KR101672238B1 - Preparation of composite membrane for dicyclopentadiene purification - Google Patents

Abstract

The present invention relates to a composite membrane for purification of dicyclopentadiene and a method for producing the same, wherein the composite membrane for dicyclopentadiene purification is prepared by introducing an intermediate layer whose average pore is controlled without forming a separation layer directly on the porous support, (CPD) which is lower than dicyclopentadiene (DCPD) by increasing the stability of the film formation and suppressing the formation of cracks and pinholes during the separation of the membrane.

Description

TECHNICAL FIELD [0001] The present invention relates to a composite membrane for purification of dicyclopentadiene,

The present invention relates to a composite membrane for purification of dicyclopentadiene and a method for producing the same.

Dicyclopentadiene (DCPD) is a dimeric compound of cyclopentadiene (CPD). DCPD and CPD are produced as byproducts from naphtha pyrolysis of petrochemical plants and are included in C ₅ - oil, which is a byproduct of pyrolysis, in a weight ratio of about 10 to 20. DCPD and CPD are derivatives of norbornene which are one of the cyclic diene compounds which can be used industrially. High purity DCPD having a purity of 98.5% or more is a DCPD series petroleum resin, ethylene-propylene-diene (EPDM) It is a basic compound used as a raw material for various fine chemical materials including Elastomer or reaction injection molding (RIM) materials. It will be used for new high value added products using CPD and DCPD through the utilization of C ₅ - The need for research is emerging. (Patent Document 001)

As a method of recovering DCPD having a purity of about 80%, pure DCPD can be obtained by dimerization of CPD and removing low boiling point mixture from the product by distillation in the presence of toluene (Patent Document 002) . However, since DCPD produced by this method has only a low boiling point mixture, it is difficult to separate isoprene or piperylene having a boiling point similar to the boiling point of DCPD and a co-dimer of CPD, It is limited to use without purification, and this method has the drawback that only DCPD of up to 85% purity can be obtained.

Also, the rate at which DCPD is decomposed into CPD in the dimerization-mono-polymerization reaction of CPD and DCPD is reported to be 36% / hr at 170 ° C., and a method of thermally decomposing the DCPD mixture at 300 ° C. or higher is commonly used . The CPD generated in the DCPD pyrolysis reaction reacts with DCPD to generate a trimer or tetramer of CPD or a polymer compound by reacting with isoprene or piperylene. When the DCPD is stuck at 150 to 160 ° C for several hours, 50 % Can be polymerized with more than CPD trimer. The polymer thus produced is not readily decomposed in the pyrolysis process and can cause a problem of obstructing the pyrolysis device (Patent Document 003).

As a method for increasing the purity of DCPD, a method of dimerizing relatively pure CPD produced by DCPD monomerization after distillation is known. This can increase the purity of DCPD up to 99% since the rate of CPD and isomerization of isoprene or piperylene during CPD addition reaction is significantly slower than the rate of diminution of CPD. However, this method has a problem in operation because it generates a large amount of coke material that blocks the pipe and the cooler in vapor phase cracking of DCPD (Patent Document 004). In order to prevent the formation of the coke material, a further process of inserting the auxiliary fluid into the CPD and DCPD to separate the auxiliary fluid into the CPD and the DCPD is required, thereby consuming a large amount of energy.

A method of pyrolyzing an auxiliary fluid into a CPD by supplying a DCPD mixture is disclosed in Patent Document 005 and Patent Document 006. The method of using such auxiliary fluid has the disadvantage that the high boiling point compound contained in the DCPD mixture is left in the auxiliary fluid and the performance of the auxiliary fluid deteriorates and the auxiliary fluid must be continuously supplied to maintain the performance. To solve this problem, a method of preventing the coke produced by using the C ₉₊ fraction, as auxiliary fluid was proposed (Patent Document 007).

In addition to the above-mentioned method, conventionally, in the method of purifying DCPD, the distillation method requires not only an expensive distillation device but also a problem of low energy consumption and low recovery of DCPD as a target material. Also, there is a problem that a high boiling point material such as a CPD trimer is generated during a long stay in a reboiler operated at a relatively high temperature (120 ° C or higher). In order to prevent the CPD trimer from being produced in the re-boiling process, the operating temperature should be lowered to 100 ° C. or lower. Accordingly, the pressure of the distillation column must be lowered to 15 torr, so that the size of the apparatus is increased and the operation is very difficult. It is necessary to provide additional auxiliary fluid recovery distillation column, which leads to an increase in energy consumption.

However, the process using a separation membrane has been widely applied to the separation and purification of the chemical industry due to the fact that the phase separation hardly accompanies the phase separation and the energy consumption is significantly smaller than that of the conventional distillation method (Non-Patent Document 001). In particular, petrochemical processes are energy-consuming processes in the separation process, so energy consumption is low, process can be easily added, and efforts are being made to apply separation membrane processes that are simple in location and low in installation cost . In the separation process described above, DCPD is pyrolyzed at 250 DEG C as a method for removing CPD or other double bond compounds to monomerize DCPD, and CPD and low boiling substances such as butadiene and isoprene are distilled And 96% of DCPD can be obtained by quantifying the CPD having a weight ratio of 60 to 85% at 83 to 89 ° C and 7 to 10 psia at a weight ratio of 83 to 89%. The 96% DCPD mixture is subjected to secondary And separating them to obtain DCPD of 98% or more in high purity (Patent Document 008). The above method can obtain high purity DCPD by using three polymer membranes such as polydimethylsiloxane (PDMS), polyvinyl alcohol (PVA) and polyester imide, but the CPD permeability is as low as 10 g / m ² * h or less. (Patent Document 008)

In order to purify dicyclopentadiene (DCPD) at a high purity, the present inventors designed a composite membrane having high permeability and selectivity for cyclopentadiene rather than conventional polymer membranes, and used a DCPD The present inventors have completed the present invention.

Korean Patent Publication No. 10-2002-0035816 European Patent No. 2,334,633 Korean Patent Publication No. 10-2010-0022724 U.S. Patent No. 3,772,396 U.S. Patent No. 5,877,366 U.S. Patent No. 5,321,177 Korean Patent Publication No. 10-2004-0053649 U.S. Patent No. 5,401,891

 Desalination, Volume 235, Issues 13, 15 January 2009, Pages 199244

It is an object of the present invention to provide a composite membrane for dicyclopentadiene purification and a method for producing the same, and more particularly to a high selectivity to cyclopentadiene from a mixture of dicyclopentadiene (DCPD) and cyclopentadiene (CPD) And a method of manufacturing a separator which increases the purity of DCPD by removing a material other than DCPD by using the composite membrane having high permeability.

The present invention relates to a method for preparing a coating solution, which comprises preparing a coating solution containing alumina powder and silica-zirconia sol, immersing the porous support in the coating solution and then performing a first heat treatment to form an intermediate layer; And forming a separation layer by immersing the porous support having the intermediate layer in a silicon precursor solution and then subjecting the porous support to a secondary heat treatment; The present invention provides a method for producing a composite membrane for dicyclopentadiene purification.

According to an embodiment of the present invention, the step of forming the intermediate layer comprises a first coating solution containing an alumina powder having an average diameter of 1 to 10 mu m and a second coating solution containing an alumina powder having an average diameter of 50 to 500 nm May be sequentially coated to form an intermediate layer in which the average pore of the porous support is controlled.

According to an embodiment of the present invention, the step of forming the intermediate layer may include at least one or more repetitions of coating with the first coating solution, and then coating with the second coating solution at least once or more It can be done repeatedly.

According to an embodiment of the present invention, the silica-zirconia sol may include silica-zirconia particles having an average diameter of 50 to 300 nm.

According to an embodiment of the present invention, the first heat treatment may be performed at 300 to 800 ° C, and the second heat treatment may be performed at 200 to 500 ° C.

The present invention relates to a porous support; An intermediate layer formed on the porous support and containing alumina powder and silica-zirconia; And a separation layer formed on the intermediate layer and containing silica; To provide a composite membrane for dicyclopentadiene purification.

According to one embodiment of the present invention, the composite membrane may have a porosity gradient that reduces from the porous support to the separation layer.

According to an embodiment of the present invention, the composite membrane may have a gas permeability of 10 ^-7 to 10 ^-5 mol / m ² * s * Pa.

According to one embodiment of the present invention, the permeability of the composite membrane to cyclopentadiene is 100 To 500 g / m ² * h.

The present invention provides a method for purifying dicyclopentadiene using the composite membrane.

The composite membrane for purification of dicyclopentadiene according to the present invention can improve the stability of the separation layer by introducing an intermediate layer having an average pore size controlled without forming the separation layer directly on the porous support, It is possible to provide excellent selectivity and high transmittance to cyclopentadiene.

The composite membrane according to the present invention has excellent selectivity to cyclopentadiene and high permeability and removes molecules smaller than dicyclopentadiene from the C ₅ fraction which is a by-product of pyrolysis resulting from naphtha pyrolysis, Pentadiene can be obtained in high purity.

1 is a schematic view of a composite membrane for DCPD purification according to the present invention.
2 is a flowchart of a method for producing a composite membrane for DCPD purification according to the present invention.
FIG. 3 is an electron microscope (FE-SEM, Field Emission Scanning Electron Microscope) photograph of the intermediate layer formed in each step in Comparative Example 1. FIG.
4 is an electron microscope (FE-SEM, Field Emission Scanning Electron Microscope) photograph of the intermediate layer formed in each step in Example 1. FIG.
5 is an electron microscope (FE-SEM, Field Emission Scanning Electron Microscope) photograph of the composite membrane produced in Example 1. Fig.
FIG. 6 is a graph showing the result of analyzing components of the composite membrane section prepared in Example 1 by an electron microscope (FE-SEM, Field Emission Scanning Electron Microscope) (a) and EDS (Energy Dispersive X-ray Spectroscopy).
7 shows the results of the permeability and selectivity of the composite membrane prepared in Example 1 and Comparative Example 2. Fig.

The composite membrane for purification of dicyclopentadiene according to the present invention and the method for producing the composite membrane will be described in detail below. However, unless otherwise defined in the technical terms and scientific terms used herein, And a description of well-known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted in the following description.

The present invention relates to a method for preparing a coating solution, which comprises preparing a coating solution containing alumina powder and silica-zirconia sol, immersing the porous support in the coating solution and then performing a first heat treatment to form an intermediate layer; And forming a separation layer by immersing the porous support having the intermediate layer in a silicon precursor solution and then subjecting the porous support to a secondary heat treatment; The present invention provides a method for producing a composite membrane for dicyclopentadiene purification.

In the case of the composite membrane according to the present invention, it is possible to suppress the formation of cracks and pinholes when the separation layer is formed by forming the intermediate layer, and the average pore size of the separation layer can be precisely controlled.

The composite membrane according to the present invention has substantially no cracks, pinholes, life span, cracks, cracks, and the like, so that it can have uniform physical properties and high densities. The composite membrane may be a porous inorganic composite membrane of a ceramic material, and it may have properties superior in heat resistance, durability, and chemical resistance to conventional polymer membranes. It is important to precisely control the structure of the composite membrane of such a ceramic material. Accordingly, the composite membrane according to the present invention has an advantage that the size of the pores can be easily controlled according to the size of the molecule to be separated by introducing the intermediate layer, and the permeability and selectivity to the desired molecule can be controlled.

The porous support according to an embodiment of the present invention is not limited as long as it is suitable for use as a support, and may be any shape or geometry, and the shape may be tubular or plate-like. In this case, the non-limiting example of the tubular shape may be a rectangular, square, or cylindrical tubular shape. In a preferred embodiment, the porous support may be a cylindrical tubular shape.

The porous support may also be a ceramic or a porous metallic material, and non-limiting examples of the ceramic may be mullite, alumina, silica, titania, zirconia or silicon carbide, May be stainless steel, sintered nickel or a mixture of sintered nickel and iron, but is not limited thereto.

According to an embodiment of the present invention, the porous support may include alpha-alumina (alpha -Al ₂ O ₃ ) or gamma-alumina (gamma -Al ₂ O ₃ ). The average pore size of the α-Al ₂ O ₃ or γ-Al ₂ O ₃ may be 100 nm to 100 μm, preferably 500 nm to 10 μm, Preferably from 600 nm to 5 탆.

In addition, the silica-zirconia sol according to an embodiment of the present invention may be manufactured by the following method, or may be manufactured by methods known to those skilled in the art.

The silica-zirconia sol may be prepared by dissolving a first silicon precursor in a (C1-C4) alcohol and then adding an acid catalyst to prepare a silica sol by primary hydrolysis; Adding a first zirconium precursor to perform secondary hydrolysis; And further adding a hydrolysis solution to perform tertiary hydrolysis and condensation; The silica-zirconia particles thus prepared may be used in the form of a silica-zirconia sol dispersed in a reaction solution without any further purification after the reaction without carrying out the drying step. As described above, By subdividing the decomposition step, the silica-zirconia sol has a uniform particle size distribution and low cohesive strength, and can be maintained in a stable state without formation of a long-term precipitation. In this case, the silica-zirconia sol may be dispersed in an amount of 0.5 to 5.0% by weight based on the total weight of the silica-zirconia particles.

In the above-described method for producing a silica-zirconia sol, the first silicon precursor and the first zirconium precursor are not limited as long as they are capable of performing a sol-gel reaction. However, as a non-limiting example of the first silicon precursor Includes tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraisopropoxy silane, methoxytriethoxysilane, dimethoxydiethoxysilane, ethoxytrimethoxysilane, methyl tri But are not limited to, methoxysilane, methyltriethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldethoxysilane, diethyldiethoxysilane, tetramethoxymethylsilane, tetramethoxyethylsilane or tetraethoxymethylsilane And non-limiting examples of the first zirconium precursor include zirconium acetylacetonate, zirconium acetate, But may be zirconium butoxide or zirconium chloride.

In the method for producing a silica-zirconia sol according to an embodiment of the present invention, when the molar ratio of the first silicon precursor to the first zirconium precursor and water is Si: Zr = 1: 1, (Si + Zr) ₂ O may be from 1:10 to 80, preferably from 1:20 to 60, more preferably from 1:30 to 50, which is a preferred embodiment, and is suitably adjusted according to the size of the desired silica-zirconia Of course. At this time, the silica-zirconia sol adjusted to the above ratio includes silica-zirconia particles in the range of 50 to 300 nm.

The silica-zirconia may be mixed with the alumina powder and coated on the porous support to control the pore size of the porous support and controlled by the ratio of the first silicon precursor and the first zirconium precursor in the above- The performance of the intermediate layer may depend on the size of the silica-zirconia. Further, the intermediate layer is excellent in heat resistance, corrosion resistance and acid resistance, and can precisely control the pore size of the composite membrane, so that the permeability and selectivity of the desired molecule can be appropriately controlled.

The intermediate layer may be mixed with the alumina powder and the silica-zirconia water dispersion solution at a ratio of 1:10 to 1: 100, preferably 1:20 to 1: 100, more preferably 1:40 to 1: 60 to prepare a coating solution.

At this time, the immersion time is not limited, but may be 1 second to 10 minutes, preferably 1 to 60 seconds, and more preferably 1 to 20 seconds.

In the method for preparing a composite membrane for purification of dicyclopentadiene according to an embodiment of the present invention, the step of forming the intermediate layer includes a first coating solution containing alumina powder having an average diameter of 1 to 10 mu m, A second coating solution containing 500 nm of alumina powder may be sequentially coated to control the average pore size.

In this case, the alumina powder contained in the first coating solution is preferably larger than the average pore size of the porous support, and the average size of the surface pores of the intermediate layer is adjusted using the first coating solution and the second coating solution, A flat surface state can be realized.

The step of forming the intermediate layer according to an embodiment of the present invention may form a linear or stepped void gradient depending on the particle size of the alumina powder and the silica-zirconia, The step of coating with the coating solution may be repeated at least once and then the step of coating with the second coating solution may be repeated at least once or more. This is for controlling the average size of the surface pores of the intermediate layer and can be appropriately modified according to the size of the molecule to be separated.

The forming of the separation layer according to an embodiment of the present invention may be performed by immersing the porous support having the intermediate layer formed thereon in a silicon precursor solution. At this time, as a non-limiting example of the silicon precursor forming the separation layer, 1,1,3,3-tetramethoxy-1,3-dimethyl-1,3-disilachpropane (TMDMDP) 3, 3-tetra-methoxy-1-methyl-3-hexyl-1,3-sila propane (TMMHDP), 1,1,3,3- tetra-methoxy-1,3-di - n - hexyl -1 , 3-disilapropane (TMDHDP), 1,1,3,3-tetramethoxy-1-methyl-3-cyclohexyl-1,3-disilafluoropropane (TMMCDP) Tetramethoxy-1,3-dicyclohexyl-1,3-disilafluoropropane (TMDCDP), 1,1,8,8-tetramethoxy-1,8-dicyclohexyl- (TMDCDO), 1,1,3,3-tetramethoxy-1,3-dimethyldisiloxane (TMDMDS) or 1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane (TEDMDS) Tetramethoxy-1,3-dimethyldisiloxane (TMDMDS) or 1,1,3,3-tetraethoxy-1, 2, 3, 3-dimethyldisiloxane (TEDMDS).

In the step of forming the intermediate layer according to an embodiment of the present invention, the silicon intermediate is preferably used in an amount of 1 to 5% by weight in a (C1-C4) alcohol.

At this time, the immersion time is not limited, but may be 1 second to 10 minutes, preferably 1 to 60 seconds, and more preferably 1 to 20 seconds.

Also, the heat treatment according to an embodiment of the present invention may be performed at 200 to 800 ° C, preferably 300 to 800 ° C for the first heat treatment and 200 to 500 ° C for the second heat treatment, The heat treatment may be 400 to 600 占 폚 and the second heat treatment may be 250 to 450 占 폚.

The time of the heat treatment is not limited, but may be 10 minutes to 12 hours, preferably 10 minutes to 6 hours, more preferably 30 minutes to 2 hours.

The composite membrane according to the present invention preferably has a dense structure having a high porosity in terms of high selectivity to cyclopentadiene and high permeability, which can be controlled by the secondary heat treatment. At this time, it is preferable that the secondary heat treatment temperature can be appropriately adjusted in consideration of the permeability and selectivity of the target molecule, and it is preferable to reduce the area of the composite membrane and shorten the permeation purification time, thereby being economically efficient .

Accordingly, the present invention relates to a porous support; An intermediate layer formed on the porous support and containing alumina powder and silica-zirconia; And a separation layer formed on the intermediate layer and containing silica; Wherein the porous support has a pore gradient reduced to the separation layer.

In the composite membrane, the intermediate layer having an average pore control is introduced without forming the separation layer directly on the porous support, thereby improving the film forming stability of the separation layer and suppressing the formation of cracks and pinholes when the separation layer is formed, It is possible to realize high selectivity and high transmittance for pentadiene, and it is expected to be useful for gas separation because of excellent heat resistance, durability and chemical resistance.

The intermediate layer may form a linear or stepwise void gradient depending on the alumina powder and the silica-zirconia particle size, and such void gradient may be formed in a gradient that is smaller than the average porosity of the porous support by 10 to 90% , Preferably 30 to 80%, more preferably 50 to 80%.

The intermediate layer according to the present invention may be formed by mixing a first coating solution containing alumina powder having an average diameter of 1 to 10 mu m and silica-zirconia of 50 to 300 nm and a second coating solution containing an alumina powder having an average diameter of 50 to 500 nm The average pore size of the intermediate layer can be controlled by sequentially coating the alumina powder and the second coating solution containing 50 to 300 nm silica-zirconia.

The composite membrane produced by the above-described production method can have an excellent gas permeability of 10 ^-7 to 10 ^-5 mol / m ² * s * Pa. A non-limiting example of the gas may be a single gas selected from H ₂ , He, CH ₄ , O ₂ , N _2, and CO ₂ , or a mixture of two or more gases.

The composite membrane according to one embodiment of the present invention is characterized in that for a feed comprising a high content of DCPD, And a low dicyclopentadiene permeability in the range of 20 g / m ² * h.

The composite membrane was also found to have a < RTI ID = 0.0 > 100 & To 500 g / m < ² > * h and high selectivity.

Due to the properties described above, the composite membrane according to the present invention has the advantage that dicyclopentadiene can be refined in a short period of time, and it is possible to obtain dicyclopentadiene from the C ₅ -fluid, a by-product of pyrolysis produced as a byproduct obtained from naphtha pyrolysis It can be purified with high purity.

The thickness of the composite membrane according to one embodiment of the present invention includes an intermediate layer and a separation layer formed on the porous support and may range from 0.1 to 100 mu m. In the thickness of the composite membrane, the ratio of the porous support to the intermediate layer may be in the range of 300: 1 to 100: 1, and the ratio of the porous support coated with the intermediate layer to the separation layer may range from 200: 1 to 100: Lt; / RTI > to form a composite membrane.

The present invention also provides a method for purifying dicyclopentadiene using the composite membrane. The method of purifying the dicyclopentadiene may be one which is purified by a pervaporation method.

In the pervaporation method according to the present invention, a mixture containing a target substance to be separated on one side with a membrane therebetween is vacuum-dried on the other side by a pump or vacuum, and a liquid containing the target substance is permeated by a pressure difference or a temperature difference, And evaporates them on the opposite side to separate the target material from the mixture. This method is independent of azeotropic mixture formation because it is dominated by molecular kinetics, not gas-liquid equilibrium, because phase change occurs when liquid molecules selectively diffuse through the membrane. And there is no need to use toxic additives in the distillation.

The cyclopentadiene can be selectively removed from the C ₅ -four oil, which is a by-product obtained from naphtha pyrolysis and is a by-product of pyrolysis, and the purification method described above can purify dicyclopentadiene with high purity from 95 to 99.99% And purification can be performed at a higher purity than that of conventional polymer membranes, which is a more economical method.

Hereinafter, a method of manufacturing a dissimilar metal composite of the present invention and an electrode using the same will be described with reference to specific examples, but the scope of the claims of the present invention is not limited thereto.

(Production Example 1)

Process for producing silica-zirconia sol

1.0 g of TEOS (Tetraethoxysilane) is dissolved in 93.62 g of ethanol, and a mixed solution of 3.47 g of ethanol, 8.02 g of water and 0.21 g of a hydrochloric acid catalyst is slowly added to a flask containing TEOS, to a 500-mL 2-neck round bottom flask And subjected to primary hydrolysis at 70 DEG C for 1 hour. 1.0 g of zirconium (IV) tert -butoxide (Zr (OC ₄ H ₉ ) ₄ , ZrTB) was dissolved in 3.47 g of ethanol and 8.02 g of water was added to the reaction flask to carry out the secondary hydrolysis reaction at 70 ° C Lt; / RTI > 8.02 g of water was further added to the solution subjected to the second hydrolysis reaction, and a tertiary hydrolysis reaction was carried out at the same temperature for 2 hours to synthesize a silica-zirconia sol having an average particle size of 100 nm. After the reaction, the reaction solution was stabilized by heating at 100 DEG C for 30 minutes. The reaction mixture was transferred to a distillation apparatus and the solvent was replaced with distilled water for 12 hours to finally obtain silica-zirconia sol (1.0 wt% SiO ₂ -ZrO ₂ sol in water).

(Example 1)

2 g of 3 탆 α-Al ₂ O ₃ powder was mixed with 98 g of the silica-zirconia sol prepared in Preparation Example 1 to prepare a first coating solution. A porous alpha-alumina support (? -Al ₂ O _3, OD: 10 mm, L: 50 mm) was immersed in the first coating solution for 5 seconds and then heat-treated at 550 ° C. The first coating solution was coated 5 times in the same manner. Then, 2 g of 150 nm alpha-alumina (? -Al ₂ O ₃ ) powder was mixed with 98 g of the silica-zirconia sol prepared in Preparation Example 1 to prepare a second coating solution. The porous alpha-alumina support coated with the second coating solution was immersed for 5 seconds and then heat-treated at 550 ° C. The second coating solution was coated five times in the same manner to form an intermediate layer.

The porous α-alumina support having the intermediate layer was immersed in a 1.0 wt% TEDMDS solution (in EtOH) for 5 seconds, and then heat-treated at 450 ° C. A TEDMDS solution (in EtOH) was coated 10 times in the same manner to form a separation layer to prepare a composite membrane for purification of dicyclopentadiene. FIGS. 1 and 2 show flow diagrams of the composite membrane for dicyclopentadiene purification and the method for producing the composite membrane.

Alumina _{(α-Al 2 O 3 -} 3 ㎛ alpha _{(50 mm α-Al 2 O} 3, OD:: 10 mm, L) if the dicyclopentadiene purification composite membrane for prepared in Example 1, the porous support It was coated with a first coating solution comprising zirconia sol was observed by FE-SEM in the intermediate layer (Fig. 4 (a) and (b)), porous alpha-) powder and a silica-alumina (α-Al ₂ O ₃ ) of alpha surface pore-alumina (α-Al ₂ O ₃₎ powder and the silica-was confirmed that filling the zirconia particles evenly, 150 nm alpha-alumina (α-Al ₂ O ₃₎ powder and the silica-zirconia sol (FIG. 4 (c) and FIG. 4 (d)). As a result, a 150 nm α-Al ₂ O ₃ powder And silica-zirconia particles were smoothly coated and the intermediate layer was formed without pinholes or cracks.

5 (a) and (b)). As a result, it was confirmed that the separation layer having a more dense surface without pinholes or cracks was formed even at a low magnification.

It was confirmed that the composite membrane for purification of dicyclopentadiene formed on the porous support in Example 1 had a thickness of 10 μm. As a result of analyzing the components by EDS (Energy Dispersive X-ray Spectroscopy), the elements of Si, C and Zr Confirming that the silica separating layer was well coated on the porous support (see FIG. 6).

(Example 2)

A composite membrane for purification of dicyclopentadiene was prepared in the same manner as in Example 1 except that the heat treatment temperature in the step of forming the separation layer was 300 캜.

In the case of the composite membrane for purification of dicyclopentadiene prepared in Example 2, it was confirmed from the gas permeation test result that the intermediate layer was formed without pinholes or cracks (see FIG. 7).

(Comparative Example 1)

A porous alum-alumina support (? -Al ₂ O _3, OD: 10 mm, L: 50 mm) was prepared by dissolving 2.0 g of 3 탆 α-Al ₂ O ₃ powder in 98 ml of water, Lt; RTI ID = 0.0 > 550 C. < / RTI > Five times coating was carried out in the same manner. Then, 2.0 g of 150 nm alpha-alumina (? -Al ₂ O ₃ ) powder was evenly dispersed in 98 ml of water, and the coated porous alpha-alumina support was immersed for 5 seconds and then heat-treated at 550 ° C. The coating was carried out 5 times in the same manner.

The porous alpha-alumina support having the intermediate layer was immersed in a 1.0 wt% TEDMDS solution (in EtOH) for 5 seconds and then heat-treated at 300 ° C. A TEDMDS solution (in EtOH) was coated 10 times in the same manner to form a separation layer to prepare a composite membrane for purification of dicyclopentadiene.

In the case of the composite membrane for purification of dicyclopentadiene prepared in Comparative Example 1, FE-SEM was observed after coating 3 탆 α-Al ₂ O ₃ powder (FIGS. 3 (a) and 3 b)) and 150 nm of alpha-alumina (α-Al ₂ O ₃₎ was coated with the powder was observed with FE-SEM (Fig. 3 (alpha in c) and (d)) - alumina powder is porous alpha-alumina (α-Al ₂ O ₃ ) surface evenly. However, when the silica-zirconia sol prepared in Preparation Example 1 was coated (FIGS. 3 (e) and 3 (f)), it was confirmed that an uneven coating state including pinholes and cracks was formed.

This porous alpha-can be expected to have been a part of the coating layer disappears in the process of being re-dispersed zirconia sol to form a crack-alumina (α-Al ₂ O ₃₎ of alumina particles simply physically distributed on the surface of the silica.

The gas permeability and selectivity were confirmed using the composite membrane for purification of dicyclopentadiene prepared in Example 1 and Example 2, and the results are shown in Table 1 below.

As shown in Table 1, it was confirmed that the gas permeability can be controlled according to the second heat treatment temperature. When the heat treatment temperature is 450 ° C., the methyl organic functional group of TEDMDS is partially decomposed to affect the pore size of the composite membrane Can be used to provide a higher gas permeability. By using a composite membrane having such a high permeability, it is possible to provide an economical purification method capable of removing a target material in a shorter time.

The pervaporation test was carried out using the composite membrane for purification of dicyclopentadiene prepared in Examples 1 and 2 and Comparative Example 1, and the results are shown in Table 2 and FIG.

As a result, as shown in Table 2, it was confirmed that the composite membrane according to Examples 1 and 2 had better permeability than the composite membrane according to Comparative Example 1. Therefore, the composite membrane according to the present invention can be an economical method of obtaining high purity dicyclopentadiene in a short time by having a high transmittance.

Claims (10)

Preparing a coating solution containing alumina powder and silica-zirconia sol, immersing the porous support in the coating solution, and then performing a first heat treatment to form an intermediate layer; And
Forming a separation layer by immersing the porous support having the intermediate layer in a silicon precursor solution and subjecting the porous support to a secondary heat treatment; Wherein the step of forming the intermediate layer comprises dipping the porous support in a first coating solution containing alumina powder having an average diameter of 1 to 10 mu m and then subjecting the resulting product to heat treatment to obtain an intermediate layer having an average diameter of 50 to 500 nm Wherein the porous support is immersed in a second coating solution containing alumina powder and then heat-treated to control an average pore size of the porous support. delete The method according to claim 1,
The step of forming the intermediate layer may include repeating at least one or more times of coating with the first coating solution and then coating with the second coating solution at least once or more. The dicyclopentadiene A method for producing a composite membrane for purification. The method of claim 3,
Wherein the silica-zirconia sol comprises silica-zirconia particles having an average diameter of 50 to 300 nm. The method according to claim 1,
Wherein the first heat treatment is performed at 300 to 800 캜 and the second heat treatment is performed at 200 to 500 캜. delete delete delete delete delete

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