KR20100014144A - Method for separating olefin/paraffin using porous nickel phosphate and food packaging material including porous nickel phosphate - Google Patents

Abstract

PURPOSE: An olefin/paraffin separation method using porous nickel phosphate and food packing materials containing the porous nickel phosphate are provided to recover and separate olefin and paraffin with high purity by using the porous nickel phosphate. CONSTITUTION: An olefin/paraffin separation method includes a step for passing an olefin/paraffin compound through a porous nickel phosphate molecular sieve in which metal is substituted. The nickel phosphate molecular sieve is manufactured from a reactant containing metal of 0.001-1.0 molar ratio and a phosphorus compound of 0.3-3.0 molar ratio. A food wrapping material contains the porous nickel phosphate molecular sieve.

Description

Method for separating olefin / paraffin using porous nickel phosphate and food packaging material including porous nickel phosphate}

The present invention relates to a method for separating olefins and paraffins from an olefin and paraffin gas mixture, and more particularly, to an olefin / paraffin separation method using porous nickel phosphate substituted with various metal ions.

The present invention also relates to a food packaging material containing porous nickel phosphate adsorbing ethylene gas generated during food waste disposal.

Currently, the separation of olefins and paraffins from olefin / paraffin mixtures in the oil and petrochemical industries is mostly by distillation. The boiling point of the olefin and paraffin are very similar, so a lot of energy is consumed in order to separate by distillation and the number of stages of the distillation column is large, so the apparatus cost is high.

Accordingly, in Korean Patent Invention No. 828137, a method for preparing an adsorbent in which silver nitrate (AgNO ₃ ) is supported on a pellet-type substrate selected from aluminosilica gel and silica gel and mixtures thereof has been proposed. In Patent Invention Nos. 6,315,816 and 6,468,329, the adsorbents used in the adsorptive separation process are characterized by a substrate having a large specific surface area (silica gel, etc.) that binds olefins with olefins to selectively adsorb olefins (Ag ⁺ , Cu ^+, etc.). , Alumina, alumino silica gel, mesoporous material, and the like) have been proposed. The metal ion supported is obtained by impregnating a silver nitrate (AgNO ₃ ) or copper chloride (CuCl) solution to the substrate and then drying. In addition, Korean Patent Invention No. 787210 has proposed a method for preparing an adsorbent in which aluminosilicate is loaded with silver nitrate as an adsorbent suitable for olefin / paraffin separation, but among the small pores of the alumino silica gel, the size of the adsorbent is supported. Since silver nitrate was difficult to contact with olefins or the material transfer rate was very slow, it did not act on adsorption. Therefore, expensive silver nitrate was wasted, which did not significantly improve the price competitiveness of the adsorbent.

On the other hand, C ₄ olefins (butene-1, trans-2-butene, cis-2-) from a C ₄ mixed gas containing butene-1, trans-2-butene, cis-2-butene, normal butane, isobutane and the like Butene, etc.) and C4 paraffins (normal butane, isobutane, etc.) have been mainly used in the distillation process. Since the boiling point difference between the C ₄ components is small, a single distillation column with a large number of energy and equipment costs is high. It takes

In the prior art, it is known to use silica gel, alumina, alumino silica gel, mesoporous materials, etc. for olefin / paraffin separation, but there is a need for development of a material capable of separating olefin / paraffin with higher efficiency.

On the other hand, in recent years, a problem that the freshness of food sharply drops due to the ethylene gas generated in a small amount of food waste. In order to overcome this problem, when using PE (polyethylene) packaging material containing a small amount of zeolite, charcoal, etc., there has been a report to improve the freshness of food by adsorbing a small amount of ethylene gas generated from the containing zeolite, charcoal, etc. have. However, PE packaging material containing charcoal has a black color, which decreases the consumer's selectivity when using it as a food packaging material. Especially, when using zeolite or charcoal, there is a limit to the adsorption amount of ethylene. This is required.

In order to solve the above problems, an object of the present invention is to provide an olefin / paraffin separation method that can be separated at a low cost and high efficiency.

In addition, by increasing the adsorption amount of the ethylene gas generated in the food waste process to provide a food packaging material that can maintain the freshness of the food for a long time.

In order to achieve the above object, the present invention provides an olefin / paraffin separation method comprising passing an olefin / paraffin mixture through a metal-substituted porous nickel phosphate molecular sieve.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. First of all, it should be noted that in the drawings, the same components or parts denote the same reference numerals as much as possible. In describing the present invention, detailed descriptions of related well-known functions or configurations are omitted in order not to obscure the subject matter of the present invention.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are intended to aid the understanding of the invention. Accurate or absolute figures are used to assist in the prevention of unfair use by unscrupulous infringers.

The nickel phosphate molecular sieve is a metal-containing nickel phosphate molecular sieve having a nickel phosphate molecular sieve structure composed of nickel, phosphorus, oxygen, and metal components to prepare a multi-metal-containing nickel phosphate molecular sieve containing a high concentration of specific metal ions. have. In particular, nickel phosphate molecular sieves having various concentrations of metal ions capable of selectively adsorbing olefins, for example, Cu ⁺ , Fe ²⁺ , Ag ^+, etc., are prepared to prepare olefins using such nickel phosphate molecular sieves. And paraffin can be separated respectively.

The metal-containing nickel phosphate molecular sieve may be VSB-1 and VSB-5 molecular sieves in which metal ions are substituted, and the VSB-1 and VSB-5 molecular sieves are nickel phosphates including nickel and phosphorus. Is a nanoporous material composed of 24 oxygens (24-membered ring structure) and is known to be synthesized in the presence of nickel, phosphorus, water and suitable organic template materials [C. R. Acad. Sci. Paris, vol. 2, p. 387, 1999; Angew. Chem. Int. Ed. vol. 40, pp. 2831-2834, 2001].

First, the VSB-1 is synthesized by adding a base such as pyridine and TREN (tris (2-aminoethyl) amine) to nickel, phosphorus and fluorine compounds [C. R. Acad. Sci. Paris, vol. 2, p. 387, 1999 are known. VSB-1 containing metals is known to synthesize a reactant composed of metal, nickel, phosphorus, ammonium fluoride and distilled water using microwave [Chem. Mater. vol. 16, p. 5552, 2004.

The VSB-5 is synthesized by adding a base of diamines ranging from 1,2-ethylenediamine to 1,8-octanediamine to nickel and phosphorus compounds. Am. Chem. Soc., Vol. 125, pp. 1309-1312, 2003; Angew. Chem. Int. Ed. vol. 40, pp. 2831-2834, 2001 are known. Recently, synthetic results have been reported even in the absence of organic template material [Chem. Mater. vol. 16, p. 1394, 2004; Korean Patent Invention No. 525208]. VSB-5 containing metal is known to synthesize a reactant composed of metal, nickel, phosphorus, base or salt, and distilled water using microwave [J. Phys. Chem. B vol. 109, 845, 2005; Korean Patent Invention No. 525209]. In addition, Korean Patent Invention No. 680889 describes a method for producing a nickel phosphate molecular sieve in which multiple metals are contained in a skeleton.

As used herein, various metal-substituted nickel phosphate molecular sieves can be prepared by reference to known methods. Preferably, it may be prepared using the manufacturing method disclosed in Korean Patent Invention No. 680889.

The olefin / paraffin separation method of the present invention may be applied to the separation of various olefin / paraffin mixtures, and specifically, may be applied to the separation of C2 to C8 olefins and C1 to C8 paraffin mixtures. In particular, the olefin / paraffin separation method of the present invention can be efficiently applied to the separation of ethane / ethene, propane / propene, butane / butene and the like.

The porous nickel phosphate molecular sieve used in the present invention may be a metal-containing nickel phosphate molecular sieve prepared from a nickel compound, a reactant containing 0.3 to 3.0 molar ratios of phosphorus compound and 0.001 to 1.0 molar ratio of metal with respect to the nickel compound. . The molecular sieve reactant may further contain 0.5 to 10 molar ratio of the fluorine compound relative to the nickel compound.

In addition, it is possible to produce a specific multi-metal-containing nickel phosphate molecular sieve by the above production method. Specifically, the nickel compound used as a raw material has some solubility in a solvent. For example, inorganic nickel compounds such as nickel chloride hydrate and nickel nitrate hydrate, and organic nickel compounds such as nickel oleate and nickel oxalate may be used. And preferably nickel chloride hexahydrate.

As another raw material, phosphorus compounds also have some solubility in solvents. For example, inorganic and organic phosphorus compounds such as phosphoric acid and tri-butyl phosphate may be used. Preferably, phosphoric acid is good.

In the amount of nickel compound and phosphorus compound used as raw materials, it is preferable to maintain the molar ratio of P / Ni at 0.3 to 3.0 molar ratio by using phosphorus compound at 0.3 to 3.0 molar ratio with respect to nickel compound. If the amount is less than 0.3, then nickel is present so that a material having nanopores is obtained. Instead, a material without pores is obtained. If the molar ratio exceeds 3.0, nanoporous material is difficult to obtain or a large amount of base or salt is required. In addition, the material that can be crystallized is also dissolved, a problem that is difficult to obtain a solid.

The metal that can be used in addition to the raw material may be selected from transition metals, typical metals, Group VIII precious metals and lanthanum. More specifically, two or more selected from transition metals such as titanium, vanadium, chromium, manganese, iron, cobalt, zinc, typical metals such as silicon and magnesium, precious metals such as palladium, and lanthanum such as lanthanum and cerium Can be used. More preferably, a transition metal is preferable, and copper, iron, silver, etc. are especially preferable.

The metal is preferably used in a molar ratio of 0.001 to 1.0 with respect to the nickel compound, and when the amount is less than 0.001 molar ratio, it is difficult to expect the role of metal components. When the molar ratio exceeds 1.0 molar ratio, the metals themselves gather together to prevent pores of the molecular sieve. Difficult to have characteristics For example, in the case of Cu-VSB-5, Fe-VSB-5, or Ag-VSB-5, Cu, Fe, or Ag / Ni = 20 to 0.1%, and Cu-VSB-1, Fe-VSB In the case of -1, or Ag-VSB-1, Cu, Fe, or Ag / Ni = 30 to 0.1% may be substituted.

 The metal may be used as a metal compound having some solubility in a solvent, for example, at least two selected from nitrate, chloride, acetate, sulfate, and oxide. These may be used, more preferably nitrates, chlorides and acetates.

The metal source may be used by dissolving it in a solvent or by dissolving it in phosphoric acid, and adding a metal component in a state in which a raw material for preparing a nickel phosphate molecular sieve containing a base or a salt is prepared.

In the nickel phosphate molecular sieve, an organic amine, an inorganic base or an inorganic salt may be used as a pH adjusting material, and the inorganic base is convenient because it is easy to price or post-treatment.

Examples of the organic amines include tertiary amines such as triethylamine, tripropylamine, diisopropylethylamine and triethanolamine, secondary amines such as dibutylamine and dipropylamine, heptylamine, octylamine and nonyl Primary amines such as amines and organic amines having a cyclic structure such as morpholine, cyclohexyl amine, pyridine and the like can be used.

The inorganic base or inorganic salt may include hydroxides or oxides of alkali metals and alkaline earth metals, or ammonia, for example, sodium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, ammonia, ammonia water, and the like.

In the nickel phosphate molecular sieve, as the pH adjusting material, more preferably, an inorganic base which can omit the heat treatment process after manufacture is used, and particularly preferably, ammonia water and sodium hydroxide are used. The inorganic base, inorganic salt or organic amine is used in a molar ratio of 1.0 to 10.0 with respect to the nickel compound.

Meanwhile, in the preparation of the nickel phosphate molecular sieve in which the raw material of the nickel compound and the phosphorus compound is crystallized in the presence of an inorganic base or an inorganic salt, a specific metal is added to the raw material and crystallized, but the ion is more than the ion radius of nickel or phosphorus. By adding a metal with a large radius and a metal with a small ionic radius at the same time, it is possible to increase the concentration of the metal to be substituted or to prepare a multimetal-containing nickel phosphate molecular sieve with increased thermal stability. First, nickel compounds, phosphorus compounds, metals, fluorine compounds, bases or salts and solvents are mixed in a constant molar ratio. The molar ratio is 1.0 Ni: (0.3 to 3.0) P: (0.001 to 1.0) Metal: (0.0 to 10.0) F: (1.0 to 10.0) Base or salt: (10 to 1000) The solvent is mixed in the composition of VSB- 1 adjusts the pH to 2.0-6.0 and VSB-5 adjusts the pH to 6.0-1.0. As the solvent, one or two or more selected from alcohols such as water, ethylene glycol, isopropanol and butanol, hydrocarbons such as benzene and n-hexane, ketones such as acetone and methyl ethyl ketone, carbon tetrachloride and chloroform may be used. Water and butanol are preferable, and water is more preferable. Next, the mixture is heated to high temperature to crystallize. The reaction temperature for crystallization is 50 ~ 300 ℃, preferably 100 ~ 250 ℃, more preferably 150 ~ 200 ℃. If the reaction temperature is less than 50 ℃ reaction is too slow to require a very long time for the synthesis is not practical, if the temperature exceeds 300 ℃ there is a problem that a material without a fine pore containing nickel and phosphorus is obtained. In addition, the reactor used for heating may be used, such as microwave or electric heater. The reaction of the present invention can be continuous or batch, but a small amount of synthesis is suitable for a batch reactor and a large amount of synthesis is suitable for a continuous reactor, when a significant amount of solvent evaporation pressure reactor for preventing the loss of solvent, An autoclave or the like is required. Next, the reactant crystallized under the above reaction conditions is cooled to obtain a nickel phosphate molecular sieve containing multiple metals dried after solid-liquid separation. The cooling temperature is 0 ~ 100 ℃, the method of separating the solid product from the liquid may be carried out using a centrifuge or a reduced pressure filter. The heat treatment temperature is preferably 200 to 500 ° C, more preferably 300 to 450 ° C. If the heat treatment temperature is lower than 200 ℃, the removal of the organic matter is insufficient, the adsorption capacity is low, and if it exceeds 500 ℃, the decomposition of the structure of the produced multi-metal containing nickel phosphate molecular sieve may occur.

When inorganic bases or inorganic salts are used as the pH adjusting agent, the inorganic bases or inorganic salts are not strongly bound to exist in the molecular sieve, and they are easily dissolved in water and are easily removed from the molecular sieve during washing. Pure multi-metal-containing nickel phosphate molecular sieve can be obtained by performing a process such as washing and drying without the heat treatment process performed as a lithography process.

In the olefin / paraffin separation method of the present invention, an olefin / paraffin mixture is passed through a specific metal-substituted nickel phosphate molecular sieve prepared as described above, and the nickel phosphate molecular sieve may be used in the form of powder, pellet, membrane, and the like. . For example, by forming an adsorption layer comprising powder or pellets of a specific metal-substituted nickel phosphate molecular sieve and passing the olefin / paraffin mixture through the adsorption layer, the specific metal ions and olefins substituted in the nickel phosphate molecular sieve The olefin may be selectively adsorbed in the pores of the nickel phosphate molecular sieve by the electrostatic attraction between π-electrons to separate the paraffins, and then the olefins and the paraffins may be separated and recovered, respectively, by desorbing the adsorbed olefins.

In addition, in the separation of the present invention, it is preferable to perform the pretreatment for reducing the metal ions to proceed with the separation. This is because the electrostatic attraction between the reduced metal species and the π-electrons of the olefin can be increased.

In the olefin / paraffin separation method of the present invention, one or more adsorption layers comprising powder or pellets of the specific metal-substituted nickel phosphate molecular sieves may be used.

On the other hand, as the olefin / paraffin separation conditions are separated at 30 ~ 100 ℃, the pressure is transformed to 1 ~ 10bar. The flow rate of olefins / paraffins is controlled at 1 to 5 cc / min, and the catalyst is preferably used at 0.5 to 5 g.

The nickel phosphate nanoporous body can be used as a powder or a molded body. The shape of the molded body is preferably in the form of pellets, beads, honeycomb, mesh or membrane. Appropriate organic or inorganic binders can be used to produce shaped articles such as pellets, beads, honeycombs, meshes, membranes and the like, and the added organic or inorganic binders preferably do not exceed 50% of the weight of the powder. As the inorganic binder, silica, alumina, layered compounds, metal alkoxides, metal halides, and the like may be used. As the organic binder, one or more alcohols and cellulose, polyvinyl alcohol, polyacrylate, and the like are preferable.

In addition, the present invention provides a food packaging material containing porous nickel phosphate, which can maintain the freshness of food for a long time by adsorbing a large amount of ethylene gas generated in the process of food waste.

Preferably, the porous nickel phosphate contained in the food packaging material is the porous nickel phosphate substituted with the metal used in the olefin / paraffin separation method of the present invention.

As described above, by selectively adsorbing and separating olefins by using porous nickel phosphate molecular sieve substituted with various metal ions by the olefin / paraffin separation method of the present invention, olefins and paraffins are separated and recovered with high purity, respectively. There is an effect of improving the efficiency of the / paraffin separation process.

In addition, since the method of the present invention exhibits a high separation effect without expensive cost, the economic efficiency is improved.

In addition, by using the food packaging material containing the porous nickel phosphate of the present invention, it is possible to adsorb a large amount of ethylene gas generated in the process of food waste, there is an effect that can maintain the freshness of the food for a long time.

Through the following examples will be described in more detail.

Preparation Example 1

Preparation of Cu-VSB-5

After dissolving 3.40 g of nickel chloride hexahydrate (NiCl ₂ · 6H ₂ O) and 0.08 g of copper chloride (CuCl ₂ ) in 22.89 g of distilled water, 1.02 g of 85% phosphoric acid was added dropwise to the mixed solution, followed by addition of 2.53 g of ammonia water. The composition of 1.0 Ni: 0.63 P: 0.17 Cu: 3.0 NH ₃ : 100 H ₂ O. 30 g of the reaction product obtained above was encapsulated in a Teflon reactor and sealed, and then crystallized by maintaining at a microwave reactor (CEM, MARS5) at 180 ° C. for 3 minutes, cooling at 25 ° C., and separating a solid and liquid to obtain a Cu-VSB-5 molecular sieve. The BET surface area and composition of the Cu-VSB-5 molecular sieve obtained above are shown in Table 1 below.

Preparation Example 2

Preparation of Fe-VSB-5

3.39 g of nickel chloride hexahydrate (NiCl ₂ · 6H ₂ O) and 0.143 g of iron chloride 4 water (FeCl ₂ · 4H ₂ O) were dissolved in 24.62 g of distilled water, and 1.00 g of 85% phosphoric acid was added dropwise to the mixed solution. 2.52 g of ammonia water was added to make the composition of the reactant 1.0 Ni: 0.63 P: 0.17 Fe: 3.0 NH ₃ : 100 H ₂ O, to obtain a Fe-VSB-5 molecular sieve in the same manner as in Preparation Example 1. The BET surface area and composition of the Fe-VSB-5 molecular sieve obtained above are shown in Table 1 below.

Preparation Example 3

Preparation of Ag-VSB-5

3.40 g of nickel chloride hexahydrate (NiCl ₂ · 6H ₂ O) and 0.086 g of silver chloride (AgCl) were dissolved in distilled water, and then 1.02 g of 85% phosphoric acid was added dropwise to the mixed solution, and 2.53 g of ammonia water was added. Ni: 0.63 P: 0.17 Ag: 3.0 NH ₃ : 100 H ₂ O and then Ag-VSB-5 molecular sieve was obtained in the same manner as in Preparation Example 1. The BET surface area and composition of the Ag-VSB-5 molecular sieve obtained above are shown in Table 1 below.

Preparation Example 4

Preparation of Cu-VSB-1

Prepared similarly to Preparation Example 1, 1.29 g of fluoroammonium was used in place of ammonia water, and the composition of the reactant was 1.0 Ni: 1.0 P: 0.22 Cu: 2.5 NH 4 F: 100 H ₂ O. After crystallization by holding at 190 ° C. for 3 minutes, the mixture was cooled at 25 ° C. and solid-liquid separation to obtain Cu-VSB-1 molecular sieve. The BET surface area and composition of the Cu-VSB-1 molecular sieve obtained above are shown in Table 1 below.

Preparation Example 5

* Preparation of Fe-VSB-1

In the same manner as in Preparation Example 2, 1.27 g of fluoroammonium was used instead of ammonia water, and the composition of the reaction was 1.0 Ni: 1.0 P: 0.22 Fe: 2.5 NH ₄ F: 100 H ₂ O. Crystallization was carried out at 190 ° C. for 3 minutes, followed by cooling at 25 ° C. and solid-liquid separation to obtain Fe-VSB-1 molecular sieve. The BET surface area and the composition of the Fe-VSB-1 molecular sieve obtained above are shown in Table 1 below.

Preparation Example 6

Preparation of Ag-VSB-1

In the same manner as in Preparation Example 3, 1.27 g of fluoroammonium was used in place of ammonia water, and the composition of the reactant was 1.0 Ni: 1.0 P: 0.22 Ag: 2.5 NH 4 F: 100 H ₂ O. After crystallization by holding at 190 ° C. for 3 minutes, the mixture was cooled at 25 ° C. and solid-liquid separation to obtain Cu-VSB-1 molecular sieve. The BET surface area and composition of the Ag-VSB-1 molecular sieve obtained above are shown in Table 1 below.

Preparation Example 7

Preparation of Cu Ion Exchange Catalyst of VSB-5

3 g of synthesized VSB-5 was added to 50 cc of 1 mol of aqueous Cu solution, and stirred at 70 ° C. to ion exchange Cu. This method was carried out three times. After the ion exchange, the mixture was cooled at 25 ° C., and the solid-liquid separation gave an ion-exchanged Cu-VSB-5 molecular sieve. The BET surface area and composition of the Cu-VSB-5 molecular sieve obtained above are shown in Table 1 below.

Comparative Production Example 1

Preparation of VSB-5

3.42 g of nickel chloride / hexahydrate (NiCl ₂ · 6H ₂ O) is dissolved in distilled water, and 1.01 g of 85% phosphoric acid is added dropwise, followed by the addition of 2.55 g of ammonia water. The composition is 1.0Ni: 0.63P: 3.0NH ₃ : 100H ₂ O. , a reaction product having a pH of 7.7 was obtained. 30 g of the reaction product obtained above was placed in a Teflon reactor, sealed, and kept in a microwave reactor at 180 ° C. for 4 hours to crystallize. The mixture was cooled to room temperature (25 ° C.) to be solid-liquid separated to obtain VSB-5 molecular sieve. The BET surface area and composition of the VSB-5 molecular sieve obtained above are shown in Table 1 below.

Comparative Production Example 2

Preparation of VSB-1

3.30 g of nickel chloride / hexahydrate (NiCl ₂ · 6H ₂ O) was dissolved in 23.86 g of distilled water, 2.45 g of ammonia water was added, and 3.29 g of HF was added. Finally, 85% of phosphoric acid was added dropwise. P: 1.5 HF: 3.0 NH ₃ : 100 H ₂ O. 30 g of the reaction product obtained above was placed in a Teflon reactor, sealed, and then crystallized by maintaining at 180 ° C. in a microwave oven (CEM, MARS5) for 1 hour, and then cooled at 25 ° C. and separated into a solid solution to obtain VSB-1 molecular sieve.

TABLE 1

Catalyst Name Composition of Substituted Metal (wt%) ^* BET surface area (m ² / g) ^** Preparation Example 1 Cu-VSB-5 3.1 380 Preparation Example 2 Fe-VSB-5 3.4 410 Preparation Example 3 Ag-VSB-5 3.0 370 Preparation Example 4 Cu-VSB-1 7.8 158 Preparation Example 5 Fe-VSB-1 12.4 172 Preparation Example 6 Ag-VSB-1 6.8 149 Preparation Example 7 Cu-VSB-5 (ion-exchange) 3.3 390 Comparative Production Example 1 VSB-5 0 420 Comparative Production Example 2 VSB-1 0 180

* The composition of the substituted metal is analyzed by EDS (Energy Dispersive Spectroscopy)

** BET surface area (m ² / g) is measured after dehydration in a vacuum at 300 ℃ before measurement.

Example 1

Separation of propane / propene using Cu-VSB-5 of Preparation Example 1

1 is a separation apparatus diagram according to a preferred embodiment of the present invention. Referring to Figure 1, the device for separating the paraffin / olefin of the present invention, the flow rate of each gas was precisely controlled using MFC (Mass Flow Controller), the 6-port valve to determine the direction of the flow rate Pretreatment, reaction gas stabilization, and adsorption reaction were controlled. Above and below the catalyst layer, inert silica was used to reduce the catalyst layer volume. In order to control the pressure during paraffin / olefin separation, BPR (back pressure regulator) was used to adjust the pressure to 1 ~ 10bar. The reaction gas that passed through the adsorption was analyzed using FID of GC (Gas Chromatograph). Analysis was performed using an alumina column of GC for separation analysis of paraffins / olefins.

The experiment was carried out using a specially prepared tube reactor (diameter = 3/8 ", SUS, length 30 cm) to separate olefin / paraffin. The reaction conditions for separating propane / propene were 40 ° C. 1 bar of Cu-VSB-5 powder of Preparation Example 1 was pelletized, and heated for 6 hours at 300 ° C. for pretreatment of the catalyst, followed by copper (Cu). To reduce from monovalent to monovalent, reduced in a 5% hydrogen atmosphere at 200 ° C. After reduction of the catalyst, it was cooled to 40 ° C. and purged with helium (He). The propene / helium ratio was stabilized at a ratio of 90/5/5 and then separated using a catalyst bed, at which time the flow rate was kept constant at 30 cc / min.

Example 2

Separation of Butane / Butene Using Fe-VSB-5 of Preparation Example 2

The experiment was carried out using a tube-type reactor (diameter = 3/8 ", SUS, length 30 cm) specially prepared for separating olefin / paraffin. The reaction conditions for separating butane / butene were 40 ° C., The catalyst for separation was used by pelletizing 1 g of Fe-VSB-5 powder of Preparation Example 2. The catalyst was heated at 300 ° C. for 6 hours for pretreatment of the catalyst and at 200 ° C. to reduce Fe. After the reduction of the catalyst, the catalyst was cooled down to 40 ° C. and purged with He.The catalyst layer was stabilized at a ratio of butane / butene / helium at a ratio of 90/5/5 with a pretreated catalyst. At this time, the flow rate was kept constant at 30 cc / min, and the adsorption leap experiment showed that the Fe-VSB-5 homo-substituted Fe-VSB-5 showed twice as high butene separation efficiency as VSB-5.

Example 3

Separation of Ethane / Ethene Using Ag-VSB-5 of Preparation Example 3

The experiment was carried out using a tube-type reactor (diameter = 3/8 ", SUS, length 30 cm) specially prepared for separating olefin / paraffin. The reaction conditions for separating ethane / ethene were 40 ° C., The catalyst for separation was used by pelletizing 1 g of Ag-VSB-5 powder of Preparation Example 3. Heat treatment at 300 ° C. for 6 hours for pretreatment of the catalyst was performed to reduce silver (Ag). It was reduced in a 5% hydrogen atmosphere at 200 ° C. After reduction of the catalyst, it was cooled to 40 ° C. and purged with helium (He) .The ratio of ethane / ethene / helium with the pretreated catalyst was 90 / After stabilization at a ratio of 5/5, the adsorbent layer was separated and the flow rate was kept constant at 30 cc / min As a result of the above adsorption jump test, silver (Ag) was homo-substituted Ag-VSB-5 was VSB-5. It showed 2 times higher separation efficiency of ethene.

Example 4

Separation of propane / propene using Cu-VSB-1 of Preparation Example 4

As in Example 1, 1g of Cu-VSB-1 of Preparation Example 1 was used instead of Cu-VSB-5 as a catalyst for the separation.

Example 5

Separation of Butane / Butene Using Fe-VSB-1 of Preparation Example 5

As in Example 2, 1g of Cu-VSB-1 of Preparation Example 5 was used instead of Fe-VSB-5 as a catalyst for the separation.

Example 6

Separation of Ethane / Ethene Using Ag-VSB-1 of Preparation Example 6

As in Example 3, 1g of Ag-VSB-1 of Preparation Example 6 was used instead of Ag-VSB-5 as a catalyst for the separation.

Example 7

Separation of propane / propene using ion exchanged Cu-VSB-5 of Preparation Example 7

Experiments were carried out using a tube-type reactor specially prepared for separating olefins / paraffins. Reaction conditions for separating propane / propene were carried out at 40 ° C., 1 bar, and 1 g of the ion-exchanged Cu-VSB-5 of Preparation Example 7 was used as a catalyst for separation. Heat treatment was performed at 300 ° C. for 6 hours for pretreatment of the catalyst, and reduction was performed at 200 ° C. under 5% hydrogen atmosphere to reduce Cu. After the reduction of the catalyst was cooled to 40 ℃ and purged with helium (He). After the pretreatment was completed, the propane / propene / helium ratio was stabilized at a ratio of 90/5/5, and then separated using a catalyst layer. At this time, the flow rate was kept constant at 30 cc / min. As a result of the adsorption leap experiment, Cu showed homopropane separation effect of 3 times higher than that of VSB-5.

Example 8

Adsorption of Ethylene with VSB-5

Adsorption data of small gas molecules in the pressure range of 5 to 760 Torr was obtained using standard volumetric techniques. Prior to the gas adsorption experiment, 1.0 g of VSB-5 obtained in Comparative Preparation Example 1 was maintained at room temperature under vacuum (<10 to 5 Torr), and then heated to a temperature of 250 ° C. to activate slowly (1 K / min). Highly pure gas was used for the adsorption measurement. Adsorption and desorption experiments of ethylene were conducted while reducing the pressure after adsorption at 760 Torr. It was confirmed that the amount of ethylene adsorbed to VSB-5 at 780 torr (2.1 mmol / g) was higher than the ethylene adsorption amount (2.0 mmol / g) of the existing commercial zeolite zeolite X. Through this, it could be confirmed that the PE packaging material used in the food packaging material can be used as a mixed material.

Example 9

Adsorption of Ethylene with Cu-VSB-5

Adsorption data of small gas molecules in the pressure range of 5 to 760 Torr was obtained using standard volumetric techniques. Prior to the gas adsorption experiment, 1.0 g of Cu-VSB-5 obtained in Comparative Preparation Example 1 was maintained at room temperature under vacuum (<10 to 5 Torr), and then heated to a temperature of 250 ° C. to activate slowly (1 K / min). Highly pure gas was used for the adsorption measurement. Adsorption and desorption experiments of ethylene were conducted while reducing the pressure after adsorption at 760 Torr. It was confirmed that the amount of ethylene adsorbed to Cu-VSB-5 at 780 torr (2.3 mmol / g) was higher than the ethylene adsorption amount (2.0 mmol / g) of the existing commercial zeolite zeolite X. Through this, it could be confirmed that the PE packaging material used in the food packaging material can be used as a mixed material.

Comparative Example 1

Same as Example 1, VSB-5 of Comparative Preparation Example 1 was used instead of Cu-VSB-5 as a catalyst for the separation.

Comparative Example 2

Same as Example 1, VSB-1 of Comparative Preparation Example 2 was used instead of Cu-VSB-1 as a catalyst for the separation.

2 is a resolution graph showing the adsorption fraction over time of propane / propene using a porous molecular sieve according to a preferred embodiment of the present invention. According to the adsorption breakingthrough curve graph with time in FIG. 5-ion exchange) was found to have a resolution of 2-3 times higher than VSB-5 of Comparative Example 1. This confirms that Cu (I) in the Cu-VSB-5 structure selectively adsorbs propene as compared to propane.

The present invention described above is not limited to the above-described embodiment and the accompanying drawings, and various substitutions, modifications, and changes are possible within the scope without departing from the technical spirit of the present invention. It will be evident to those who have knowledge of.

1 is a separator according to a preferred embodiment of the present invention.

Figure 2 is a resolution graph showing the adsorption fraction over time of propane / propene using a porous molecular sieve according to an embodiment of the present invention.

Claims (9)

An olefin / paraffin separation method comprising passing an olefin / paraffin mixture through a metal substituted porous nickel phosphate molecular sieve. The method of claim 1, The nickel phosphate molecular sieve is 0.3 to 3.0 molar ratio of the phosphorus compound relative to the nickel compound; Process for the separation of olefins / paraffins prepared from reactants containing 0.001 to 1.0 molar ratio of metal. The method of claim 2, The nickel phosphate molecular sieve is VSB-1 or VSB-5 olefin / paraffin separation method. The method of claim 2, The reactant is an olefin / paraffin separation method further comprises a fluorine compound in a 0.5 to 10 molar ratio with respect to the nickel compound. The method of claim 1, The metal is olefin / paraffin separation method of at least one selected from the group consisting of iron (Fe), copper (Cu) and silver (Ag). The method of claim 1, The nickel phosphate molecular sieve is used in the form of a powder layer, pellet or membrane olefin / paraffin separation method. Food packaging containing porous nickel phosphate molecular sieve. The method of claim 7, wherein The nickel phosphate molecular sieve is VSB-1 or VSB-5. Food packaging material containing the porous nickel phosphate molecular sieve substituted with the metal of any one of Claims 1-6.

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