KR102411367B1 - ALUMINUM BASED Organic-Inorganic Hybrid nanoporous materials FOR SEPERATION OF OLEFIN/PARAFFIN COMPOUND AND SEPERATION METHOD OF OLEFIN/PARAFFIN COMPOUND - Google Patents

Abstract

According to one embodiment of the present invention, aluminum ions; and an organic ligand connected to the aluminum ion, wherein the organic ligand is a polycyclic aromatic compound and a heterocyclic aromatic compound including at least one carboxylate group bonded to a ring. at least one selected from the group consisting of, wherein the aluminum ion and the organic ligand form a crystal structure including pores, and the polycyclic aromatic compound or the heterocyclic aromatic compound provided in the crystal structure is an olefin compound and paraffin An organic-inorganic hybrid nanoporous body that selectively adsorbs a paraffin compound in a mixture of compounds is provided.

Description

ALUMINUM BASED Organic-Inorganic Hybrid nanoporous materials FOR SEPERATION OF OLEFIN/PARAFFIN COMPOUND AND SEPERATION METHOD OF OLEFIN/PARAFFIN COMPOUND

The present invention relates to an organic-inorganic hybrid nanoporous body for separating aluminum-based olefin/paraffin and a method for separating olefin/paraffin using the same.

Currently, in the oil refining and petrochemical industries, olefin molecules with 2 to 4 carbon atoms such as ethylene, propylene, and butylene are used to produce synthetic resins such as polyethylene, polypropylene, and polybutene, and chemical products such as ethylbenzene, ethylene glycol, and propylene glycol. It is known as one of the most important raw materials in the petrochemical industry as the compound with the highest production volume. In particular, ethylene and propylene monomers are produced annually in the petrochemical and gas chemical industries at an annual scale of 200 million tons, and they are recognized as one of the most important chemical products supporting the modern industrial society. These olefin compounds are produced by various raw materials and processes such as pyrolysis and catalytic cracking of naphtha, ethane cracking, propane dehydrogenation, ethane/propane cracking and dehydrogenation of shale gas, olefin conversion of methanol, and fluidized bed catalytic cracking of heavy oil. is becoming However, in order to be used as a raw material for a synthetic polymer resin, ethylene, propylene, and butylene monomers having a purity of 99.5% or more must be prepared.

The separation technology of the olefin and paraffin mixture has been operated by a distillation process for the past several decades in spite of low energy efficiency and excessive equipment cost. However, due to the excessive energy consumption of the distillation process currently in use, the continuous development of an alternative process has been required. The currently used olefin separation and purification process is the separation of hydrocarbons by carbon number and olefin/paraffin separation of the same carbon number, and is performed by a multi-step distillation method using the difference in boiling point of each hydrocarbon. The problem with the separation and purification process in the current ethylene and propylene production process is that the boiling points of the ethylene/ethane and propylene/propane molecules to be separated are very similar. to be.

Therefore, there is a need to develop an adsorbent capable of effectively separating ethane from an ethane/ethylene mixture.

An object of the present invention is to provide an adsorbent capable of selectively adsorbing ethane from a mixture of ethane and ethylene as an organic-inorganic hybrid nanoporous body for aluminum-based olefin/paraffin separation.

An object of the present invention is to provide a method for separating olefins and paraffins using an organic-inorganic hybrid nanoporous body, in particular, by selectively adsorbing ethane from a mixture of ethane and ethylene to produce high-purity ethylene.

According to an embodiment of the present invention, aluminum ions; an organic ligand connected to the aluminum ion, wherein the organic ligand includes at least one selected from the group consisting of a polycyclic aromatic compound and a heterocyclic aromatic compound, and the aluminum ion and the organic ligand forms a crystal structure including pores, and the polycyclic aromatic compound or the heterocyclic aromatic compound provided in the crystal structure selectively adsorbs a paraffin compound in a mixture of an olefin compound and a paraffin compound, An organic-inorganic hybrid nanoporous body is provided.

According to an embodiment of the present invention, the organic ligand is 2,6-naphthalenedicarboxylate, 4,4'-biphenyldicarboxylate, 3,5 -Pyridine dicarboxylate (3,5-Pyridinedicarboxylate), 2,5-furandicarboxylate (2,5-Furandicarboxylate), 2,5-thiophenedicarboxylate (2,5-Thiophenedicarboxylate), and 3,5 An organic-inorganic hybrid nanoporous body comprising at least one selected from the group consisting of -1H-pyrazoledicarboxylate (3,5-1H-pyrazoledicarboxylate) is provided.

According to an embodiment of the present invention, an organic-inorganic hybrid nanoporous body having a specific surface area of 1000m ² /g to 2400m ² /g is provided.

According to an embodiment of the present invention, the organic-inorganic hybrid nanoporous body selectively adsorbs a paraffin compound from a mixture of an olefin compound having 3 or less carbon atoms and a paraffin compound having 3 or less carbon atoms, and the organic-inorganic hybrid nanoporous body is subjected to pressure Depending on the conditions, the difference between the adsorption amount of the olefin compound having 3 or less carbon atoms and the paraffin compound adsorption amount having 3 or less carbon atoms is 0.5 mmol/g or more at or below the liquefaction pressure of the olefin compound, an organic-inorganic hybrid nanoporous body is provided.

According to an embodiment of the present invention, a first step of loading a mixture of an olefin compound and a paraffin compound; a second step of selectively adsorbing a paraffin compound in the mixture loaded in the first step using a complex including an organic-inorganic hybrid nanoporous body; and a third step of regenerating the organic-inorganic hybrid nanoporous body and separating the paraffin compound and the olefin compound, wherein the organic-inorganic hybrid nanoporous body includes aluminum ions; and an organic ligand connected to the aluminum ion, wherein the organic ligand is a polycyclic aromatic compound and a heterocyclic aromatic compound including at least one carboxylate group bonded to a ring. There is provided a method for separating olefins and paraffins including at least one selected from the group, wherein the aluminum ions and the organic ligands form a crystalline structure including pores.

According to an embodiment of the present invention, there is provided a method for separating olefins and paraffins, wherein the composite further includes a polymer compound and an inorganic compound provided in combination with the organic-inorganic hybrid nanoporous body.

According to an embodiment of the present invention, in the second step, ethane is selectively adsorbed by the organic-inorganic hybrid nanoporous body in the mixture of ethane and ethylene, or in the organic-inorganic hybrid nanoporous body in the mixture of propane and propylene A method for separating olefins and paraffins by selectively adsorbing propane is provided.

According to the present invention, it is possible to provide an organic-inorganic hybrid nanoporous body capable of selectively adsorbing and separating olefins and paraffins, and a process for separating olefins and paraffins using the same.

1 is a flowchart illustrating a method for separating olefins and paraffins according to an embodiment of the present invention.
2A to 2D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 1. FIG.
3A to 3D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 2.
4A to 4C are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 3.
5A to 5D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 4.
6a to 6d are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 5;
7A to 7D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 6.
8A to 8D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 7.
9A to 9D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Comparative Example.
10A and 10B are graphs of the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 1. FIG.
11a and 11b are graphs of the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 2.
12a and 12b are graphs of the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 3.
13 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 4.
14 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 5;
15 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 6.
16 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 7.
17 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Comparative Example.
18 to 20 are results of breakthrough separation experiments of organic-inorganic hybrid nanoporous bodies according to an embodiment of the present invention.

Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

According to Figure 1, the olefin / paraffin separation method according to the present invention is a first step (S100) of loading a mixture of an olefin compound and a paraffin compound, a paraffin compound in the mixture loaded in the first step (S100) organic-inorganic hybrid nano and a second step (S200) of selectively adsorbing using the pore body.

In the first step ( S100 ), a mixture including an olefin compound and a paraffin compound is loaded into the chamber. At this time, the chamber may be implemented in various shapes as a device for performing separation of the olefin compound and the paraffin compound. For example, the chamber may be provided in the form of a column or a pipe in which an organic-inorganic hybrid nanoporous body for adsorption is provided in the form of a fluidized bed. The shape of the chamber is not limited.

The loading of the mixture in the first step (S100) may be performed continuously. For example, in the first step ( S100 ), a mixture for separation is continuously loaded, and the loaded mixture is sequentially separated and discharged out of the chamber. Accordingly, the entire olefin/paraffin separation process may be a continuous process, and thus the efficiency of the entire process may be improved.

In order to continuously supply the mixture in the first step ( S100 ), the chamber may be connected to a member of another process. For example, the chamber may be connected to a distillation column. The distillation column is supplied with crude oil to perform cracking and fractional distillation, and a mixture of olefin compounds and paraffin compounds, which are part of the cracked and fractionated products, may be supplied to the chamber of the first step (S100). Accordingly, the olefin compound and the paraffin compound may be substances having a similar carbon number. For example, the olefin compound and the paraffin compound may be hydrocarbons having 2 to 3 carbon atoms. Since it is difficult to separate these materials by fractional distillation using a conventional boiling point difference, a separate separation process according to the present invention is required.

The mixture loaded in the first step (S100) is selectively adsorbed and separated in the second step (S200).

In the second step (S200), the olefin compound and the paraffin compound included in the mixture are separated using the organic-inorganic hybrid nanoporous body provided in the chamber. Separation of the olefin compound and the paraffin compound can therefore be performed through an adsorption separation process. The adsorptive separation process may be, for example, a pressure swing adsorption (PSA) process, or pressure adsorption or atmospheric pressure adsorption.

When the second step ( S200 ) includes the pressure separation process described above, the second step ( S200 ) in the adsorption chamber may be performed under a pressure condition below the liquefaction pressure of the olefin compound.

The second step (S200) may be performed at a temperature condition of about 273K to about 373K. By performing the second step (S200) in the above-mentioned range, the organic-inorganic hybrid nanoporous body is not thermally decomposed, and the adsorption amount difference by controlling the equilibrium adsorption amount of the paraffin compound and the olefin compound of the adsorbent through the adsorption pressure and adsorption temperature control can be maximized.

In the second step (S200), the olefin compound and the paraffin compound may each have 3 or less carbon atoms. For example, the olefin compound may be ethylene and/or propylene and the paraffin compound may be ethane and/or propane.

The third step (S300) is a method of regenerating the adsorbent after adsorption, and may be performed by a reduced pressure, an elevated temperature, and a gas purge method. In the third step (S300), the organic-inorganic hybrid nanoporous body may be regenerated to separate the paraffin compound and the olefin compound included in the mixture. In this case, separating the paraffin compound and the olefin compound includes both completely separating the paraffin compound and the olefin compound and significantly increasing the concentration of one type of compound in the mixture compared to the other compounds. For example, after the third step (S300) is performed, a gas having a content of a paraffin compound higher than that of an olefin compound may be recovered.

The degree of pressure reduction in the regeneration method of the third step (S300) may vary depending on the degree of pressure of the adsorption method of the second step (S200). For example, when the adsorption process is performed at 1 atmosphere, the pressure reduction process may be performed in the range of 0.3 bar to 0.5 bar. In addition, when the adsorption process is performed at 1 atmosphere or more, the reduced pressure process may be performed in the range of 0.5 bar to 1 bar.

The degree of temperature increase in the regeneration method of the third step (S300) may be performed at 50 degrees to 150 degrees.

The gas used for the gas purge method among the regeneration methods of the third step (S300) may be an inert gas such as nitrogen, helium, argon, or high-purity ethylene of 99.5% or more, which is recovered as a product.

As the regeneration method of the third step (S300), a reduced pressure, an elevated temperature, and a gas purge method may be used in combination.

The process from the first step (S100) to the third step (S300) of the separation method through adsorption may include two or more process units. Accordingly, while the regeneration process of the third step (S300) is performed after the adsorption of the first step (S100) and the second step (S200) in one process unit is completed, the adsorption of the mixture in the other process unit is performed The process may be performed. Accordingly, a plurality of process units can be alternately regenerated, and ethylene can be continuously produced.

The organic-inorganic hybrid nanoporous body includes an aluminum ion and an organic ligand connected to the aluminum ion.

The organic ligand may include at least one selected from the group consisting of a polycyclic aromatic compound and a heterocyclic aromatic compound.

Organic ligands include, for example, 2,6-naphthalenedicarboxylate, 4,4'-biphenyldicarboxylate, 3,5-pyridinedicarboxylate ( 3,5-Pyridinedicarboxylate), 2,5-furandicarboxylate (2,5-Furandicarboxylate), 2,5-thiophenedicarboxylate (2,5-Thiophenedicarboxylate), and 3,5-1H-pyrazole It may include at least one selected from the group consisting of dicarboxylate (3,5-1H-pyrazoledicarboxylate).

When the organic ligand is the above-mentioned material, the porosity of the organic-inorganic hybrid nanoporous body is improved and the adsorption amount may be improved together. In addition, the organic-inorganic hybrid nanoporous body including the above-described organic ligand may selectively adsorb a paraffin compound in a mixture of an olefin compound and a paraffin compound. Accordingly, it is possible to produce a high-purity olefin compound through the selective adsorption of paraffin using the organic-inorganic hybrid nanoporous body.

The adsorbent according to the prior art usually selectively adsorbs olefins among olefins and paraffins. For example, a hybrid nanoporous body called ZIF-8, in which the central metal zinc forms a three-dimensional framework compound in the form of coordination with imidazole-based ligands, is an adsorbent known to have propylene adsorption selectivity compared to propane. It selectively adsorbs olefin compounds rather than compounds. Accordingly, adsorbents according to the prior art, such as ZIF-8, are not suitable for producing high-purity olefin compounds. Specifically, when using the above-described conventional adsorbent, a process of separating the adsorbed olefin compound from the adsorbent must be additionally performed. In addition, it is difficult to produce a high-purity olefin compound because impurities may be mixed in the process of performing the additional process.

In addition, in the case of the adsorbent according to the prior art, it was difficult to operate the pressure circulation type adsorption process because the equilibrium adsorption amount for olefin and the equilibrium adsorption amount for paraffin were similar.

Specifically, taking the representative olefin/paraffin separation field in the chemical material adsorption separation as an example, zeolite adsorbent has been studied most extensively as a novel adsorption material for separation, but over the past several decades, propylene work adsorption capacity, propylene adsorption selectivity, and propylene desorption ease problems could not be resolved.

As an alternative, research on the development of an adsorbent for a hybrid nanoporous MOF material, which is a coordination metal compound, which is a new type of nanopore, has been continuously conducted since the early and mid-2000s. Until now, studies on the selective adsorption of olefins have been mainly conducted in MOF adsorbents using the unsaturated metal coordination site in the backbone as the adsorption site. For example, J.S Chang's research team published a study on propane/propylene separation and ethane/ethylene separation using MIL-100(Fe) material, and proposed the possibility of propane/propylene separation by applying the above concept, and in 2012, J.R. Long's research team proposed MOF-74(Fe) as an olefin adsorbent with high selectivity compared to paraffin, and suggested the possibility of PSA process application by using CuBTC(HKUST-1) as an adsorbent for ethane/ethylene separation. In 2016, the KAUST research team applied NbOFFIVE MOF and discovered the phenomenon of selective separation of olefins by the concept of "Molecular selective exclusion", but in this case, it is difficult to apply it to the actual process due to the low working adsorption capacity and high vacuum desorption problem.

As such, most of the ethane/ethylene adsorption separation technology adsorbs ethylene and proceeds in a manner of purging with nitrogen gas or vacuum desorption in order to recover the adsorbed ethylene again. Therefore, it is necessary to obtain ethylene again from the desorbed ethylene and nitrogen, or a process for recovering ethylene from vacuum is required, which consumes a lot of energy and usually needs to recover a high content of ethylene. There is a disadvantage in that olefins with olefin purity (99.5% or more) for polymer synthesis can be recovered only after recovery including phosphorus adsorption/desorption process.

Therefore, in order to obtain high-purity ethylene, if the purity of ethylene is increased by selectively adsorbing and recovering ethane contained in 50 mol% or less or in a small amount from the ethane/ethylene mixture, the process simplification and adsorbent consumption can be reduced. Accordingly, it is possible to reduce energy consumption. Table 1 below is data comparing the adsorption amounts of ethane selective adsorbent materials reported so far, and the adsorption amount difference is a comparison of the adsorption amount difference between ethane and ethylene adsorbed at 1 bar pressure.

Adsorbent Temp. pressure ethane
adsorption amount
(mmol/g) ethylene
adsorption amount
(mmol/g) adsorption amount
difference -Qst, C ₂ H ₆
(KJ/mol) -Qst, C ₂ H ₄
(KJ/mol) Ref. ZIF-7 298K 1 bar 1.7 ≒0 1.7 < - - One ZIF-8 293K 1 bar 2.5 1.3 1.2 - - 2 ZIF-69 293K 1 bar 2.2 1.8 0.4 26.0 23.0 3 IRMOF-8 293K 1 bar 4.5 3.1 1.4 52.5 49.5 4 MAF-49 316K 1 bar 2.6 1.7 0.9 56.7 45.5 5 MIL-142A 298K 1 bar 3.8 2.9 0.9 25.1 23.8 6 BasoliteA100 (MIL-53-bdc) 303K 1 bar 2.5 1.6 0.9 29.0 27.0 7 MIL-53-FA 308K 1 bar 3.7 3.35 0.35 29.0 27.0 8 Fe ₂ (O ₂ )(dobdc) 298K 1 bar 3.3 2.6 0.75 66.8 37.0 9 PCN-245 298K 1 bar 3.27 2.39 0.88 23.0 20.5 10 PCN-250 298K 1 bar 5.21 4.22 0.99 23.6 21.1 11 MUF-15 293K 1 bar 4.69 4.15 0.54 37.5 33.0 12 Cu(Qc) ₂ 298K 1 bar 1.9 0.8 1.1 29.0 25.4 13 ZJU-30 298K 1 bar 2.12 1.96 0.16 29.7 28.1 14 UTSA-35a 296K 1 bar 2.43 2.16 0.27 29.0 28.9 15 UiO-66-2CF3 318K 1 bar 0.6 0.5 0.1 28.0 5.0 16 Glc-A carbon 298K 1 bar 6.09 5.34 0.75 52.9 36.5 17 C-PDA-3 carbon 298K 1 bar 6.09 5.34 0.75 22.0 21.0 18 A-AC CarbonC-700-3 298K 1 bar 7.2 5.9 1.3 30.8 28.9 19 MGA-750-3 298K 1 bar 7.02 5.68 1.34 28.4 21.8 20 Nibdc (TED) _0.5 273K 1 bar 6.9 5.6 1.3 21.5 18.5 21 NiTMBDC (TED) _0.5 298K 1 bar 5.45 5.02 0.43 39 32 22 ZJU-120a 296K 1 bar 4.91 3.93 0.9 27.6 26.5 23

Materials such as ZIF-7, ZIF-8, and ZIF-69 and MAF-49, which are Zn-based adsorbents known as conventional ethane-selective adsorbents, have lower pore inlet sizes (0.5 nm or less) compared to their pore size (1.16 nm or less). ) is relatively small, so the adsorption amount of ethane is quite low at 2.5 mmol/g. On the other hand, IRMOF-8, Nibdc(TED)0.5, NiTMBDC(TED)0.5, and ZJU-120a adsorbents, which show high ethane adsorption capacity, show 4.5 mmol/g performance, but the difference in ethane/ethylene adsorption capacity is relatively low. There is this. In addition, among carbon-based materials, materials suggested as ethane-selective adsorbents have been studied, and although the difference in adsorption amount between ethane and ethylene is 1 mmol/g or more, high performance is achieved. It is expensive compared to the precursor price, and it is environmentally disadvantageous because decomposition products are generated during the high-temperature carbonization process.

The organic-inorganic hybrid nanoporous body is used in the adsorption separation process in the second step (S200) as described above. The adsorptive separation process may be, for example, a Pressure Swing Adsorption (PSA) process. In the pressure cycle adsorption process, for example, a mixture containing an olefin compound and a paraffin compound is introduced at a high pressure into a chamber including an organic-inorganic hybrid nanoporous body, and the paraffin compound is adsorbed to the organic-inorganic hybrid nanoporous body to a saturated state. make it possible As the paraffin compound is adsorbed, only the olefin compound remains in the mixture. Accordingly, it is possible to produce an olefin compound of high purity from the mixture. With respect to the organic-inorganic hybrid nanoporous body to which the paraffinic compound is adsorbed in the chamber, the adsorbed paraffinic compound can be desorbed by lowering the pressure in the chamber thereafter.

In particular, the process of producing a high-purity olefin compound using the organic-inorganic hybrid nanoporous body may be performed by adjusting the conditions of the adsorption process and the conditions of the desorption process. For example, the pressure of the depressurization process for performing the desorption may vary depending on the pressure conditions of the process for performing the adsorption. In addition, in the decompression process, temperature increase through heating, inert gas purging, etc. may be additionally performed. Through this, it is possible to selectively recover more paraffin and partially adsorbed olefin compounds adsorbed to the adsorbent. Paraffin compounds and/or all? It is possible to increase the recovery rate of the compound.

In the present invention, in order to increase the purity of the produced olefin compound and paraffin compound, the separation process may be repeated several times.

In order to use the organic-inorganic hybrid nanoporous body in the above-described pressure cycle adsorption process, the difference between the equilibrium adsorption amount for olefin and the equilibrium adsorption amount for paraffin under the same adsorption conditions must be large. In the organic-inorganic hybrid nanoporous body according to the present invention, since the equilibrium adsorption amount for paraffin is larger than the equilibrium adsorption amount for olefin under the same adsorption conditions, the paraffin compound can be efficiently separated from the olefin compound by using the pressure cycle adsorption process. have.

The organic-inorganic hybrid nanoporous body may be used to adsorb and separate an olefin compound having 3 or less carbon atoms and a paraffin compound having 3 or less carbon atoms, according to an embodiment. In this case, the organic-inorganic hybrid nanoporous body may adsorb ethane in a mixture of ethane and ethylene, and may adsorb propane in a mixture of propane and propylene. In this case, the difference between the adsorption amount of the organic-inorganic hybrid nanoporous body to the olefin compound having 3 or less carbon atoms and the paraffin compound having 3 or less carbon atoms may be about 0.5 mmol/g or more. As the organic-inorganic hybrid nanoporous body has a difference in adsorption amount as described above, it is possible to effectively separate olefins and paraffins by using an adsorption separation process such as a pressure cycle adsorption process.

The organic-inorganic hybrid nanoporous body may have a specific surface area of about 1000 m ² /g to about 2400 m ² /g. The organic-inorganic hybrid nanoporous body according to the present invention has a high specific surface area as described above. Accordingly, the organic-inorganic hybrid nanoporous body has the advantage of a large adsorption capacity. In addition, in the synthesis of an aluminum-based organic-inorganic hybrid nanoporous body, it can be easily synthesized at a temperature of less than 120 degrees, and the aluminum precursor and organic ligand used as the synthesis precursor are inexpensive and have the advantage of being mass-produced commercially. It is advantageous in terms of price of the adsorbent. In particular, the water-solvent-based adsorbent has advantages in terms of commercial use because it can be manufactured using an eco-friendly synthesis method and a simple reflux reaction system.

In the above, an organic-inorganic hybrid nanoporous body according to an embodiment of the present invention and an olefin/paraffin separation process using the same have been examined. Hereinafter, the advantageous effects of the organic-inorganic hybrid nanoporous body according to the present invention will be examined in detail through Examples and Comparative Examples.

Synthesis of organic-inorganic hybrid nanoporous body

Example 1. Preparation of CAU-3-NDCA

In this example, the synthesis of an Al-based organic-inorganic hybrid nanoporous body having a CAU-3-NDCA structure was performed. To prepare a synthetic solution, 20.485 g of AlCl ₃ *6H ₂ O and 4.586 g of 2,6-Naphthalenedicarboxylic acid (NDCA) were put into a 1L Teflon line-autoclave reactor, and then 441 g of methanol (99.5% purity) was added. and stirred. Thereafter, caustic soda (NaOH) of 2.8 was added to the reaction solution and further stirred. After stirring at room temperature for 20 minutes, the autoclave reactor was sealed and reacted at 130° C. for 6 hours to prepare a CAU-3-NDCA organic-inorganic hybrid nanoporous body. After completion of the reaction, the crystals formed in the reaction solution were first filtered, and then redispersed in methanol solution to remove unreacted residue fractions, followed by stirring for 3 hours to perform a secondary filter. The obtained crystals were dried at 100 degrees for 12 hours to recover CAU-3-NDCA organic-inorganic hybrid crystal powder.

Example 2. Preparation of MIL-53-NDCA

An Al-based organic-inorganic hybrid nanoporous body having a MIL-53-NDCA crystal structure was synthesized. To prepare a synthetic solution, 10.5 g of Al(NO ₃ ) ₃ *9H ₂ O and 5.19 g of 2,6-Naphthalenedicarboxylic acid were dissolved in 565 g of N,N-dimethyleformamide solvent. The solution was put into a Teflon line-ontoclave reactor, and then the reaction was performed at 120 degrees for 24 hours. After completion of the reaction, the crystals formed in the reaction solution were first filtered, and then redispersed in N,N-dimethyleforamide solution, and purification was performed for 3 hours. The crystals recovered through purification were dried at 100 degrees for 12 hours to recover MIL-53-NDCA organic-inorganic hybrid crystal powder.

Example 3. Preparation of MIL-53-BPDC

An Al-based organic-inorganic hybrid nanoporous body having a MIL-53-BPDC crystal structure was synthesized. To prepare a synthetic solution, 10.5 g of Al(NO3)3*9H2O and 5.19 g of 4,4'-Biphenyldicarboxylic acid were dissolved in 565 g of N,N-dimethyleformamide solvent. The solution was put into the Teflon line-ontoclave reactor, and then the reaction was performed at 120 degrees for 24 hours. After completion of the reaction, the crystals formed in the reaction solution were first filtered and then redispersed in N,N-dimethyleforamide solution, and purification was performed for 3 hours. The crystals recovered through purification were dried at 100 degrees for 12 hours to recover MIL-53-BPDC organic-inorganic hybrid crystal powder.

Example 4. Preparation of Al-Pyridinedicarboxylate (Al-PDC)

For the synthesis of an Al-based organic-inorganic hybrid nanoporous body having an Al-Pyridinedicarboxylate crystal structure, 16.663 g of Al ₂ (SO ₄ ) ₃ *18H ₂ O was dissolved in 135 g of distilled water to prepare a metal precursor solution. Then, after dissolving 6.0 g of caustic soda (NaOH) in 135 g of distilled water, 8.356 g of 3,5-Pyridinedicarboxylic acid was further added to prepare a ligand precursor solution. After putting the metal precursor solution in a round flask, the ligand precursor solution was slowly added to prepare a synthesis solution. Thereafter, a round flask was mounted on an oil bath equipped with a reflux cooling device, the temperature was raised to 120°C, and the reaction was completed after maintaining for 15 hours. After cooling the reaction solution, the Al-Pyridinedicarboxylate organic-inorganic hybrid nanoporous crystals generated in the round flask were washed once with distilled water and ethanol, respectively, and dried at 100°C for 12 hours to obtain a crystal powder.

Example 5. Preparation of Al-Furanedicarboxylate (Al-FDC)

The organic-inorganic hybrid nanoporous body Al-Furanedicarboxylate was synthesized as follows. First, put 4.683 g of 2,5-Furandicarboxylic acid, 7.243 g of AlCl ₃ *6H ₂ O, 1.20 g of NaOH and 60 g of distilled water in a 100 mL round-bottom flask and mix at room temperature for 3 hours. It was synthesized by stirring under reflux for 24 hours while heating to 100 °C. Then, the solution was cooled to room temperature, purified using distilled water and ethanol, and centrifuged to recover the product.

Example 6. Preparation of Al-Thiophendicarboxylate (Al-TDC)

The organic-inorganic hybrid nanoporous body Al-Furanedicarboxylate was synthesized as follows. First, 5.013 g of 2,5-Thiophenedicarboxylic acid, 7.243 g of AlCl ₃ *6H ₂ O, 1.20 g of NaOH, and 60 g of distilled water were added to a 100 mL round-bottom flask and mixed with each other at room temperature for 3 hours. After being mounted in a Teflon line-autoclave reactor, it was synthesized by reflux stirring for 18 hours while heating to 120 °C. Then, the solution was cooled to room temperature, purified using distilled water and ethanol, and centrifuged to recover the product.

Example 7. Preparation of Al-Pyrazoledicarboxylate (Al-PDA)

For the synthesis of an Al-based organic-inorganic hybrid nanoporous body having an Al-Pyrazoledicarboxylate crystal structure, 4.83 g of AlCl ₃ *6H ₂ O was dissolved in 167 g of distilled water to prepare a metal precursor solution. Thereafter, 1.21 g of caustic soda (NaOH) was dissolved in 167 g of distilled water, and then 3.48 g of 3,5-1H-pyrazoledicarboxylic acid was further added to prepare a ligand precursor solution. After putting the metal precursor solution in a round flask, the ligand precursor solution was slowly added to prepare a synthesis solution. Thereafter, a round flask was installed in the oil bath, a reflux cooling device was connected, and the temperature was raised to 120 degrees and maintained for 15 hours, and then the reaction was completed. After cooling the reaction solution, the Al-Pyrroledicarboxylate organic-inorganic hybrid nanoporous crystals produced in the round flask were washed once with distilled water and ethanol, respectively, and dried at 100°C for 12 hours to obtain a crystal powder.

comparative example. Manufacture of Al-Isophthalate (Al-IPA)

For the synthesis of an Al-based organic-inorganic hybrid nanoporous body having an Al-isophthalate crystal structure, 11.48 g of Al ₂ (SO ₄ ) ₃ *18H ₂ O was dissolved in 33.7 g of distilled water to prepare a metal precursor solution. Then, after dissolving 3.8 g of caustic soda (NaOH) in 113 g of distilled water, 7.55 g of Isophthalic acid was additionally added. A precursor solution was prepared by further adding 0.96 g of NaAlO 2 to the solution. After putting the metal precursor solution in a round flask, the precursor solution was slowly added to prepare a synthesis solution. Thereafter, after mounting a round flask in the oil bath, a reflux cooling device was connected, the temperature was raised to 120°C, and the reaction was completed by maintaining it for 6 hours. After cooling the reaction solution, the Al-Isopthalate organic-inorganic hybrid nanoporous crystals generated in the round flask were washed once with distilled water and ethanol, respectively, and then dried at 100°C for 12 hours to obtain a crystal powder.

Analysis of structure and physical properties of organic-inorganic hybrid nanoporous body

The compounds of Examples and Comparative Examples synthesized above were evaluated by analyzing their structures and physical properties. The analysis method is as follows.

The crystal structure analysis of the Al-based organic-inorganic hybrid nanoporous body according to Examples and Comparative Examples can be easily performed using an X-ray diffraction pattern. The equipment used in the present invention was measured using an X-ray diffractometer (Rigaku Diffractometer D/MAX IIIB, Ni-filtered Cu Kα-radiation).

In addition, the thermal stability analysis of the sample was measured using a thermogravimetric analyzer (N-1000, Shinko Co., Ltd.) equipment while raising the temperature at a temperature increase rate of 5°C/min under a nitrogen flow of 30 ml/min. .

Nitrogen adsorption isotherm is measured at a liquid nitrogen temperature of -196 degrees using Tristar 3020 (Micromeritics) equipment after pre-treating about 0.15 g of a sample in a high vacuum (~10 ^-6 torr) condition at a temperature of 150 to 200 degrees at 150 degrees for 12 hours. and the surface area of the sample was calculated using the BET (Brunauer-Emmett-Teller) equation.

Scanning electron microscope images were measured using Carl Zeiss, Sigma HD after Pt coating in a high vacuum chamber.

Test Example 1-1. Evaluation of the structure and properties of CAU-3-NDCA

2A to 2D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 1. FIG.

As a result of X-ray diffraction analysis of the sample prepared in Example 1, it was confirmed that a CAU-3-NDCA structure having high crystallinity was prepared as shown in FIG. 2a. The size of the crystal was confirmed to be at the level of 100 nm through the scanning electron microscope image shown in FIG. 2D. In addition, in the thermogravimetric analysis presented in Fig. 2b, a weight decrease was observed in the region of 250-350 °C, which is a decrease in weight due to the decomposition of -OCH3 (methoxy) coordinated to the structure, and then NDCA at a temperature of 500 °C or higher It was confirmed that the structure was collapsed by decomposition of the organic linker. In addition, referring to FIG. 2c , the surface area calculated from the nitrogen adsorption isotherm was 2290 m ² /g, indicating a very high value.

Test Example 1-2. Evaluate the structure and properties of MIL-53-NDCA

3A to 3D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 2.

As a result of X-ray diffraction analysis of the sample prepared in Example 2, it was confirmed that a MIL-53-NDCA structure having high crystallinity was prepared as shown in FIG. 3a . The size of the crystal was confirmed to be at the level of 100 nm through the scanning electron microscope image shown in FIG. 3D. In addition, in the thermogravimetric analysis presented in Fig. 3b, it was confirmed that the structure collapsed at a temperature of 500 degrees or more. In addition, referring to FIG. 3C , the surface area calculated from the nitrogen adsorption isotherm was 1670 m ² /g, indicating a high surface area value.

Test Example 1-3. Evaluate the structure and properties of MIL-53-BPDC

4A to 4C are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 3.

As a result of X-ray diffraction analysis of the sample prepared in Example 3, it was confirmed that a MIL-53-BPDC structure having high crystallinity was prepared as shown in FIG. 4A . In addition, in the thermogravimetric analysis presented in Fig. 4b, it was confirmed that the structure collapsed at a temperature of 500 degrees or more. In addition, referring to FIG. 4c , the surface area calculated from the nitrogen adsorption isotherm was 1780 m ² /g, indicating a high surface area value.

Test Example 1-4. Evaluate the structure and properties of Al-PDC

5A to 5D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 4.

As a result of X-ray diffraction analysis of the Al-PDC prepared in Example 4, it can be confirmed that an Al-PDC having high crystallinity was prepared as shown in FIG. 5a, generated from the scanning electron microscope image of FIG. 5d It was confirmed that the crystals were synthesized with a size of a micrometer level. From the thermogravimetric analysis result of FIG. 5B, it was confirmed that the Al-PDC was stable up to 500 degrees Celsius, and the surface area calculated from the nitrogen adsorption isotherm result of FIG. 5C was 1030 m ² /g.

Test Example 1-5. Evaluate the structure and properties of Al-FDC

6a to 6d are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 5;

As a result of X-ray diffraction analysis of Al-FDC prepared in Example 5, it can be confirmed that Al-FDC having high crystallinity was prepared as shown in FIG. 6a, generated from the scanning electron microscope image of FIG. 6d It was confirmed that the crystals were synthesized with a size of 1 μm. From the thermogravimetric analysis result of FIG. 6b, it could be confirmed that the Al-FDC was stable up to 450 degrees, and the surface area calculated from the nitrogen adsorption isotherm of FIG. 6c was 1260 m ² /g.

Test Example 1-6. Evaluate the structure and properties of Al-TDC

7A to 7D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 6.

As a result of X-ray diffraction analysis of the Al-TDC prepared in Example 6, it can be confirmed that Al-TDC having high crystallinity was prepared as shown in FIG. 7a, generated from the scanning electron microscope image of FIG. 7d It was confirmed that the crystals were synthesized with a size of 100 nm level. From the thermogravimetric analysis result of FIG. 7b , it was confirmed that the Al-TDC thermal stability was stable up to 450°C, and the surface area calculated from the nitrogen adsorption isotherm result of FIG. 7c was 1200 m ² /g.

Test Example 1-6. Evaluate the structure and properties of Al-PDA

8A to 8D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Example 7.

As a result of X-ray diffraction analysis of the Al-PDA prepared in Example 7, it can be confirmed that an Al-PDA having high crystallinity was prepared as shown in FIG. 8a, generated from the scanning electron microscope image of FIG. 8d It was confirmed that the crystals were synthesized with a size of 100-300 nm. From the thermogravimetric analysis result of FIG. 8B, it was confirmed that the Al-PDA was stable up to 450 degrees, and the surface area calculated from the nitrogen adsorption isotherm of FIG. 8C was 1380 m ² /g.

Comparative Test Example 1. Evaluating the structure and physical properties of Al-IPA

9A to 9D are graphs and photographs evaluating the structure and physical properties of the organic-inorganic hybrid nanoporous body according to Comparative Example.

As a result of X-ray diffraction analysis of the Al-IPA prepared in Example 4, it can be confirmed that Al-IPA having high crystallinity was prepared as shown in FIG. 9A, generated from the scanning electron microscope image of FIG. 9D It was confirmed that the obtained crystals were synthesized with a size of 2 μm or more. From the thermogravimetric analysis result of FIG. 9b, it was confirmed that the Al-IPA was stable up to 550 degrees Celsius, and the surface area calculated from the nitrogen adsorption isotherm result of FIG. 9c was 670 m ² /g.

Therefore, as a result of comparing the structure of the organic-inorganic hybrid nanoporous body according to the example and the comparative example, the organic-inorganic hybrid nanoporous body according to the example has a crystal size relatively higher than that of the organic-inorganic hybrid nanoporous body according to the comparative example. Although small, it was confirmed that the specific surface area was rather large. Therefore, it can be seen that the organic-inorganic hybrid nanoporous body according to the embodiment can provide more in the same volume and has an excellent adsorption capacity because the specific surface area is also larger.

Olefin/paraffin separation performance test of organic-inorganic hybrid nanoporous body

Through the above comparative experiment, it was confirmed that the organic-inorganic hybrid nanoporous body according to the example had superior structural characteristics compared to the organic-inorganic hybrid nanoporous body according to the comparative example. Hereinafter, in relation to olefin/paraffin separation, the performance of the organic-inorganic hybrid nanoporous body according to Examples and Comparative Examples is to be confirmed.

The olefin/paraffin separation performance test was performed by confirming the ethane, ethylene, propane, and propylene adsorption performance as follows. The adsorption isotherms of ethane, ethylene, propane, and propylene are about 0.15 g of the organic-inorganic hybrid nanoporous sample according to the Examples and Comparative Examples in a high vacuum (~10 ^-6 torr) condition at a temperature of 150 to 200 degrees 150 degrees 12 After time pre-treatment, it was measured using Micromeritics' Tristar 3020 equipment, and in the case of a high pressure region of 1 bar or higher, it was measured using HIDEN's Intelligent Gravimetric analyzer (IGA) equipment.

Test Example 2-1. Olefin/paraffin separation performance test of CAU-3-NDCA

10A and 10B are graphs of the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 1. FIG.

The adsorption selectivity of the Al-based adsorbent prepared from the above invention was confirmed by measuring the adsorption isotherm of ethane/ethylene or propane/propylene. In the case of the organic-inorganic hybrid nanoporous body having the CAU-3-NDCA structure prepared in Example 1, the ethane/ethylene adsorption amount was measured by changing the adsorption pressure to 0.01-12 bar at the adsorption temperature of 293-313K. In the result of FIG. 10A , the adsorbent had a higher adsorption amount of ethane than that of ethylene, and a difference in adsorption amount of at most 1.5 mmol or more was observed. In addition, in the propane/propylene adsorption results measured in FIG. 10b, it can be seen that more propane is adsorbed in the 0.01-1 bar region at a temperature of 303 K or higher, and more propane is adsorbed in the low pressure region at a temperature of 303 K or less. However, it was observed that the adsorption amount of propylene was increased above a certain pressure.

Test Example 2-2. Olefin/paraffin separation performance test of MIL-53-NDCA

11a and 11b are graphs of the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 2.

In the case of MIL-53-NDCA prepared in Example 2, as shown in FIG. 11a, the adsorption amount of ethane was greater than that of ethylene in all temperature conditions, and a difference of up to 1.5 mmol/g was observed. In the case of the adsorbent, the difference between the adsorbents of ethane and ethylene was increased at a relatively low adsorption temperature (273K). In the propane/propylene adsorption result of FIG. 11b, a difference in the adsorption amount of propane and propylene was observed to be 0.5 mmol/g or less, propane-selective properties were observed in the low pressure region (0.4 bar or less), and in the high pressure region, the adsorption amount of propylene was propane higher was observed. It was confirmed that the adsorbent exhibited higher adsorption amounts of ethane and propane than ethylene and propylene under specific pressure and temperature conditions.

Test Example 2-3. Olefin/paraffin separation performance test of MIL-53-BPDC

12a and 12b are graphs of the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 3.

In the case of MIL-53-BPDC prepared in Example 3, a high ethane adsorption amount was observed at all measured temperatures in the ethane/ethylene adsorption isotherm results shown in FIG. 12a, and the maximum adsorption amount difference was observed to be 1.25 mmol/g. became In the case of the adsorbent, since it is not saturated with ethane or ethylene in the measurement region, there is a possibility that the adsorbent may show a greater difference in adsorption amount in the high-pressure region. In the result of the propane/propylene adsorption isotherm of FIG. 12b, the pressure range in which the adsorption amount of propane is observed to be higher was observed in the range of 0.2-0.8 bar, and the difference in the amount of adsorption was observed at the level of 0.5 mmol/g.

Test Example 2-4. Olefin/paraffin separation performance test of Al-PDC

13 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 4.

In the case of Al-PDC prepared in Example 4 of FIG. 13 , an increase in the adsorption amount of ethane was observed by nitrogen introduced into the benzene ring of the ligand. In addition, an increase in the adsorption amount of ethane was observed in a relatively low pressure region. The difference in adsorption amount between ethane and ethylene was observed as high as 0.8 mmol/g.

Test Example 2-5. Olefin/paraffin separation performance test of Al-FDC

14 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 5;

In the ethane/ethylene adsorption isothermal test result of the Al-FDC adsorbent prepared in Example 5 of FIG. 14, the adsorption amount of ethane was observed to be higher than that of ethylene, and the adsorption amount of ethane at 303K was observed to be as high as 4.0 mmol/g. The difference in the maximum adsorption amounts of ethane and ethylene of the adsorbent was observed to be 0.7 mmol/g.

Test Example 2-6. Olefin/paraffin separation performance test of Al-TDC

15 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 6.

In the case of the Al-TDC adsorbent prepared in Example 6, ethane showed a higher adsorption amount than ethylene at 293-303K, but at 283K temperature, ethane showed a higher adsorption amount in the pressure range of 0.7 bar or less, and at a pressure higher than that The adsorption amount of ethylene was observed to be higher than that of ethane.

Test Example 2-7. Olefin/paraffin separation performance test of Al-PDA

16 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Example 7.

The Al-PDA prepared in Example 7 showed a very good adsorption amount. In addition, at a temperature of 293-303 K, a high adsorption amount of ethane was observed in the pressure range of 0.01-1 bar. At a temperature of 283K, ethane adsorption was observed to be higher than that of ethylene in the region of 0.7 bar or less. The difference in the adsorption amount of the adsorbent was observed to be as high as 0.8 mmol/g.

Comparative Test Example 2. Olefin/paraffin separation performance test of Al-IPA

17 is a graph showing the results of testing the olefin/paraffin separation performance of the organic-inorganic hybrid nanoporous body according to Comparative Example.

17 shows the results of ethane/ethylene adsorption of the Al-IPA adsorbent of the comparative example. In the case of the Al-IPA adsorbent, ethane adsorbed more than ethylene in the temperature range of 283-303K, but the difference in adsorption amount was observed to be 0.3 mmol/g or less. The adsorption amount of ethane at 303K was observed to be about 3 mmol/g.

It can be seen from the results of the difference in adsorption amount for each gas in Examples and Comparative Examples for olefin/paraffin separation that the adsorbent developed in the present invention has paraffin adsorption selectivity under pressure or temperature conditions in a specific region. In particular, in the separation of ethane/ethylene, a larger difference in adsorption amount was observed in the organic-inorganic hybrid nanoporous body according to the embodiment. Specifically, according to the comparative example, the difference in adsorption amount between ethane and ethylene was about 0.3 mmol/g or less, so that the difference in adsorption amount was insufficient to separate ethane/ethylene. According to the implementation, the difference in the adsorption amount of ethane and ethylene was about 0.7 mmol/g to about 1.5 mmol/g, showing a performance difference of about 2 times or more compared to the comparative example.

Therefore, by using the adsorbent, conventional ethane can be effectively separated from the ethane/ethylene mixture.

Test Example 3-1. Breakthrough separation experiment of MIL-53-NDCA adsorbent (50% ethane mixture_high concentration)

MIL-53-NDCA adsorbent was prepared in the form of pellets and a breakthrough test was performed to confirm the separation performance of the ethane/ethylene mixture. After loading 1 g of the adsorbent into the adsorption column, nitrogen gas was flowed at a temperature of 150°C to remove the adsorbed impurity gas and moisture on the surface to activate the adsorbent. Thereafter, after fixing the adsorption column temperature to a temperature of 273 K, ethane/ethylene gas hops with a gas composition of 1:1 ethane/ethylene molar ratio was flowed at a flow rate of 4.4 ml/min under 1 bar conditions to pass through the adsorbent. At this time, the gas discharged through the adsorbent was connected to gas chromatography (GC) to measure the concentration of the exhaust gas in real time. After that, the same breakthrough curve was obtained by repeating the activation process to adjust the adsorption pressure in the range of 3-7 bar.

Test Example 3-2. Breakthrough separation experiment of MIL-53-NDCA adsorbent (10% ethane mixture_low concentration)

In the process of Test Example 3-1, a breakthrough experiment was performed in the same manner except that the molar ratio of the ethane/ethylene mixture was adjusted to 1:9 and the flow rate of the ethane/erylene mixed gas was adjusted to 22 ml/min.

The experimental results of Test Examples 3-1 to 3-2 are shown in FIGS. 18 to 20 . When an ethane/ethylene mixture of 1:1 molar ratio is passed through an adsorbent at a pressure of 1-7 bar in FIG. 18 , it can be confirmed that ethylene is detected through a gas chromatography analyzer and then ethane is detected. This characteristic means that ethylene is detected first because ethane adsorbs more in a 1:1 molar ratio of ethane/ethylene mixture, which means that the adsorbent is an ethane-selective adsorbent. In the case of 1 bar pressure, in 28 minutes, more than 99.5% of ethylene starts to be produced after passing through the adsorbent, meaning that high-purity ethylene can be produced for about 6 minutes until 34 minutes when ethane is detected. In addition, even when the pressure is increased from 1 bar to 3-7 bar, more ethane is adsorbed, and ethane and ethylene can be effectively separated using the adsorbent of MIL-53-NDCA.

The results of FIG. 19 are results obtained by increasing the gas flow rate in an adsorption experiment using an ethane/ethylene mixture under a 1:9 molar ratio condition. Similarly, looking at the concentration curve of the gas discharged through the adsorbent, it is possible to produce high-purity ethylene from the gas mixed with ethane of low concentration from the first discharge of ethylene in all pressure ranges.

From the results of the breakthrough experiments performed in Experimental Examples 3-1 to 3-2, the productivity of high-purity ethylene of 99.5% or more per weight of the adsorbent was calculated and shown in FIG. 20 . In the case of the adsorbent, when the adsorption separation was performed using an ethane/ethylene mixture in a molar ratio of 1:9, high productivity of 20 L/kg per unit weight of the adsorbent was exhibited, and no significant difference was observed in the change in adsorption pressure. This property means that the adsorbent effectively removes ethane over a wide range of pressures. When the ethane/ethylene mixed gas ratio is 5:5, the productivity of ethylene tends to decrease as the pressure increases. This characteristic is because the ability of the adsorbent to selectively remove ethane at high pressure adsorption pressure gradually decreases when ethane is present in a high concentration in the mixture gas composition. However, in the adsorption separation using a 5:5 mixed gas, the high-purity ethylene productivity of the adsorbent is maintained at a level of 17 L/kg even at a pressure of 5 bar or less, so that ethylene can be effectively produced.

Although the above has been described with reference to a preferred embodiment of the present invention, those skilled in the art or those having ordinary skill in the art will not depart from the spirit and scope of the present invention described in the claims to be described later. It will be understood that various modifications and variations of the present invention can be made without departing from the scope of the present invention.

Accordingly, the technical scope of the present invention should not be limited to the contents described in the detailed description of the specification, but should be defined by the claims.

Claims (7)

aluminum ions;
and an organic ligand linked to the aluminum ion,
The organic ligand is 2,6-naphthalenedicarboxylate (2,6-Naphthalenedicarboxylate), 4,4'-biphenyldicarboxylate (4,4'-Biphenyldicarboxylate), 3,5-pyridine dicarboxylate (3, 5-Pyridinedicarboxylate), 2,5-furandicarboxylate (2,5-Furandicarboxylate), 2,5-thiophenedicarboxylate (2,5-Thiophenedicarboxylate), and 3,5-1H-pyrazoledicarboxylate rate (3,5-1H-pyrazoledicarboxylate) comprising at least one selected from the group consisting of,
The aluminum ion and the organic ligand form a crystal structure including pores,
The organic-inorganic hybrid nanoporous body, wherein the polycyclic aromatic compound or the heterocyclic aromatic compound provided in the crystal structure selectively adsorbs a paraffin compound in a mixture of an olefin compound and a paraffin compound. delete According to claim 1,
An organic-inorganic hybrid nanoporous body having a specific surface area of 1,000 m ² /g to 2,400 m ² /g. According to claim 1,
The organic-inorganic hybrid nanoporous body selectively adsorbs a paraffin compound from a mixture of an olefin compound having 3 or less carbon atoms and a paraffin compound having 3 or less carbon atoms,
In the organic-inorganic hybrid nanoporous body, the difference between the adsorption amount of the olefin compound having 3 or less carbon atoms and the paraffin compound adsorption amount having 3 or less carbon atoms is 0.5 mmol/g or more at or below the liquefaction pressure of the olefin compound, depending on the pressure conditions, organic-inorganic hybrid nanopores sifter. A first step of loading a mixture of an olefin compound and a paraffin compound;
a second step of selectively adsorbing a paraffin compound in the mixture loaded in the first step using a complex including an organic-inorganic hybrid nanoporous body; and
A third step of regenerating the organic-inorganic hybrid nanoporous body and separating the paraffin compound and the olefin compound,
The organic-inorganic hybrid nanoporous body is
aluminum ions;
and an organic ligand linked to the aluminum ion,
The organic ligand is 2,6-naphthalenedicarboxylate (2,6-Naphthalenedicarboxylate), 4,4'-biphenyldicarboxylate (4,4'-Biphenyldicarboxylate), 3,5-pyridine dicarboxylate (3, 5-Pyridinedicarboxylate), 2,5-furandicarboxylate (2,5-Furandicarboxylate), 2,5-thiophenedicarboxylate (2,5-Thiophenedicarboxylate), and 3,5-1H-pyrazoledicarboxylate rate (3,5-1H-pyrazoledicarboxylate) comprising at least one selected from the group consisting of,
The aluminum ion and the organic ligand form a crystal structure including pores, the separation method of olefins and paraffins. 6. The method of claim 5,
The complex is a method for separating olefins and paraffins, further comprising a polymer compound and an inorganic compound provided in combination with the organic-inorganic hybrid nanoporous body. 6. The method of claim 5,
In the second step, ethane is selectively adsorbed by the organic-inorganic hybrid nanoporous body in a mixture of ethane and ethylene, or propane is selectively adsorbed by the organic-inorganic hybrid nanoporous body in a mixture of propane and propylene and paraffin separation method.

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