KR101969200B1 - Method for preparating hydrogen enriched gas and acetylene enriched gas and ethylene enriched gas and gas welding, and apparatus therefor - Google Patents

Abstract

The present invention relates to a process for producing ethylene and acetylene by using an adsorbent capable of adsorbing ethylene and acetylene from a first mixed gas containing a plasma discharge gas, methane, hydrogen, ethylene and acetylene formed by a plasma- A first step of preparing a reduced or eliminated plasma discharge gas, a methane and a hydrogen-containing second mixed gas; A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And a third step of recycling the third mixed gas to the plasma-catalyzed reaction. The present invention also relates to a method and apparatus for producing a hydrogen-enriched gas, an acetylene-enriched gas, an ethylene-enriched gas, and a welding gas. INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method and an apparatus for efficiently separating a gas at a low cost by using a methane-containing gas.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for producing hydrogen-rich gas, acetylene-enriched gas, ethylene-enriched gas, and gas for welding using methane-containing mixed gas,

More particularly, the present invention relates to a method for producing hydrogen-rich gas, acetylene-enriched gas, and ethylene-enriched gas, And an apparatus therefor.

Usually, oil and natural gas are used as energy sources. Oil is getting depleted and this situation is expected to continue, but natural gas is an inexpensive energy source that is richly buried all over the world compared to oil reserves. Such natural gas has a problem in that it is difficult to transport, transport and store gas due to its large distance between the production site and the consumer site.

Natural gas is mainly composed of methane, which is used as a raw material for the production of hydrocarbons over C2, a petrochemical fuel. On the other hand, since methane is a stable compound, it requires a high energy to be converted into a C2 or higher compound by using methane, and it has been restricted to various uses due to high dissociation energy of methane C-H bond. Therefore, various studies have been conducted with respect to the activation of the C-H bond of methane. In recent years, research using plasma has been carried out, and the activation of methane using plasma can easily decompose C-H bonds due to high energy of plasma and can shorten the reaction time. On the other hand, since the methane is converted using glow discharge in a vacuum atmosphere, there is a problem that the investment cost and the operating cost of the process are high.

Methods for converting methane to a C2 or higher compound include an indirect conversion method through a reforming reaction and a direct conversion method in which each product is directly converted. The indirect conversion method is a method of converting a natural gas into a synthetic gas and then converting it into a petroleum raw material in various routes using the synthetic gas. On the other hand, the indirect conversion method is disadvantageous in that a large amount of energy is consumed to manufacture syngas and the initial investment cost is high. The direct conversion method is a method that does not go through the synthesis gas, but the oxidation reaction of methane, partial oxidation of methane (POM), and non-oxidative coupling of methane . On the other hand, such reactions have the problem that it is difficult to optimize the activation of the methane conversion to the commercial level and to selectively produce the products.

As the separation technique of gas mixture, there are pressure swing absorption, water scrubbing, methanol scrubbing, polyethylene glycol scrubbing, and membrane separation. Among them, since the adsorption method is an operation in an abnormal state, It is difficult to predict and design various operating variables in the process step, and a pre-treatment process is required to remove moisture depending on the adsorbent. Further, since the absorption method is saturated with water in the purified gas, there is a problem that a post-treatment step for removing moisture is separately required. On the other hand, the membrane separation method using a separation membrane has been developed for several decades as a process for coping with a conventional separation process. Particularly, the membrane separation method is advantageous in that the energy consumption is small and the space required for installation of the apparatus is simple and the scale-up is easy when the mixed gas is separated. In recent years, the membrane separation method has been widely used in the fields of a nitrogen generating device, a hydrogen generating device, a membrane dehumidifier, an inert gas filling device for a ship or an aircraft, a refining of natural gas or biogas, and a fuel cell.

As an example of a hydrogen / methane / argon separation technique using a separation membrane, Korean Patent Laid-Open No. 10-2011-0065038 discloses a method of separating hydrogen using a palladium-copper-nickel alloy separation membrane. Korean Patent Laid-Open No. 10-2009-0110897 discloses a method of separating hydrogen from a hydrogen-containing gas containing at least 1% of at least one of water, carbon monoxide, carbon dioxide, methane and nitrogen using a hydrogen separation membrane and a hydrogen refining apparatus A method is disclosed. The method of purifying hydrogen using the palladium-based separation membrane material has a high initial investment cost and needs to be refined at a high temperature (> 500 ° C.), so energy consumption is high and it is difficult to operate the separation apparatus energy-efficiently.

Acetylene has been used for a variety of purposes and industrially, including as a fuel gas in gas welding / cutting applications, in atomic absorption spectroscopy applications, and as a raw material gas for chemical synthesis and microelectronics production. On the other hand, acetylene is highly unstable due to its high chemical reactivity, and in the case of pure acetylene, an explosive reaction occurs spontaneously when the pressure exceeds about 2 bar. Therefore, since acetylene can not be packed at 1.3 bar or more in actual sites, it can be stored only in a small amount of units, which is a problem in commercialization.

In general, acetylene is not easy to separate, and often contains impurities such as methane, ethane, propane, carbon monoxide and other miscellaneous organic species rather than pure acetylene alone. In addition, as a result of unstable properties and extreme reactivity, acetylene can not be stored as a homogeneous gaseous phase in pressurized gas supply vessels conventionally used for the storage, transport and delivery of a wide variety of other industrial gases. Therefore, research is underway to replace acetylene used as a welding gas with LPG gas, but LPG gas has a lower heat value than acetylene.

It is an object of the present invention to provide a method for producing a hydrogen-enriched gas, an acetylene-enriched gas, an ethylene-enriched gas and a welding gas using a methane-containing mixed gas.

Another object of the present invention is to efficiently separate a methane-containing mixed gas to provide a high-purity hydrogen-enriched gas and an acetylene-enriched gas, an ethylene-enriched gas, and a gas for welding.

It is still another object of the present invention to provide an apparatus for producing a hydrogen-enriched gas and an acetylene-enriched gas, an ethylene-enriched gas, and a welding gas using a methane-containing mixed gas.

Another object of the present invention is to provide a welding gas containing argon in an amount of 20 vol% or less while being easy to store and store.

According to one aspect of the present invention, embodiments of the present invention are directed to a method of producing a hydrogen enriched gas, the method comprising the steps of generating a plasma discharge gas, methane, hydrogen, ethylene, and an acetylene- A first step of preparing a plasma discharge gas in which ethylene and acetylene are reduced or removed, a second mixed gas containing methane and hydrogen, using an adsorbent capable of adsorbing ethylene and acetylene from one mixed gas; A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And a third step of recycling the third mixed gas to the plasma-catalyzed reaction.

Further, the step of storing the ethylene and acetylene-enriched gas separated through the adsorbent by the gas for welding may be further included.

Further, the ethylene and acetylene concentrated gas separated through the adsorbent may further include a step of separating and storing high purity acetylene in which ethylene is reduced or removed using an adsorbent capable of selectively adsorbing acetylene.

Further, the step of converting the ethylene and acetylene-enriched gas separated through the adsorbent into an ethylene-enriched gas by an acetylene conversion reaction may be further included. The method of producing the hydrogen enriched gas may further include storing the hydrogen enriched gas. The hydrogen-enriched gas may be supplied to the acetylene conversion reaction and reacted with the ethylene and acetylene enriched gas.

Embodiments in accordance with another aspect of the present invention are directed to a method of producing an acetylene enriched gas comprising the steps of forming a plasma discharge gas, methane, hydrogen, an ethylene and an acetylene-containing material formed by a plasma- A first step of preparing a plasma discharge gas in which ethylene and acetylene are reduced or removed, a second mixed gas containing methane and hydrogen, using an adsorbent capable of adsorbing ethylene and acetylene from one mixed gas; A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And a third step of recycling the third mixed gas to the plasma-catalyzed reaction, wherein the first step further comprises an acetylene conversion reaction, wherein the ethylene and acetylene enriched gas separated through the adsorbent is passed through the acetylene conversion Can be converted into ethylene-enriched gas by reaction. The ethylene and acetylene enriched gas separated through the adsorbent may be stored as a gas for welding. Further, the ethylene and acetylene concentrated gas separated through the adsorbent may further include a step of separating and storing high purity acetylene in which ethylene is reduced or removed using an adsorbent capable of selectively adsorbing acetylene.

Embodiments in accordance with yet another aspect of the present invention may include a hydrogen-enriched gas and an acetylene-enriched gas production apparatus comprising a plasma-catalyzed reactor into which a methane-containing gas is introduced and under which a plasma reaction is performed; A plasma discharge gas in which ethylene and acetylene are reduced or removed, a second mixed gas containing methane and hydrogen is passed from a first mixed gas containing plasma discharge gas, methane, hydrogen, ethylene, and acetylene formed in the plasma-catalytic reactor, And an adsorbent capable of adsorbing acetylene; A gas separation membrane for separating the second mixed gas into a plasma discharge gas and a third mixed gas containing methane rich gas and a hydrogen rich gas; And an acetylene conversion reactor for converting an ethylene and an acetylene mixed gas adsorbed by the adsorbent into an ethylene concentrated gas; And a step of storing the mixed gas of ethylene and acetylene adsorbed by the adsorbent with a gas for welding, and the ethylene and acetylene concentrated gas separated through the adsorbent is adsorbed by using an adsorbent capable of selectively adsorbing acetylene, And separating and storing the reduced or eliminated high purity acetylene. The third mixed gas may be recycled to the plasma-catalyzed reactor.

As described above, according to the present invention, it is possible to provide a method of producing a hydrogen-enriched gas, an acetylene-enriched gas, an ethylene-enriched gas and a welding gas using a methane-containing mixed gas, Acetylene-enriched gas, ethylene-enriched gas, and welding gas depending on the content of the hydrogen-rich gas, the ethylene-enriched gas, and the welding gas.

Further, according to the present invention, a methane-containing mixed gas can be efficiently separated to provide a high-purity hydrogen-rich gas, an acetylene-enriched gas, an ethylene-enriched gas, and a welding gas.

Further, according to the present invention, it is possible to provide an apparatus for producing a hydrogen-enriched gas, an acetylene-enriched gas, an ethylene enriched gas, and a welding gas using a methane-containing mixed gas. The apparatus can directly utilize the hydrogen-enriched gas produced in the reaction, and the by-products remaining after the reaction can be recycled, thereby reducing the process cost.

In addition, according to the present invention, it is possible to provide a welding gas containing argon in an amount of 20 vol% or less while being easily stored and stored.

1 is a schematic diagram of a method for producing a hydrogen-enriched gas, an acetylene-enriched gas, an ethylene-enriched gas, and a welding gas according to an embodiment of the present invention.
2 is a view showing a plasma-catalyzed reaction apparatus according to a preferred embodiment of the present invention.
3 is a view of the rotary arc plasma reactor of FIG.
4 is a schematic view of an apparatus having an adsorbent capable of adsorbing ethylene and acetylene according to an embodiment of the present invention.
FIG. 5 is a schematic view of a PVSA (pressure-vacuum circulation adsorption) apparatus capable of separating a C2 mixture gas and hydrogen, methane, and argon gas using a first mixed gas according to an embodiment of the present invention.
6 is an embodiment of an apparatus composed of a separation membrane module for separating into a third mixed gas and a hydrogen-enriched gas according to an embodiment of the present invention.
FIG. 7 is a view showing the gas separation membrane module shown in FIG.
8 is a graph showing the adsorption fractions of acetylene / ethylene / methane / hydrogen / argon (gas produced from 10% methane gas) as a function of time using MIL-100 (Cr) adsorbent according to this embodiment.
9 is a graph showing the adsorption fractions of acetylene / ethylene / propane / propylene / methane / hydrogen / argon (gas produced from a 20% methane gas) as a function of time using an MIL-100 (Cr) adsorbent according to an embodiment of the present invention Lt; / RTI >
10 is a graph showing the adsorption fraction of acetylene / ethylene / methane / hydrogen / argon (gas produced from methane 10% reaction gas) with time using an MIL-100 (Fe) adsorbent according to an embodiment of the present invention to be.
11 is a graph showing the adsorption fraction of acetylene / ethylene / methane / hydrogen / argon (gas produced from a 20% methane gas) as a function of time using a MIL-100 (Fe) adsorbent according to an embodiment of the present invention to be.
FIG. 12 is a graph showing the analysis of the separation performance while controlling the stage-cut (stage-cut) under hydrogen, methane, and argon compositions according to the present embodiment.
FIG. 13 is a graph illustrating the separation performance of the stage-cut according to an embodiment of the present invention while controlling the stage-cut under the assumption that acetylene impurities are present.
FIG. 14 shows the permeability of the PSf membrane to the mixed gas containing acetylene at a pressure of 1 bar over a long period of time.
FIG. 15 shows the selectivity when the incoming gas (incoming gas composition: hydrogen (39.67%), argon (54.79%), methane (5.54%)) is separated using a zeolite separation membrane.

The details of other embodiments are included in the detailed description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention and the manner of achieving them will become apparent with reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the exemplary embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, Like parts are denoted by the same reference numerals throughout.

Hereinafter, the present invention will be described with reference to the accompanying drawings.

FIG. 1 is a schematic view of a method for manufacturing a hydrogen-rich gas, an acetylene-enriched gas, an ethylene-enriched gas, and a welding gas according to an embodiment of the present invention. FIG. 3 is a view showing the rotary arc plasma reactor of FIG. 1; FIG.

Referring to FIG. 1, a method for producing a hydrogen-enriched gas according to an embodiment of the present invention includes the steps of: preparing a first mixture containing plasma discharge gas, methane, hydrogen, ethylene, and acetylene, formed by plasma- A first step of preparing a plasma discharge gas in which ethylene and acetylene are reduced or removed, a second mixed gas containing methane and hydrogen, using an adsorbent capable of adsorbing ethylene and acetylene from the gas; A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And a third step of recycling the third mixed gas to the plasma-catalyzed reaction. The plasma-catalyzed reaction may be performed in the plasma-catalyzed reaction apparatus shown in FIG. 2 and FIG. Also, in the method according to an embodiment of the present invention, the plasma-catalyzed reaction may be performed by a non-thermal plasma treatment under a catalyst and may include a C-H bond cleavage reaction.

A typical process for pyrolyzing methane (or natural gas) using plasma is the Huels process. The Hughes process is a pyrolysis process using a DC (direct current) arc. When an arc is generated by injecting a discharge gas, methane is injected into the high temperature region formed by the arc and pyrolyzed, Liquid propane or the like is used for rapid cooling to complete the reaction.

In this embodiment, the plasma-catalyzed reaction may be modified and used. In this embodiment, a low-temperature plasma having a relatively higher electron temperature than the temperature of the gas is preferable, and a dielectric barrier discharge barrier discharge (DBD), pulse corona discharge, spark discharge, and the like. Here, dielectric barrier discharge is widely used in industry because it can discharge at atmospheric pressure and room temperature, operate in a very large non-equilibrium condition at atmospheric pressure, can discharge a high output power, and does not require a complex pulse power supply.

The dissociative activation energy for decomposing the strong CH bonds of methane (CH ₄ ) in the methane-containing gas introduced into the plasma-catalytic reaction can be converted into various radicals by the plasma provided by the discharge plasma. gas may be used as the inert gas. Non-limiting examples of the inert gas include nitrogen, argon, helium, neon, krypton, or mixtures thereof.

When the argon gas is used as the carrier gas in the process of performing the CH bond decomposition reaction in the presence of the catalyst after the low temperature plasma treatment of the methane-containing gas, the CH bond of methane is more decomposed than the case of using another inert gas as the carrier gas It has been confirmed that more methane can be converted, and therefore, it is preferable to use argon gas as an inert gas.

The methane-containing gas may be introduced alone into the plasma-catalyzed reaction, or may be introduced with the carrier gas or with the addition of hydrogen, water (steam), hydrocarbons, or mixtures thereof. Preferably, the hydrocarbon introduced with the methane-containing gas may be a C ₂ to C ₆ hydrocarbon, for example, ethane, ethylene or propane, or propylene . When hydrogen or hydrocarbons are added to the methane-containing CAS, a large number of CC-bonded compounds may be added to increase the amount of olefins or aromatic hydrocarbons in the product. Since the aromatic hydrocarbons are relatively expensive compounds, they are also economically advantageous.

The content of methane contained in the methane-containing gas may be 5 vol% to 50 vol%, preferably 10 vol% to 30 vol%, more preferably 15 vol% 25 vol%.

When the content of methane contained in the methane-containing gas is less than 10 vol%, the content of methane as an object of the plasma-catalyzed reaction is low to lower the reaction efficiency. When the content of methane exceeds 30 vol%, the plasma- A large number of hydrocarbons of more than C2 out of the first mixed gas to be produced at the time of the subsequent separation may be produced, which may reduce the efficiency of the subsequent separation process. In the method for producing hydrogen-enriched gas according to an embodiment of the present invention, in order to efficiently produce a hydrogen-enriched gas using the methane-containing gas to be charged, the methane content in the methane-containing gas is preferably 10 vol% to 30 vol% . In the third step, the third mixed gas may be mixed with the methane-containing gas and introduced into the plasma-catalyzed reaction. When the content of methane contained in the methane-containing gas is 15 vol% to 25 vol% , It is not necessary to adjust the concentration separately when the third mixed gas is mixed with the methane-containing gas, so that the process efficiency can be improved.

In the present invention, the type of the catalyst is not limited as long as it can lower the activation energy upon decomposition of the C-H bond under the plasma state. In the present invention, the complex system of the plasma and the catalyst can work together to improve the efficiency of the reaction and improve the selectivity of the product.

Non-limiting examples of catalysts usable in the present invention include noble metals, transition metals and typical metals as active materials. In particular, the active material is Pt, Ru, Ni, Co, V, Fe, Cu, Ti, Nb, Mo, W, Ta, Pd, ZrO _2, CoO, Co ₃ as the active material or carrier comprises a Cu or Zn Transition metal oxides such as O ₄ , MnO, NiO, CuO, ZnO, TiO ₂ , V ₂ O ₅ , Ta ₂ O ₅ , ZnO, Cr ₂ O ₃ , FeO, Fe ₂ O ₃ and Fe ₃ O ₄ , may include CaO, BaO, Al ₂ O _3, Ga ₂ O _3, SnO, SnO _2, typical elements such as oxides of SiO ₂ or the like. The catalyst or carrier that can be used may include metal complex oxides such as SrTiO ₃ , BaTiO ₃ , (LaSr) ₂ TiO _4, and the like. Examples of the porous catalyst and carrier include zeolite, mesoporous material, activated carbon, layered double hydroxides (LDH), and the like. Particularly, catalyst materials include zeolites, acid catalysts including ionic liquids, MgO, LDH, and ionic liquid-containing base catalysts, and redox catalysts such as Fe ₃ O ₄ and V ₂ O ₅ . The active material and the carrier may be appropriately selected depending on the kind of reaction such as oxidation-quantization reaction, partial oxidation reaction or non-oxidation reaction.

In one embodiment of the present invention, the catalyst may be in the form of spheres, pellets, monoliths, honeycombs, fibers, porous solid foams, . The catalyst having the above-described shape may be filled in the plasma reactor to form a packed-bed reactor. In addition, the catalyst may be coated on the inner wall of the reactor where the plasma-catalyzed reaction is performed to form a catalyst layer.

The plasma-catalyzed reaction may be performed in the rotary arc plasma reactor of FIG. The rotary arc plasma reactor is composed of a high-voltage electrode and a ground electrode, and generates an arc in a three-dimensional shape as compared with a gliding arc. The reactor of this embodiment is characterized in that heat generated by gradually decreasing the inner diameter in a downward direction in an arc generating region can be concentrated. A discharge gas is injected into the reactor to generate a rotating arc, and a methane-containing gas is injected into the high temperature region generated by the rotating arc to pyrolyze. The generated gas passes through the reaction space, is heat-transferred to the wall surface, is cooled, and completes the reaction.

The reactor shown in FIG. 3 can be set to an apparatus in which the plasma-catalyzed reaction as shown in FIG. 2 is performed. The device may be a power supply, a plasma reactor, a mass flow controller (MFC), a gas chromatograph (GC), and an oscilloscope. The power measurement apparatus can measure power using a 1000: 1 high voltage probe and a current probe, and can be calculated by the following equation (1).

(식 1)

(Equation 1)

The gas supplied into the reactor in the apparatus may be supplied through a gas supply unit (MFC), and the gas supply unit may be calibrated through a flow compensator before use. The components of the gas are TCD (Thermal Conductivity Detector-H ₂ , O ₂ , N ₂ , CO, CO ₂ ) and FID (Flame Ionization Detector-CH ₄ , C ₂ H ₄ , C ₂ H ₂ , C ₂ H ₆ , C ₃ H ₆ , C ₃ H ₈ , nC ₄ H ₁₀ , and iC ₄ H ₁₀ ). For example, the purity of the gas supplied into the reactor may be 99.999% of Ar, 99.9% of N _2, 99.95% of CH _{4, and} 99.9% of H ₂ . Conversion of methane, selectivity of hydrogen, hydrocarbons, and specific energy requirement can be calculated by the following equations (2) to (5).

(식 2)

(Equation 2)

(식 3)

(Equation 3)

(식 4)

(Equation 4)

(식 5)

(Equation 5)

In a method according to an embodiment of the present invention, the methane-containing gas may be produced as a first mixed gas through a plasma-catalyzed reaction, wherein the first mixed gas comprises a plasma discharge gas, methane, hydrogen, ethylene and acetylene . The first mixed gas may be prepared from a plasma discharge gas in which ethylene and acetylene are reduced or removed, a second mixed gas containing methane and hydrogen, using an adsorbent capable of adsorbing ethylene and acetylene. In another embodiment of the present invention, the step of separating the ethylene and acetylene mixture gas adsorbed by the adsorbent may further include the step of separately storing the ethylene and acetylene mixture gas. Alternatively, the ethylene and acetylene mixture gas may selectively adsorb acetylene And can be separated into ethylene-rich gas and acetylene-rich gas, respectively, through an acetylene adsorbent.

Such as ethylene and acetylene, C2 hydrocarbons are monomers for producing various polymers and are used as important chemical raw materials. In an embodiment of the present invention, hydrogen, ethylene and / or < RTI ID = 0.0 > Acetylene and ethylene can be selectively separated and stored, and the acetylene and ethylene can be concentrated and stored as welding gas. In the case of the conventional catalyst and pyrolysis process, since the composition of the feed used is completely different from the product of the plasma process including argon in the process for separating the mixed gas, It has been difficult to efficiently separate the first mixed gas obtained from the gas through the plasma-reaction. Due to the high explosibility of acetylene, an adsorbent having a low pressure (< 2 bar) and a high acetylene capacity at room temperature is required, but no adsorbent having such properties has been a problem. In addition, acetylene used as a welding gas has a risk of explosion at low pressure, which is difficult to store, and it is problematic because it requires a multi-stage expensive process for producing pure acetylene.

The sorbent according to this embodiment can efficiently adsorb ethylene and acetylene at low pressure and room temperature and can cope with the cryogenic fractional distillation traditionally used in the separation of C2 hydrocarbon mixtures to improve energy efficiency. According to the present embodiment, an acetylene-enriched gas which can be used as a welding gas can be easily produced, and an acetylene-enriched gas can be produced using the adsorbent under the condition that pressurization is not required. Gas for welding can be used. The welding gas produced according to this embodiment can contain argon in an amount of 20 vol% or less, preferably 10 vol% or less of impurities such as argon and hydrogen, .

The adsorbent may comprise porous hybrid organometallic skeletons (MOFs) and may comprise, for example, Cr (III) metal or Fe (III) metal.

The porous hybrid organometallic skeleton has Coordinatively Unsaturated Sites (CUS) and is characterized in that the porosity is much higher than that of zeolite. The porous hybrid organometallic skeleton may be an organic / inorganic hybrid material of 1-, 2- or 3-dimensional structure for metal ions or ion clusters to be mixed with organic molecules, and the metal may be Cr (III) metal or Fe III) metal. The material can be accommodated through voids in the structure of the porous hybrid organometallic skeleton. The adsorbent according to this embodiment may be a porous hybrid organic metal skeleton having a space capable of efficiently accommodating ethylene and acetylene.

The adsorbent may be pretreated prior to separating the first mixed gas. The porous hybrid organometallic skeleton may have a coordination unsaturated site, which may be formed in the skeleton or may be formed in a metal ion or an organometallic compound existing in the surface or pores of the organometallic skeleton have. The coordination unsaturated site means a ligand coordinated to the metal ion of the organometal skeleton, typically a coordination site of a metal from which water or an organic solvent has been removed, as a position at which another ligand can form a coordination bond again . It may be preferable to proceed with a pretreatment step of removing water or solvent components bound to the coordination unsaturated sites in order to secure a coordination unsaturated site of the organometallic skeleton.

Preferably, the organometallic skeleton may have a coordination unsaturation site at a density of 0.2 mmol / g to 10 mmol / g. If the density of the coordination sites of organometallic skeletons is less than 0.2 mmol / g, the adsorption capacity of ethylene and acetylene is low even though the adsorption selectivity to ethylene and acetylene is low, thereby reducing the efficiency of the separation process for ethylene and acetylene containing gas. On the other hand, when it exceeds 10 mmol / g, it is difficult to form an organic metal skeleton in a structure, and it is difficult to attain experimentally.

The organometallic skeleton having the unsaturated metal coordination site may be formed of a metal such as trivalent chromium ion, iron ion, cobalt ion, tungsten ion, molybdenum ion, ruthenium ion, niobium ion, manganese ion, nickel ion, , Titanium ions or zirconium ions. More preferably, the organometallic skeleton having the unsaturated metal coordination site may include at least one of trivalent chromium ion, iron ion, cobalt ion, tungsten ion or molybdenum ion as a metal, and ethylene and acetylene It can be utilized as a metal component having a specific adsorption power for.

The organometallic skeleton containing the metal ion may be prepared by using an organic ligand constituting a general organometal skeleton without any limitation. For example, 1,4-benzenedicarboxylic acid (BDCA), isophthalic acid, 1,3,5-benzenetricarboxylic acid (1,3,5-benzenetricarboxylic acid; BTCA), 2,5-dihydroxyterephthalic acid (2,5-dihydroxy-1,4-benzene dicarboxylic acid), 2-aminoterephthalic acid (2-nitroterephthalic acid) (2-nitroterephthalic acid), 2-methylterephthalic acid, 2-haloterephthalic acid, azobenzene tetracarboxylic acid, 1,3,5-tricarboxyphenylbenzene (1, 5-tri (4-carboxyphenyl) benzene), 2,6-naphthalene dicarboxylic acid (NDCA), benzene- 1,3,5-tribenzoic acid (BTB), fumaric acid, glutaric acid, 2,5-furanedicarboxylic acid (FDCA), 1,4- 1,4-pyridinedicarboxylic acid, 2-methylimidazole, 2-methylimidazole, alkyl-substituted imidazole, aromatic ring-substituted imidazole, 2,5-pyrazinedicarboxylic acid, 1, 4-benzene dipyrazole, 3,5-dimethyl-pyrazolate-4-carboxylate, 4- (3,5- Dimethyl-1H-pyrazol-4-yl) benzoate, 1,4- (4-bispyrazolyl) benzene (1,4 - (4-bispyrazolyl) benzene), or derivatives thereof. Benzene dicarboxylic acid, 1,3,5-benzene tricarboxylic acid, 2,5-dihydroxyterephthalic acid, 2,6-naphthalene dicarboxylic acid, azobenzene tetracarboxylic acid, or These derivatives may be used, but are not limited thereto.

4 is a schematic representation of an apparatus comprising an adsorbent capable of adsorbing ethylene and acetylene according to an embodiment of the present invention.

Referring to FIG. 4, the adsorbent may be a catalyst bed in a tube type reactor. In addition, the inside of the reactor can be filled with silica sand, which is not reactive, to reduce the volume, and the surface of the adsorbent can be treated with an inert gas. The adsorbent may be pretreated prior to use to adsorb ethylene and acetylene in the first mixed gas. For example, the pretreatment may be performed at a temperature in the range of 150 ° C to 250 ° C, and may be cooled to the adsorption separation temperature after the pretreatment. Also, after the temperature of the adsorbent is maintained at the operating temperature for a certain time (approximately 5 minutes to 10 minutes), the first mixed gas may be injected into the reactor to start the adsorption separation reaction.

At this time, an inert gas such as helium can be used as the pretreatment gas, and the pretreatment gas and the first mixed gas as the reaction gas can determine whether the adsorbent passes through a 6-port valve. During pretreatment, the reaction gas flows to the GC side to analyze the concentration of the reaction gas without passing through the adsorbent. When the adsorption starts, the 6-port valve is operated in the opposite direction so that the pretreatment gas does not pass through the adsorbent, The reaction gas passes through the adsorbent and is directed to the GC side to measure the concentration of the gas after the reaction, and the gas concentration after the reaction is analyzed using this. The pressure can be controlled using a back pressure regulator to operate the reactor pressure above 1 bar.

Preferably, the organometallic skeleton having ethylene and acetylene selective adsorption capacity of the present invention may be pretreated at 130 to 300. [ More preferably 150 to 300, but it is not limited to the above-mentioned pretreatment conditions as long as it exhibits higher adsorption capacity for ethylene and acetylene compared with methane, oxygen, argon and the like. When the pretreatment temperature is lower than 130, the specific adsorption capacity exhibiting a remarkably high adsorption amount with respect to a specific gas is not shown as compared with other gases, and the specific adsorption capacity showing a similar adsorption amount with respect to all the gases may be lost. The unreacted residues blocked the pore openings of the organometallic skeleton so that the gas to be adsorbed could not pass through the porous organometallic skeleton and could not make sufficient contact. The pretreatment temperature is only an example, and can be adjusted when the conditions for removing the solvent and the treatment time are different.

The pretreatment of the adsorbent may be carried out by any method as long as it can remove water or solvent components without causing deformation of the organic metal skeleton. For example, the adsorbent may be heated to a temperature of 100 ° C or higher under reduced pressure, But it is not limited thereto. Or a method of removing a solvent known in the art, such as vacuum treatment, solvent exchange, ultrasonic treatment and the like. For example, in the present embodiment, the pretreatment is carried out under the conditions of 1 bar under an inert gas such as helium, 150 ° C for 12 hours, 1 bar under an inert gas, 250 ° C for 6 hours, or 1 bar under an inert gas at 100 ° C for 6 hours . Also, as described above, the above process can be performed by using a known method for removing a solvent such as a vacuum treatment, a solvent exchange, an ultrasonic treatment, etc. without limitation.

FIG. 5 is a schematic view of a PVSA (pressure-vacuum circulation adsorption) apparatus capable of separating a C2 mixture gas and hydrogen, methane, and argon gas using a first mixed gas according to an embodiment of the present invention.

Referring to FIG. 5, in the first step, the first mixed gas may be separated by pressure-vacuum swing adsorption (PVSA) separation using an adsorbent. The PVSA separation method is a method of separating and purifying a gas using a principle that a specific gas in a gas mixture is selectively adsorbed to an adsorbent at a high pressure and then the adsorbed gas is desorbed when the pressure is lowered. More particularly, to pressurization at atmospheric pressure or higher to adsorb a desired amount of the desired gas to at least one adsorption column or adsorption bed filled with an adsorbent that selectively adsorbs a desired gas, (Blowdown) for desorbing the desorbed gas, and purge for purifying the desorbed gas are successively and repeatedly carried out to selectively separate the adsorbed gas and the adsorbed gas with high purity. have. In the case of reduced pressure, a vacuum pump is used to desorb the adsorbed gas at 1 atm or less. This method is called Vacuum Swing Adsorption (VSA) separation method. The working capacity of the gas recovered from the adsorbent in the above method is defined as the adsorption amount at a predetermined adsorption temperature and pressure condition and the difference between the adsorption amount remaining in the adsorbent at the desorption temperature and pressure condition.

FIG. 6 is an embodiment of an apparatus composed of a separation membrane module for separating into a third mixed gas and a hydrogen-enriched gas according to an embodiment of the present invention, and FIG. 7 is a view illustrating the gas separation membrane module shown in FIG.

6 and 7 are separated system devices comprising one or more separation membrane modules and can be separated into a third mixed gas and a hydrogen-enriched gas, wherein the gas separation membrane, which may be included in the gas separation membrane module, Flat module, Spiral wound, etc. can be used. The gas separation membrane may be composed of a polymer membrane, an inorganic membrane, a zeolite membrane, a carbon membrane, an organic skeleton membrane, and a mixed membrane formed by mixing a polymer membrane and an inorganic material. Preferably, the membrane comprises polysulfone, May be at least one of PSf, polyimide (PI), polyetherimide (PEI), polyethersulfone (PES), and polydimethylsiloxane (PDMS).

Referring to FIGS. 6 and 7, the third mixed gas is retentate side by side along the direction in which the second mixed gas is fed, and the hydrogen rich gas is mixed with the second mixed gas May be discharged perpendicularly to the direction in which it is introduced. The gas separation membrane may be in the form of a porous hollow fiber, and a plurality of the gas separation membranes may be arranged parallel or parallel to each other as shown in FIG. 6 in the direction in which the second mixed gas flows, A separation membrane for a recovery process for re-entering the separation membrane can be further constructed.

The gas separator module may include a tube-shaped tube having an inlet for introducing the second mixed gas and a first outlet facing the inlet, the tube being provided to connect the inlet and the first outlet. The gas-separating membrane may be provided in a plurality of side-by-side directions from the inlet to the first outlet. In addition, the gas separation membrane module may further include a second outlet provided between the inlet and the first outlet, the second outlet being perpendicular to a direction from the inlet to the first outlet. The second mixed gas may be introduced into the inlet and separated into a third mixed gas and a hydrogen enriched gas through the gas separation membrane and the third mixed gas is exhausted through the first outlet, Lt; / RTI >

The second mixed gas may be separated into a third mixed gas by reducing or eliminating ethylene and acetylene by the adsorbent, and the third mixed gas may include a plasma discharge gas, methane, and hydrogen. Wherein ethylene and acetylene contained in the second mixture gas are hydrocarbon-based materials having a larger size than the third mixture gas, and when the ethylene and acetylene pass through the separation membrane, the gas selectivity of the inlet gases In particular, in the case of a polymer material, the selectivity of the separator can be significantly lowered by swelling the polymer membrane.

Meanwhile, in the method for producing hydrogen-enriched gas according to an embodiment of the present invention, ethylene or acetylene, which may degrade the performance of the gas separation membrane, is reduced or removed through the first step, The second mixed gas may be separated into a third mixed gas and a hydrogen-enriched gas by using a gas separation membrane. Therefore, the method according to the embodiment of the present invention can improve the efficiency of the process because the hydrogen enriched gas can be efficiently produced and deterioration of selectivity caused by the presence of ethylene and acetylene in the gas separation membrane can be prevented. Also, the method of producing the hydrogen-enriched gas may include a third step of recycling the third mixed gas to the plasma-catalyzed reaction.

The third mixed gas may be recycled to the first step and may be mixed with the methane-containing gas or each methane-containing gas to be introduced into the plasma-catalyzed reaction. By re-introducing the third mixed gas into the plasma-catalyzed reaction, the plasma discharge gas and the methane-enriched gas contained in the third mixed gas can be reused to improve the reaction efficiency. In addition, since the temperature of the third mixed gas is already raised during the reaction, heat can be transferred to the methane-containing gas introduced during the plasma-catalytic reaction, thereby improving energy efficiency.

According to another embodiment of the present invention, an apparatus for producing a hydrogen-enriched gas and an acetylene-enriched gas can be provided. A hydrogen-rich gas and an acetylene-enriched gas producing apparatus includes a plasma-catalytic reactor in which a methane-containing gas is introduced and a plasma reaction is performed under a catalyst; A plasma discharge gas in which ethylene and acetylene are reduced or removed, a second mixed gas containing methane and hydrogen is passed from a first mixed gas containing plasma discharge gas, methane, hydrogen, ethylene, and acetylene formed in the plasma-catalytic reactor, And an adsorbent capable of adsorbing acetylene; A gas separation membrane for separating the second mixed gas into a plasma discharge gas and a third mixed gas containing methane rich gas and a hydrogen rich gas; And an acetylene adsorbent capable of selectively adsorbing acetylene in the mixed gas of ethylene and acetylene adsorbed by the adsorbent, and acetylene adsorbed through the adsorbent. The acetylene adsorbent may separate acetylene and ethylene, and may contain a metal organic framework having an unsaturated metal site. The metal organic skeleton of the acetylene adsorbent may be represented by the following formulas (1) to (5).

 [Chemical Formula 1]

M ₃ X (H ₂ O) ₂ O [C ₆ Z _{4 -y} Z ' _y (CO ₂ ) ₂ ] ₃

Wherein X is Cl, Br, I, F or OH; Z or Z 'may be the same or different from each other, each independently represent H, NH _2, Br, I, NO ₂ or OH; 0? Y? 4; M is Fe, Cr, Mn, Al, and V.

(2)

M ₃ O (H ₂ O) ₂ X [C ₆ Z _{3 -y} Z ' _y (CO ₂ ) ₃ ] ₂

Wherein X is Cl, Br, I, F or OH; Z or Z 'may be the same or different from each other, each independently represent H, NH _2, Br, I, NO ₂ or OH; 0? Y? 3; M is Fe, Cr, Mn, Al, and V.

(3)

M ₃ O (H ₂ O) ₂ X _{1 - y} (OH) _y [C ₆ H ₃ (CO ₂ ) ₃ ] ₂

Here, 0? Y? 1; X is Cl, Br, I or F; M is Fe, Cr, Mn, Al, and V.

[Chemical Formula 4]

M ₃ X _{1 - y} (OH) _y (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃

Wherein X is Cl, Br, I, or F; 0? Y? 1; M is Fe, Cr, Mn, Al, and V.

[Chemical Formula 5]

M _a O _b X _c L _d

Here, M is Fe, Cr, Al, V, Mn; X is ^{H -, F -, Cl -} , Br -, NO 3 -, BF 4 -, PF 6 -, I -, SO4 2-, HCO 3 - , and R _n COO ^- (R _n is C ₁ -C ₆ Alkyl group); an anionic ligand selected from the group consisting of an alkyl group); L represents a carboxyl group (-COOH), a carboxylic acid anion group (-COO-), an amine group (-NH ₂ ) and an imino group (-NH), a nitro group (-NO ₂ ), a hydroxy group (-X) and a sulfonic acid group (-SO ₃ H); a is a number from 1 to 12, b is a number from 0 to 6, c is a number from 0 to 12, and d is a number from 1 to 12.

The hydrogen-enriched gas and the gas for manufacturing a gas may be introduced into the plasma-catalytic reactor using the methane-containing gas as a reactant to generate a first mixed gas. The plasma-catalytic reactor can decompose strong C-H bonds of methane using an inert gas as a carrier gas, and can be performed at a relatively low temperature (for example, several hundred K to 1000 K) by using a catalyst together. The first mixed gas may be passed through an adsorbent to separate a second mixed gas, and the adsorbent may be separated by adsorbing a mixed gas containing ethylene and acetylene. The mixed gas containing ethylene and acetylene can be manufactured and stored for energy-efficient welding. The second mixed gas may be separated into a third mixed gas and a hydrogen enriched gas through a gas separation membrane. The hydrogen-enriched gas may be stored in a reservoir for storing the hydrogen-enriched gas.

Hereinafter, examples and comparative examples of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the scope of the present invention is not limited by the following examples.

Production Example 1: Preparation of MIL-100 (Cr)

After adding 0.52 g of Cr metal and 1.41 g of 1,3,5-benzenetricarboxylic acid (BTCA) to a 100 mL Teflon reactor, 48 g of water and 4 mL of HF was added so that the final molar ratio of the reactants was Cr: BTCA: H ₂ O: HF = 1: 0.67: 289: 2. The reaction product was placed in a Teflon vessel, stirred at room temperature for 30 minutes, mounted in an autoclave reactor, and subjected to a crystallization reaction at 220 ° C for 2 days in an electric heating oven. The product cooled to room temperature was washed with boiling water, purified with ethanol at 60 캜, and dried at 100 캜 to obtain porous organic-inorganic hybrid material MIL-100 (Cr). The determined XRD pattern of the final product was consistent with the values disclosed in the literature (Angew. Chem. Int. Ed., 2004, 43: 6296).

Production Example 2: Preparation of MIL-100 (Fe)

67 mmol of iron (III) nitrate, Fe ((NO ₃ ) ₃ 6H ₂ O) and 1,3,5-benzenetricarboxylic acid (BTCA) 44 were added to a Teflon reactor. mmol, and then distilled water was added thereto so that the final molar ratio of the reaction product became Fe: BTCA: H ₂ O = 1: 0.66: 278. The reaction product was stirred at 500 rpm for 20 minutes at room temperature to obtain a homogeneous reaction product. The reactor containing the reactants was maintained at 160 ° C for 12 hours to effect crystallization. The reaction was cooled to room temperature, washed with distilled water and then dried to obtain a porous organic-inorganic hybrid material MIL-100 (Fe).

Example 1: Production of acetylene using a plasma reactor

For the production of acetylene, the plasma-catalyzed reaction apparatus shown in Figs. 2 and 3 was used.

The plasma-catalyzed reaction apparatus includes a power supply, a plasma reactor, a mass flow controller (MFC), a gas chromatograph (GC), and an oscilloscope . The Tektronix TDS 5054B uses a 1000: 1 high-voltage probe and a current probe (Tektronix Tektronix TDS 5054B) with an AC (alternating current) power supply (Max current 60A) TCP 303 current probe & TCPA 300 amplifier). The supplied gas was supplied via MFC (Brooks) and the MFC was calibrated using a flow compensator (Defender530, BIOS international) before use. The components of the gas are TCD (Thermal Conductivity Detector-H ₂ , O ₂ , N ₂ , CO, CO ₂ ) and FID (Flame Ionization Detector-Methane, acetylene, ethylene, C ₂ H ₆ , using the _{C 3 H 6, C 3 H} 8, nC 4 H 1 0, iC 4 H 10) was analyzed for reactants and products.

Each gas flow rate was precisely controlled using MFC. The methane-containing gas introduced into the plasma-catalyzed reaction apparatus was controlled by controlling the content of methane contained in the methane-containing gas to 10 to 30%. The gas generated after the reaction was analyzed by FID and mass spectrometer of GC (Gas Chromatograph).

The composition of the gas produced after the plasma-catalyzed reaction using the methane-containing gas containing 10% and 20% methane, respectively, is shown in Table 1. The contents of acetylene, hydrogen, and hydrocarbons were varied depending on the content of methane contained in the methane-containing gas introduced into the plasma-catalyzed reaction apparatus, and the content of acetylene formed after the plasma-catalyzed reaction was increased as the content of methane was increased . (25 ° C) using an adsorbent (MIL-100Cr) using a product gas made of 10% and 20% methane for the separation of the generated gas of Table 1 (plasma- ) And 10 bar, which are shown in Table 2 (third mixed gas after passing MIL-100Cr adsorbent).

CH ₄ containing gas, 10 vol% CH ₄ CH ₄ containing gas, 20 vol% CH ₄ H ₂ 18.8 37.048 CH ₄ 3.85 5.18 C ₂ H ₂ 2.25 5.946 C ₂ H ₄ 0.2 0.657 C ₂ H ₆ 0 0.017 C ₃ H ₆ 0 0.006 C ₃ H ₈ 0 0 C ₄ H ₁₀ 0 0.004 Ar 74.9 51.169

CH ₄ containing gas, 10% CH ₄ CH ₄ containing gas, 20% CH ₄ H ₂ 19.27 39.67 CH ₄ 3.95 5.55 Ar 79.78 54.79

Recycle ratio
Ar: H ₂ = 2: 1 Recycle ratio
Ar: H ₂ = 3: 1 H ₂ purity (%) 99 95 99 95 H ₂ Recovery (%) 86.9 88.6 91.2 88.8

Referring to Tables 1 and 2, it was confirmed that the produced gas after the plasma-catalyzed reaction using the methane-containing gas completely removed the C2 to C4 hydrocarbon gas in the process of passing the adsorbent.

Table 3 shows gas composition (H ₂ : 39.67%, CH ₄ : 5.55%, Ar: 54.79%) after the hydrogen separation process using the membrane system (Polysulfone, Polyimide and Zeolite) module system shown in FIG. The recycle ratio in Table 3 means the purity and recovery rate of H2 depending on the ratio of Ar: H ₂ when recirculating the gas in Table 2 to the plasma reactor. As shown in Table 3, when the separation membrane system constructed in FIG. 6 is used, purification and recovery of hydrogen of high purity are possible when 1: 2 (H ₂ : Ar) is circulated to the plasma-catalytic reactor.

Example 2: Separation of ethylene / acetylene from a reaction gas (acetylene produced from 10% methane) using MIL-100 (Cr)

As shown in Example 1, the separation apparatus shown in Fig. 4 was used to separate ethylene / acetylene from the gas (methane / hydrogen / argon / ethylene / acetylene) produced in the plasma-catalyzed reaction apparatus. The flow rate of each gas was precisely controlled using a mass flow controller (MFC), and the pretreatment, reaction gas stabilization, and adsorption reaction were controlled using a 6-port valve to determine the flow direction. Unreacted silica was used to reduce the volume of the adsorbent layer above and below the adsorbent layer. The reaction gas passed through the adsorbent was analyzed by FID and mass spectrometer of GC (Gas Chromatograph). The separation of paraffins / olefins was analyzed using an alumina column of GC.

Separation was carried out using a tube type reactor (diameter = 1/4 inch, length 30 cm) (see Fig. 4) prepared for separating acetylene / ethylene / hydrogen / methane / argon. The reaction conditions for separating ethylene / acetylene from the reaction gas were 30 ° C and 1 to 5 bar. As a catalyst for separation, 0.6 g of MIL-100 (Cr) powder of Production Example 1 was pelletized. At this time, 2 g of MIL-100 (Cr) powder was compressed by using a compressor (compression pressure within 0.1 ~ 5 ton), and then a pellet type adsorbent of a certain size was prepared by using a metal body (within a size of 50 to 500 μm). For pretreatment of adsorbents, they were heated at 100 ~ 250 ℃ for 6 hours, cooled to 30 ℃ and then purged with helium. The pretreated adsorbent was separated by a fixed bed reactor for breakthrough after stabilization at a ratio of the gas produced after the plasma reaction shown in Table 1 (produced gas composed of 10% methane) . At this time, the flow rate was kept constant at 15 cc / min. The results of the breakthrough separation experiments show that the separation performance of ethylene in Cr-containing MIL-100 is about 2 to 30 times higher than that of methane / hydrogen / argon and 10 to 80 times higher than that of acetylene . As the reaction pressure increased, the separation efficiency of ethylene / acetylene increased, which is shown in FIG.

8 is a graph showing the adsorption fractions of acetylene / ethylene / methane / hydrogen / argon (gas produced from 10% methane gas) as a function of time using MIL-100 (Cr) adsorbent according to this embodiment.

Example 3: Separation of ethylene / acetylene from a reaction gas (acetylene produced from 20% methane) using MIL-100 (Cr) (including propane and propylene)

As described in Example 1, a gas produced in a plasma-catalyzed reaction apparatus was passed through a tube made of acetylene in order to separate the gas containing propane / propylene from (methane / hydrogen / argon / acetylene / ethylene / propylene / The reaction was carried out in a tube type reactor (diameter = 1/4 inch, length 30 cm) (see FIG. 4). The reaction conditions for separating hydrocarbons having two or more carbon atoms in the reaction gas were 30 ° C, 1 The adsorbent for separation was prepared by pelletizing 0.6 g of MIL-100 (Cr) powder of Preparation 1. The catalyst was heat-treated for 6 hours at 100 to 250 ° C for pretreatment. After pretreatment, The reaction gas (product gas using 20% methane) was stabilized with a pre-treated adsorbent and then separated using an adsorption layer. The separation efficiency of ethylene in MIL-100 containing Cr was 5 ~ 20 times higher than that of methane / hydrogen / argon and the separation efficiency of acetylene was 10 ~ 50 Propane / propylene with a trace amount of 10-100 times higher than that of methane / hydrogen / argon, and it is possible to separate ethylene / acetylene from ethylene / acetylene, which is shown in FIG. 9 .

9 is a graph showing the adsorption fractions of acetylene / ethylene / propane / propylene / methane / hydrogen / argon (gas produced from a 20% methane gas) as a function of time using an MIL-100 (Cr) adsorbent according to an embodiment of the present invention Lt; / RTI >

Example 4: Separation of ethylene / acetylene from a reaction gas (gas produced from 10% methane) using MIL-100 (Fe) of Production Example 2

Except that 1.2 g of MIL-100 (Fe) of Preparation Example 2 was used instead of MIL-100 (Cr) as an adsorbent for the separation. The results of the fracture separation experiment showed that the separation efficiency of ethylene from MIL-100 containing Fe was 2 ~ 10 times higher than that of acetylene and 5-20 times higher than that of acetylene, which is shown in FIG.

10 is a graph showing the adsorption fraction of acetylene / ethylene / methane / hydrogen / argon (gas produced from methane 10% reaction gas) with time using an MIL-100 (Fe) adsorbent according to an embodiment of the present invention to be.

Example 5: Separation of ethylene / acetylene from propane (acetylene produced from 20% methane) using MIL-100 (Fe) of Production Example 2 (propane, propylene included)

Except that 1.2 g of MIL-100 (Cr) of Production Example 2 was used instead of MIL-100 (Fe) as an adsorbent for the separation. The results of the fracture separation experiments show that the separation performance of ethylene in Fe-containing MIL-100 is 2 to 10 times higher than that of methane / hydrogen / argon and 5 to 20 times higher than that of acetylene. In addition, propane / propylene has a separation efficiency of 10 to 100 times higher than that of methane / hydrogen / argon, and can be separated from ethylene / acetylene, which is shown in FIG.

11 is a graph showing the adsorption fraction of acetylene / ethylene / methane / hydrogen / argon (gas produced from a 20% methane gas) as a function of time using a MIL-100 (Fe) adsorbent according to an embodiment of the present invention to be.

Example 6: Separation of ethylene / acetylene (propane, propylene) from a reaction gas (acetylene produced from 10% and 20% methane) using MIL-100 (Fe) A PVSA tube prepared for separating acetylene from a gas containing propane / propylene (methane / hydrogen / argon / acetylene / ethylene / propylene / propane) with a gas produced in a plasma- The experiment was conducted using a tube type reactor (diameter = 3/8 inch, length 60 cm, two reactors) (see FIG. 5). The reaction conditions for separating hydrocarbons having two or more carbon atoms in the reaction gas were 25 and 50 ° C at 0.01 to 10 bar, and 23 g of MIL-100 (Fe) powder of Preparation Example 2 was used as the adsorbent for separation. The catalyst was heat-treated at 150 ° C. for 12 hours for pretreatment After pre-treatment, the mixture was cooled to 25 ° C and 50 ° C, and then purged with helium. After stabilizing the reaction gas (product gas using 10% and 20% methane) with the adsorbent finished with the pretreatment, The separation efficiency of the reaction gas (the product gas using 10% and 20% methane) is shown in Table 3. [Table 3] < EMI ID = 17.1 > Concentration of acetylene after adsorption tower showed 55 ~ 88% concentration depending on acetylene purity of reaction gas (product gas using 10% and 20% methane) and concentration of 58 ~ 92% when ethylene was included The concentration of acetylene in the reaction gas (2.3-6.0%) was 15 ~ 25 times higher than that of acetylene. The recovery rate of acetylene and ethylene in the reaction gas was 84 ~ 92% and the concentration of acetylene and ethylene The higher Showed a tendency to decrease the yield. Productivity of acetylene showed a 2.0 ~ 15.0 mol / h high productivity 1kg per adsorbent. Table 4 shows the concentration of the gas concentration after the use of vacuum pressure swing adsorption separation.

Example 7: Methane / hydrogen / argon separation using a gas separation membrane

For the methane / hydrogen / argon separation, mixed gas separation was performed using the gas separation membrane module shown in FIG. 7 and the gas separation membrane included therein. A membrane module composed of a polysulfone hollow fiber membrane was used. By controlling the stage-cut (flow rate through the inlet gas flow rate / separation membrane), some mixed gas permeated through the membrane, and retentate. The composition of methane / hydrogen / argon was 3.95% / 19.27% / 76.78% and was commissioned by Rigaku Corporation. The gas flow rate at the inlet side of the membrane module was precisely controlled using MFC, and the flow rate of the residue was adjusted using a needle valve. The gas leaving the residue was analyzed by gas chromatography (Gas Chromatograph).

Example 8: Methane / hydrogen / argon separation from the mixed gas composition used in Example 7

For the separation, the pressure difference between the inlet and outlet of the membrane module was applied at 1 bar, and the stage-cut was controlled by manipulating the needle valve of the residue.

FIG. 12 is a graph showing the separation performance of the hydrogen-methane-argon composition according to the present embodiment while controlling the stage-cut.

As shown in FIG. 12, when the stage-cut was 0.3, it was confirmed that the hydrogen / methane separation degree was 6, and the hydrogen / argon separation degree was 2.5. Therefore, it was confirmed that the gas mixture was separated through the polysulfone separation membrane. In FIG. 12, it can be seen that the separation performance improves exponentially as the stage-cut decreases. It is considered that the stage-cut is a factor related to the structure of the membrane module, and if the density of the hollow fiber membrane is increased, excellent separation performance is realized even under the condition of high stage-cut

Example 9: Methane / hydrogen / argon separation in the presence of acetylene impurities in the mixed gas composition used in Example 7

For the separation, the pressure difference between the inlet and outlet of the membrane module was applied at 1 bar, and the stage-cut was controlled by manipulating the needle valve of the residue. 0.5 vol% of acetylene was added to the inlet to the mixed gas by controlling the MFC.

FIG. 13 is a graph illustrating an analysis of separation performance while adjusting the stage-cut under the assumption that acetylene impurities are present according to an embodiment of the present invention.

As shown in FIG. 13, when the stage-cut was 0.3, the hydrogen / methane separation was found to be 5.5, and the hydrogen / argon separation was 3. Compared with the case without acetylene, it was found that there was no large difference in the separation performance, and it was confirmed that the gas mixture was separated.

Example 10: Hybrid nanoporous material adsorbent separation efficiency according to pretreatment temperature of acetylene / ethylene

FIG. 14 is a graph showing the permeability of the PSf separator for a mixed gas containing acetylene at a pressure of 1 bar for a long period of operation. FIG. 15 is a graph showing the permeability of the PSf separator by using a zeolite separator, Argon (54.79%), methane (5.54%)). In FIG. 14, the pressure was 1 bar, and the permeability of the PSf membrane to the mixed gas containing acetylene was confirmed by long-term operation. The mixed gas was composed of 19.17% hydrogen, 76.40% Ar, 3.93% methane, and 0.5% acetylene. As can be seen in FIG. 18, even in the case of long-term operation, the decrease in performance due to the presence of acetylene was found to be insignificant.

FIG. 15 shows that the separation efficiency of the mixed gas was 39.67% hydrogen, 54.79% Ar and 5.54% methane by using the zeolite membrane module shown in FIG. 7 as compared with the polysulfone polymer membrane. And the degree of separation improves as the number increases.

It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. The scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning and scope of the claims and the equivalents thereof are included in the scope of the present invention Should be interpreted.

Claims (16)

A method for producing hydrogen-enriched gas and ethylene and acetylene enriched gas,
Ethylene and acetylene are reduced or eliminated using an adsorbent capable of adsorbing ethylene and acetylene from a first mixed gas containing plasma discharge gas, methane, hydrogen, ethylene, and acetylene formed by a plasma reaction of methane-containing gas A first step of preparing a plasma discharge gas, a methane and a hydrogen-containing second mixed gas in which acetylene is present at 0.5 vol% or less;
A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And
And a third step of recycling the third mixed gas to the plasma reaction of the methane-containing gas,
Wherein after said first step, the adsorbed ethylene and acetylene enriched gas are separated from said adsorbent. The method according to claim 1,
And storing the hydrogen enriched gas separated in the second step. The method according to claim 1,
And the third mixed gas is mixed with the methane-containing gas to be introduced into the plasma reaction. The method according to claim 1,
Wherein the plasma reaction is performed by a non-thermal plasma treatment under a catalyst, and comprises a CH bond cleavage reaction of methane in the methane-containing gas. The method according to claim 1,
Wherein the adsorbent is a porous hybrid organometallic framework (MOFs) and comprises a Cr (III) metal or Fe (III) metal as the central metal. The method according to claim 1,
Wherein the gas separation membrane is at least one of a polymer separation membrane, a zeolite membrane as an inorganic membrane, a carbon membrane, an organic skeleton membrane, and a mixed membrane obtained by mixing a polymer membrane and an inorganic material. The method according to claim 6,
The polymer separator may be any one or more of polysulfone (PSf), polyimide (PI), polyetherimide (PEI), polyethersulfone (PES), and polydimethylsiloxane ≪ / RTI > The method according to claim 1,
Wherein the content of methane contained in the methane-containing gas is 5 vol% to 50 vol% based on the total volume of the methane-containing gas. The method according to claim 1,
Further comprising separating the ethylene and acetylene enriched gas adsorbed from the adsorbent after the first step and storing the gas as a welding gas. 10. The method of claim 9,
Wherein the ethylene and acetylene enriched gas comprises 20 vol% or less of argon. A method for producing a hydrogen-enriched gas, an ethylene-enriched gas, and an acetylene-enriched gas,
Ethylene and acetylene are reduced or eliminated by using an adsorbent capable of adsorbing ethylene and acetylene from a first mixed gas containing plasma discharge gas, methane, hydrogen, ethylene, and acetylene formed by plasma reaction of methane-containing gas, A first step of preparing a plasma discharge gas, a methane and a hydrogen-containing second mixed gas present in an amount of 0.5 vol% or less;
A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And
And a third step of recycling the third mixed gas to the plasma reaction of the methane-containing gas,
Wherein the ethylene and acetylene mixture gas separated from the adsorbent after the first step is separated into an ethylene-enriched gas and an acetylene-enriched gas using an adsorbent that selectively adsorbs acetylene. delete A method for producing a hydrogen-enriched gas and an ethylene-enriched gas,
Ethylene and acetylene are reduced or eliminated by using an adsorbent capable of adsorbing ethylene and acetylene from a first mixed gas containing plasma discharge gas, methane, hydrogen, ethylene, and acetylene formed by plasma reaction of methane-containing gas, A first step of preparing a plasma discharge gas, a methane and a hydrogen-containing second mixed gas present in an amount of 0.5 vol% or less;
A second step of separating the second mixed gas through a gas separation membrane into a plasma discharge gas and a third mixed gas containing methane-enriched gas and a hydrogen-enriched gas; And
And a third step of recycling the third mixed gas to the plasma reaction of the methane-containing gas,
Further comprising an acetylene conversion reaction after the first step, wherein the mixed gas of ethylene and acetylene separated from the adsorbent is converted into ethylene-enriched gas by the acetylene conversion reaction.
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