permeability in a bulk state of the material.
In general, the separation performance of the separation membrane is largely expressed as the permeability and the selection ratio, and the selectivity is defined as the ratio of the permeability.
The selectivity of the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention is the selectivity of nitrogen to sulfur hexafluoride, which is the ratio of (N 2 permeability) / (SF 6 permeability ).
In addition,
Preparing zeolite particles having a particle size of 40 nm to 70 nm and coating the zeolite particles on a porous support to form a zeolite nano seed (step 1);
Preparing a zeolite synthesis solution, immersing the porous support in which the zeolite nano seeds are formed in the zeolite synthesis solution in the step 1, synthesizing an MFI zeolite precursor, drying and firing to form an MFI zeolite layer (step 2); And
(N 2 ) and sulfur hexafluoride (SF 6 ) separation membranes comprising a step (step 3) of coating a solution containing a polymer having a nitrogen permeability of 50 barrer or more on the surface of the MFI zeolite layer formed in step 2 Of the present invention.
1 is a schematic view showing an example of a method for producing a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention,
Hereinafter, a method for producing a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention will be described in detail with reference to the schematic diagram of FIG.
First, in the method for producing a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention, step 1 is a step of preparing zeolite particles having a particle size of 40 nm to 70 nm, The particles are coated on a porous support to form a zeolite nano seed.
In step 1, zeolite seeds having a particle size of 40 nm to 70 nm are coated on a porous support as a starting point for growth for secondary growth of MFI zeolite described below.
In this case, if the size of the zeolite powder used as the seed crystal is not uniform or larger than that of the zeolite crystal in the final separation membrane state, it may be difficult to obtain a membrane having a certain thickness in the secondary growth method.
The porous support of step 1 may be alumina, zirconia, silica, or stainless steel, but it is not limited to a material capable of growing MFI zeolite and capable of permeating waste gas.
The method of forming the zeolite seeds on the porous support of step 1 may be performed by rubbing or pressing, but is not limited thereto.
The zeolite particles of step 1 may have a particle size of 40 nm to 70 nm, may have a particle size of 45 nm to 65 nm, and may have a particle size of 50 nm to 70 nm. However, effective growth of MFI zeolite It is not limited thereto.
Further, a heat treatment may be performed to form a zeolite seed in the porous support of step 1 above. The heat treatment may be performed at a temperature of 400 ° C to 600 ° C, at a temperature of 420 ° C to 580 ° C, and at a temperature of 440 ° C to 560 ° C. However, the zeolite nano seed and the porous support But the present invention is not limited thereto as long as it can be effectively coated.
Through the heat treatment, the impurities in the porous support having the zeolite nano seeds can be removed, and the adhesion between the zeolite nano seed and the porous support can be improved.
Next, in the method for producing a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention, step 2 is a step of preparing a zeolite synthesis solution, The support is immersed in the zeolite synthesis solution to synthesize an MFI zeolite precursor, followed by drying and firing to form an MFI zeolite layer.
In step 2, the MFI zeolite is grown, and in step 1, a porous support having a seed on its surface is dipped in the zeolite synthesis solution to synthesize and sinter the MFI zeolite precursor.
The zeolite synthesis solution of step 2 may further comprise a silica source and an organic base.
Examples of the silica source include tetraethylorthosilicate (TEOS), ethyl silicate (ES), and colloidal silicon dioxide. But are not limited to, fumed silicon dioxide, tetramethyl orthosilicate, aluminosilicate, silicic acid, and the like.
Examples of the organic base include tetrapropylammonium hydroxide (TPAOH), tetraethylammonium hydroxide (TEAOH), tetrapropylammonium bromide (TPABr), and the like. It is not.
The zeolite synthesis solution may be prepared by mixing a silica source, an organic base and water. The molar ratio of silica source: organic base: water may be 0.5 to 1.5: 0.02 to 0.42: 84 to 124, 0.12 to 0.32: 94 to 114, and may be 0.9 to 1.1: 0.17 to 0.28: 99 to 109, but the MFI zeolite is not limited thereto as long as it is a composition that can be effectively synthesized.
Further, the zeolite synthesis solution to which the silica source, the organic base and the water are added may be stirred for 18 to 30 hours, stirred for 20 to 28 hours, stirred for 22 to 26 hours, It is not.
In step 2, the porous support on which a zeolite seed is formed may be dipped in the zeolite synthesis solution and then synthesized at a temperature of 100 ° C to 150 ° C for 12 hours to 24 hours, At a temperature of 15 to 20 hours, and may be synthesized at a temperature of 100 to 130 DEG C for 17 to 19 hours, but the present invention is not limited thereto.
In step 2, the porous support on which the zeolite seeds are formed may be synthesized by immersing in a zeolite synthesis solution, and then dried. After washing with water for 4 to 6 minutes, Lt; RTI ID = 0.0 > 20-40 < / RTI > minutes.
Further, in step 2, the porous support on which nano seeds have been formed is synthesized by immersing it in a zeolite synthesis solution. After drying, the porous support is heat-treated at a temperature of 400 ° C to 500 ° C at a temperature rise time of 0.5 to 1.5 ° C / min in a calcination furnace And can be heat-treated at a temperature of 420 ° C. to 480 ° C. and can be heat-treated at a temperature of 440 ° C. to 460 ° C. However, the present invention is not limited thereto as long as the MFI zeolite layer can be effectively formed.
Next, in the method for producing a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention, a solution containing a polymer having a nitrogen permeability of 50 barrer or more is prepared in step 2 And coating the surface of the formed MFI zeolite layer.
In the step 3, in order to compensate for the thermal cracking of the MFI zeolite caused by the difference in thermal expansion coefficient during the heat treatment in the step 2, and to improve the separation performance of nitrogen and hexafluorosulfide, the MFI zeolite Coat the layer surface with a solution containing a polymer with a nitrogen permeability of 50 barrer or more.
In the solution containing the polymer having a nitrogen permeability of 50 barrer or more in the step 3, a polymer having a nitrogen permeability of 50 barrer or more is a poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3- dioxole- tetrafluoroethylene] (PTFE AF), poly (1-trimethylsilyl-1-propyne) (PTMSP), poly (dimethylsiloxane) (PDMS), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene ), Polyethylene tetrafluoroethylene (ETFE), and polyethylene chlorotrifluoroethylene (ECTFE) may be used, but the present invention is not limited thereto.
The solution containing the polymer having a nitrogen permeability of 50 barrer or more may further include a fluorine-based solvent. The fluorine-based solvent may be perfluoro-N-alkyl-morpholines, Perfluorocarbonether, perfluorocycloether and perfluorohexane can be used. However, since the surface energy is low, penetration into zeolite defects can be suppressed. It is not limited thereto as long as it is an easy fluorine-based solvent.
The solution containing the polymer having a nitrogen permeability of 50 barrer or more in the step 3 may be added in an amount of 1 to 3 wt% based on the total solution, and a solution having a nitrogen permeability of 50 barrer or more may be added in an amount of 1.2 to 2.8 wt% And may be added in an amount of from 1.5% by weight to 2.5% by weight, but the present invention is not limited thereto.
Further, the coating method of the solution containing the polymer having the nitrogen permeability of 50 barrer or more in the step 3 may be a slide coating, a slip coating, a spin coating, a roll coating, a spray coating, a dip coating dip coating, flow coating, doctor blade, dispensing, inkjet printing, offset printing, screen printing, pad printing, gravure printing, flexography printing, stencil printing Imprinting and the like can be used. However, the present invention is not limited thereto, so long as it can easily coat a polymer having a nitrogen permeability of 50 barrer or more on the surface of the MFI zeolite layer.
Further, the step 3 may further include a heat treatment for coating a solution containing a polymer having a nitrogen permeability of 50 barrer or more. The heat treatment may be performed at a temperature of 50 ° C to 90 ° C, at a temperature of 60 ° C to 80 ° C, or at a temperature of 65 ° C to 75 ° C, but is not limited thereto.
Further, by coating the surface of the MFI zeolite layer with a polymer having a nitrogen permeability of 50 barr or more, hydrophobicity of the surface of the MFI zeolite layer can be minimized.
MFI zeolite membranes coated with a polymer having a nitrogen permeability of 50 barrer or more on the surface prepared by the above method can effectively separate SF 6 from waste gas containing nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) And has an effect of preventing moisture adsorption due to surface hydrophobicity. In addition, it has the effect of complementing the decreasing N 2 and SF 6 separation performance due to the thermal defects that occur during the heat treatment of the conventional MFI separation membrane.
Further,
A method for separating SF 6 from a waste gas containing nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) using the above separation membrane is provided.
In the method using the separation membrane according to the invention to the invention for separating SF 6 from a waste gas containing nitrogen (N 2) and sulfur hexafluoride (SF 6), nitrogen and hexafluoride sulfur different molecular size Therefore, nitrogen having a relatively small molecular size permeates through the separation membrane, and sulfur hexafluoride can not pass through the separation membrane. The separation of nitrogen and hexafluoride may proceed by maintaining the pressure at which the waste gas flows into the separator higher than the pressure after permeation through the separator.
In the case of the pressurized method, when the waste gas flows into the separator, the pressure is applied to the separator and the pressure is different from that of the permeate. The decompression system maintains the pressure difference by lowering the pressure of the outlet to less than the normal pressure.
Hereinafter, the present invention will be described in detail with reference to the following examples and experimental examples.
It should be noted, however, that the following examples and experimental examples are illustrative of the present invention and are not intended to limit the scope of the invention.
< Example 1 > nitrogen (N 2 ) And Sulfur hexafluoride (SF 6 ) Separation of zeolite membranes for separation 1
Step 1: As shown in Fig. 1, an alumina disk was prepared with a porous support, and a zeolite nano seed having a particle size of 50 nm to 60 nm was coated on the alumina disk by rubbing Respectively. Then, the alumina disk coated with the zeolite seeds was heat-treated at 500 ° C. to improve the adhesion between the zeolite seeds and the alumina disk and to remove the impurities.
Step 2: To prepare a zeolite synthesis solution, a mixture of tetraethylorthosilicate (TEOS), tetrapropylammonium hydroxide (TPAOH) and water (H 2 O) in a molar ratio of 1: 0.22: Mixed and stirred for 24 hours to prepare a zeolite synthesis solution. An MFI zeolite precursor was synthesized by immersing the alumina disk in which the zeolite seeds of step 1 were formed in the zeolite synthesis solution prepared above and heat-treating the mixture at 100 ° C for 16 hours. Thereafter, it was washed with water for 5 minutes and dried in an oven at a temperature of 70 DEG C for 30 minutes. Then, the resultant was heat-treated in a firing furnace at a heating rate of 1 DEG C / min and a temperature of 450 DEG C for 5 hours to form an MFI zeolite layer.
Step 3: Preparation of Teflon AF2400 (Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole-co-tetrafluoroethylene] (PTFE AF) manufactured by DuPont with a polymer having a nitrogen permeability of 50 barrer or more And a solution containing a polymer having a nitrogen permeability of 50 barrer or more was prepared using 3M FC-770 (perfluoro-N-alkyl-morpholines) as a fluorine-based solvent. The solution containing the polymer having the nitrogen permeability of 50 barrer or more was applied to the surface of the MFI zeolite layer formed in the step 2 by slip coating and the solution containing the polymer having a nitrogen permeability of 50 barrer or more was applied, A zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) was prepared by heat treatment.
< Example 2> nitrogen (N 2 ) And Sulfur hexafluoride (SF 6 ) Separation of zeolite membranes for separation 2
The procedure of Example 1 was repeated except that the alumina disk on which the zeolite seeds were formed was immersed in the zeolite synthesis solution and the synthesis time was changed to 18 hours in the step 2 of Example 1 to prepare nitrogen (N 2 ) and flesh A zeolite separation membrane for separating sulfur hexafluoride (SF 6 ) was prepared.
< Example 3> nitrogen (N 2 ) And Sulfur hexafluoride (SF 6 ) Separation of zeolite membranes for separation 3
The procedure of Example 1 was repeated except that the alumina disk on which the zeolite seeds were formed was immersed in the zeolite synthesis solution and the synthesis time was changed to 20 hours in the step 2 of Example 1 to prepare nitrogen (N 2 ) and flesh A zeolite separation membrane for separating sulfur hexafluoride (SF 6 ) was prepared.
< Comparative Example 1> Preparation of zeolite membrane
(N 2 ) and sulfur hexafluoride (SF 6 ) separation membranes were carried out in the same manner as in Example 2, except that the polymer coating having a nitrogen permeability of 50 barrer or more was not performed in Step 3 of Example 2 .
< Experimental Example 1> Comparison of selectivity and permeability of zeolite membrane
In order to confirm the selectivity ((N 2 permeability) / (SF 6 permeability)) of the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention, And the permeability of the zeolite membrane prepared in Comparative Example 1 was measured with a bubble flow meter at a pressure of 2 bar at a time of introducing nitrogen and sulfur hexafluoride and a pressure of 1 bar after permeation of the membrane was measured. .
As shown in Table 1, the selectivity of Comparative Example 1, which is a zeolite membrane having no surface coated with a polymer having a nitrogen permeability of 50 barrer or more, was 7.13, and the selectivity of the zeolite membrane coated with a polymer having a nitrogen permeability of 50 barrer or more The selectivity of the zeolite membrane coated with a polymer having a nitrogen permeability of 50 barrer or more on the surface is 47.3, the selectivity of the zeolite membrane of Example 2 is 47.3, the selectivity of the zeolite membrane coated with the polymer having a nitrogen permeability of 50 barrer or more And 40.7, respectively. Thus, it was confirmed that the separation performance of nitrogen and sulfur hexafluoride was improved by coating a polymer having a nitrogen permeability of 50 barrer or more on the surface of the zeolite layer, and it was confirmed that the most effective separation performance was obtained in Example 2 where the seed crystal growth time was 18 hours I could.
As a result, the zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) according to the present invention exhibits superior nitrogen and sulfur hexafluoride separation performance compared to conventional zeolite separation membranes due to a polymer coating having a nitrogen permeability of 50 barrer or more Respectively.
Claims (10)
(N 2 ) and sulfur hexafluoride (SF 2 ) using a zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ) containing a polymer having a nitrogen permeability of 50 barrer or more coated on the surface of the MFI zeolite layer. a method for separating SF 6 from the waste gas containing 6),
The zeolite separation membrane for separating nitrogen (N 2 ) and sulfur hexafluoride (SF 6 )
(N 2 ) and sulfur hexafluoride (SF 6 ), which is prepared by applying a solution containing a polymer having a nitrogen permeability of 50 barrer or more to the surface of an MFI zeolite layer and heat-treating the resulting solution at a temperature of 50 ° C to 90 ° C. method for separating SF 6 from the waste gas containing.
The polymer having a nitrogen permeability of not less than 50 barrer may be at least one selected from the group consisting of Poly [4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxole-co-tetrafluoroethylene] (PTFE AF), Poly (1-trimethylsilyl- (PTMSP), poly (dimethylsiloxane) (PDMS), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE) A method for separating SF 6 from a waste gas containing nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ), characterized in that it is at least one selected from the group consisting of polyethylene chlorotrifluoroethylene (ECTFE).
Method for separating SF 6 Sulfur hexafluoride (SF 6) permeability of the zeolite separation membrane is from the waste gas containing the nitrogen (N 2) and sulfur hexafluoride (SF 6), characterized in that 7 gpu to 63 gpu.
Wherein the nitrogen (N 2 ) permeability of the zeolite separation membrane is from 700 gpu to 900 gpu. A method for separating SF 6 from a waste gas comprising nitrogen (N 2 ) and sulfur hexafluoride (SF 6 ).
The solution containing the polymer having a nitrogen permeability of 50 barrer or more may further include a fluorinated solvent, and the fluorinated solvent may include perfluoro-N-alkyl-morpholines, perfluorocarbon ), perfluoro roteuri pentylamine (perfluorotripentylamine), perfluoro cyclopropyl ether (perfluorcycloether) and perfluoro-hexane (perfluorohexane), characterized in that at least one member selected from the group, nitrogen (N 2) and sulfur hexafluoride composed of ( method for separating SF 6 from the waste gas containing SF 6).
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