WO2018004314A1 - Membrane de séparation de gaz sélective d'oxyde nitreux et procédé de purification d'oxyde nitreux l'utilisant - Google Patents

Membrane de séparation de gaz sélective d'oxyde nitreux et procédé de purification d'oxyde nitreux l'utilisant Download PDF

Info

Publication number
WO2018004314A1
WO2018004314A1 PCT/KR2017/007000 KR2017007000W WO2018004314A1 WO 2018004314 A1 WO2018004314 A1 WO 2018004314A1 KR 2017007000 W KR2017007000 W KR 2017007000W WO 2018004314 A1 WO2018004314 A1 WO 2018004314A1
Authority
WO
WIPO (PCT)
Prior art keywords
nitrous oxide
polymer
gas separation
membrane
separation membrane
Prior art date
Application number
PCT/KR2017/007000
Other languages
English (en)
Korean (ko)
Inventor
김정훈
이수복
Original Assignee
한국화학연구원
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2018004314A1 publication Critical patent/WO2018004314A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/06—Tubular membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/10—Spiral-wound membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/04—Tubular membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/108—Inorganic support material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/30—Improvements relating to adipic acid or caprolactam production

Definitions

  • the present invention relates to a nitrous oxide selective gas separation membrane, and in particular, to separate high-purity nitrous oxide from a nitrous oxide-containing gas mixture produced during the production of nitrous oxide by pyrolysis of ammonium nitrate, or to prepare adipic acid, nitric acid and caprolactam
  • the present invention relates to a nitrous oxide selective gas separation membrane that can be used industrially to separate high-purity nitrous oxide from nitrous oxide-containing exhaust gas mixture discharged from industrial processes such as processes.
  • Nitrous oxide has been in great demand in the microelectronic process of the semiconductor, liquid crystal display (LCD) and organic light emitting diode (OLED) fields.
  • Nitrous oxide is used for the production of silicon oxide layers formed from a gas mixture of silane and nitrous oxide chemically or by plasma deposition under low pressure. Nitrous oxide is also used for nitriding thin film silicon films.
  • Oxygen and nitrogen are the major impurities containing nitrous oxide that have a significant impact on quality in the silicon oxidation process.
  • nitrous oxide is prepared by pyrolyzing ammonium nitrate, which must be purified by removing impurities such as nitrogen and oxygen contained in the pyrolysis product.
  • Nitrous oxide is contained in the exhaust gas emitted from the adipic acid production process, the nitric acid production process, and the caprolactam production process.
  • the main impurities of the exhaust gas are oxygen and nitrogen. It is desired to recover nitrous oxide from nitrous oxide-containing exhaust gas and reuse it. This is because the recovery and reuse of nitrous oxide can not only reduce greenhouse gas emissions but also provide economic benefits.
  • Membrane separation technology is the most promising technique for separating and concentrating nitrous oxide discharged from industrial processes from mixed oxygen and nitrogen.
  • Membrane separation technology has advantages in that impurities can be efficiently separated from existing separation technologies such as adsorption and distillation, as well as a small device, low energy consumption, and continuous operation.
  • separator materials presented in the documents cited in the above papers are silicone rubber, polydimethylsiloxane, perpulouro (2-methylene-4-methyl-1,3-dioxocyclopentane) and poly [bis (tripulolu).
  • Roethoxy) phosphazenene] and the like also have low selectivity and permeability and are not effective for the separation of nitrous oxide.
  • the present inventors have effectively utilized nitrous oxide from nitrous oxide-containing gas mixture produced by pyrolysis of ammonium nitrate and nitrous oxide-containing exhaust gas emitted from industrial processes such as adipic acid manufacturing process, nitric acid manufacturing process and caprolactam manufacturing process. While studying a gas separation membrane that can be economically separated, a nitrous oxide selective gas separation membrane was found to have excellent separation performance of nitrous oxide, and the present invention was completed.
  • An object of the present invention is to efficiently treat nitrous oxide from nitrous oxide-containing gas mixtures produced by pyrolysis of ammonium oxyoxide and nitrous oxide-containing exhaust gases emitted in industrial processes such as adipic acid, nitric acid, and caprolactam. And economic separation.
  • a gas separation layer comprising a polymer material which is a polysulfone polymer or a polyimide polymer.
  • nitrous oxide selective gas separation membrane characterized by exhibiting nitrous oxide separation characteristics.
  • separator module comprising at least one nitrous oxide selective gas separator comprising a; and a gas separation layer comprising a polymer material which is a polysulfone polymer or a polyimide polymer.
  • It provides a method for purifying nitrous oxide comprising the step (step 2) of separating the nitrous oxide in the gas mixture supplied in step 1.
  • the nitrous oxide selective gas separation membrane according to the present invention can efficiently and economically separate or concentrate nitrous oxide from a gas mixture containing nitrous oxide, nitrogen, oxygen or other gas as a main component.
  • the present invention is a.
  • a gas separation layer comprising a polymer material which is a polysulfone polymer or a polyimide polymer.
  • nitrous oxide selective gas separation membrane characterized by exhibiting nitrous oxide separation characteristics.
  • the nitrous oxide selective gas separation membrane according to the present invention is characterized by exhibiting nitrous oxide separation characteristics, in particular, characterized in that it comprises a gas separation layer comprising a polymer material which is a polysulfone-based polymer or a polyimide-based polymer.
  • the gas separation layer including the polymer material of the polysulfone-based polymer or the polyimide-based polymer proposed in the present invention has not only a high nitrous oxide / nitrogen selectivity but also a high nitrous oxide permeation rate.
  • the gas separation layer has a separation coefficient of nitrous oxide / nitrogen at a permeation temperature of 0 ° C. to 100 ° C. and a permeation pressure of 0 bar to 100 bar ( ⁇ , P N 2 O / P N 2). ) May be 30 or more, 35 or more are preferred, more preferably 40 or more, even more preferably more than 40, most preferably 40-50.
  • the gas permeation separation performance of the gas separation membrane depends on the permeation selectivity and the permeation rate relative to the relative ratio of permeability between the gas mixture components to be separated and the gas mixture components to be separated.
  • ⁇ the permeability coefficient
  • ⁇ the ratio
  • P N 2 O / PN 2 the ratio
  • the membrane material is coated in the form of a composite membrane or processed into an asymmetric structure having a thin film layer to increase the permeation rate of gases per unit time.
  • the gas separation layer preferably has a permeation rate of nitrous oxide of 100 GPU or more, more preferably 150 GPU or more, and more preferably 200 GPU to 1,000 GPU, in a range of a permeation temperature of 0 ° C. to 100 ° C. and a permeation pressure of 0 bar to 100 bar. Most preferred.
  • the gas separation layer may be in the form of a mixture of at least one inorganic material selected from the group consisting of zeolite, carbon molecular sieve, metal organic structure (MOF) and aluminophosphate molecular sieve.
  • the gas separation membrane further includes a porous support layer.
  • the gas separation membrane including the porous support layer and the gas separation layer may have a form in which the gas separation layer is present in a thin film form on the surface of the porous support layer.
  • the porous support layer may mean a support made of a membrane having perforated fine pores connecting the front and back of the membrane, and its shape and material are not specified.
  • the porous support layer may be, for example, a hollow fiber porous support layer, a spiral porous support layer, a flat porous support layer, a nonwoven support layer, and the material may be a polysulfone polymer, a polyimide polymer, a cellulose acetate polymer, or a polycarbonate It may be one kind of polymer selected from the group consisting of a polymer, a polyamide-based polymer, a polyphenylene oxide-based polymer, and a polybenzimidazole-based polymer, a copolymer, a blend combination thereof, zeolite, carbon molecular sieve, metal organic structure (MOF) and an inorganic substance selected from the group consisting of aluminophosphate molecular sieves, mixtures thereof and the like.
  • a polysulfone polymer a polyimide polymer
  • a cellulose acetate polymer or a polycarbonate
  • It may be one kind of polymer selected from the group consisting
  • the porous support layer is preferably made of a polymer material, but a support made of an inorganic material or a metal component such as ceramic or metal powder may be used alone or together with a polymer in order to increase mechanical strength or heat resistance.
  • the gas separation membrane may be one type selected from the group consisting of hollow fiber membranes, spiral wound membranes, and tubular membranes.
  • separator module comprising at least one nitrous oxide selective gas separator comprising a; and a gas separation layer comprising a polymer material which is a polysulfone polymer or a polyimide polymer.
  • the membrane module according to the present invention is characterized in that it comprises at least one nitrous oxide selective gas separation membrane.
  • the nitrous oxide selective gas separation membrane including the polymer material of the polysulfone-based polymer or the polyimide-based polymer proposed in the present invention has not only a high nitrous oxide / nitrogen selectivity but also a high nitrous oxide permeation rate.
  • the membrane module has a separation coefficient ( ⁇ , P N2O / P N2 ) of nitrous oxide / nitrogen in a range of 0 ° C. to 100 ° C. and a permeation pressure of 0 bar to 100 bar of 30 or more. It is preferable that it is 35 or more, It is more preferable that it is 40 or more, It is still more preferable that it is more than 40, It is most preferable that it is 40-50.
  • the gas permeation separation performance of the gas separation membrane depends on the permeation selectivity and the permeation rate relative to the relative ratio of permeability between the gas mixture components to be separated and the gas mixture components to be separated.
  • ⁇ the permeability coefficient
  • ⁇ the ratio
  • P N 2 O / PN 2 the ratio
  • the membrane material is coated in the form of a composite membrane or processed into an asymmetric structure having a thin film layer to increase the permeation rate of gases per unit time.
  • the separator module preferably has a permeation rate of nitrous oxide in the range of 0 ° C. to 100 ° C. and a permeation pressure of 0 bar to 100 bar, preferably 100 GPU or more, more preferably 150 GPU or more, and 200 GPU to 1,000 GPU. Most preferred.
  • the gas separation layer may be in the form of a mixture of at least one inorganic material selected from the group consisting of zeolite, carbon molecular sieve, metal organic structure (MOF) and aluminophosphate molecular sieve.
  • the gas separation membrane preferably further comprises a porous support layer.
  • the gas separation membrane including the porous support layer and the gas separation layer may have a form in which the gas separation layer is present in a thin film form on the surface of the porous support layer.
  • the porous support layer may mean a support made of a membrane having perforated fine pores connecting the front and back of the membrane, and its shape and material are not specified.
  • the porous support layer may be, for example, a hollow fiber porous support layer, a spiral porous support layer, a flat porous support layer, a nonwoven support layer, and the material may be a polysulfone polymer, a polyimide polymer, a cellulose acetate polymer, or a polycarbonate It may be one kind of polymer selected from the group consisting of a polymer, a polyamide-based polymer, a polyphenylene oxide-based polymer, and a polybenzimidazole-based polymer, a copolymer, a blend combination thereof, zeolite, carbon molecular sieve, metal organic structure (MOF) and an inorganic substance selected from the group consisting of aluminophosphate molecular sieves, mixtures thereof and the like.
  • a polysulfone polymer a polyimide polymer
  • a cellulose acetate polymer or a polycarbonate
  • It may be one kind of polymer selected from the group consisting
  • the porous support layer is preferably made of a polymer material, but a support made of an inorganic material or a metal component such as ceramic or metal powder may be used alone or together with a polymer in order to increase mechanical strength or heat resistance.
  • the gas separation membrane may be one type selected from the group consisting of hollow fiber membranes, spiral wound membranes, and tubular membranes.
  • It provides a method for purifying nitrous oxide comprising the step (step 2) of separating the nitrous oxide in the gas mixture supplied in step 1.
  • step 1 is a step of supplying a gas mixture containing nitrous oxide to the separator module.
  • the method for purifying nitrous oxide is obtained from exhaust gas generated in a nitrogen-containing material production process such as nitrous oxide (N 2 O) production process, adipic acid production process, nitric acid production process, caprolactam production process by pyrolysis of ammonium nitrate.
  • a nitrogen-containing material production process such as nitrous oxide (N 2 O) production process, adipic acid production process, nitric acid production process, caprolactam production process by pyrolysis of ammonium nitrate.
  • a gas mixture containing nitrous oxide of step 1 is supplied to the membrane module.
  • the membrane module of step 1 comprises a gas separation layer comprising a polymer material which is a polysulfone-based polymer or a polyimide-based polymer as described in the present invention as described above, and nitrous oxide characterized in that it exhibits nitrous oxide separation characteristics
  • a separator module comprising at least one nitrogen selective gas separator.
  • the membrane module has a separation coefficient (?, P N2O / P N2 ) of 40 to 50 in the range of the permeation temperature of 0 °C to 100 °C and the permeation pressure of 0 bar to 100 bar, the nitrous oxide Since the transmission rate of 100 to 1,000 GPU, it can exhibit excellent nitrous oxide separation performance.
  • step 2 is a step of separating nitrous oxide from the gas mixture supplied in step 1 above.
  • Step 2 is a step of selectively separating the nitrous oxide contained in the gas mixture including the nitrous oxide supplied in step 1 through the membrane module.
  • the gas mixture contains about 0.3% by volume to 60% by volume of nitrous oxide, and the most impurities may contain 5% by volume to 60% by volume of nitrogen and 0% by volume to 40% by volume of oxygen.
  • nitrous oxide may be separated from nitrogen and oxygen, and concentrated to a concentration of 80% by volume or more.
  • Polysulphone PSF; Polysulfone (BASF) was manufactured on a self-made porous polyimide support with a thin film coating having a thickness of 1 to 5 ⁇ m to prepare a gas separation membrane, and the prepared gas separation membrane had an area of 330 cm 2 . It was prepared.
  • Polyimide (PI; Polyimide, Hunstman, USA) was produced by coating a thin film with a thickness of 1 to 5 ⁇ m on a self-made porous polyimide support to prepare a gas separation membrane, and the prepared gas separation membrane had an area of 330 cm 2 . Prepared to size.
  • PSF polysulfone
  • Polyimide (PI; Polyimide, P84 from Evonik, Germany) was coated with a thin film having a thickness of 1 to 5 ⁇ m to a porous polyimide support, and a gas separation membrane was prepared. Prepared to the size of 2 .
  • Polyimide (PI; Polyimide, Upilex, Ube, Japan) was applied to the self-made porous polyimide support to prepare a gas separation membrane by thin-film coating, and the prepared gas separation membrane was an area of 330 cm 2. Prepared to the size of.
  • a cellulose acetate polymer membrane (Cellulose Acetate, Kodak Film Co., Ltd.) was prepared in a size of 330 cm 2 .
  • Polycarbonate (PC; Polycarbonate, LG Chemical Co., Ltd.) on the self-made porous polyimide support was a thin film coating to a thickness of 1 to 5 ⁇ m to prepare a gas separation membrane, the prepared gas separation membrane having an area of 330 cm 2 Prepared to size.
  • Polydimethylsiloxane (PDMS; Dow Corning, USA) was manufactured by coating a thin film with a thickness of 1 to 5 ⁇ m on a self-made porous polyimide support to prepare a gas separation membrane, and the prepared gas separation membrane had an area of 330 cm. Prepared to the size of 2 .
  • the self-made porous polyimide support was coated with a natural rubber (NR, Korea LG Chemical Co., Ltd.) to a thickness of 1 to 5 ⁇ m thickness to prepare a gas separation membrane, the prepared gas separation membrane area 330 cm 2 Prepared to the size of.
  • a natural rubber NR, Korea LG Chemical Co., Ltd.
  • Polybutadiene (Polybutadiene; PBD, Korea Daelim Industrial Co., Ltd.) on a self-made porous polyimide support was a thin film coating to a thickness of 1 to 5 ⁇ m to prepare a gas separation membrane, the prepared gas separation membrane having an area of 330 cm 2 Prepared to size.
  • a gas separation membrane was prepared by coating a self-made porous polyimide support with a thin film of polyethylene (PE; LG Chemical Co., Ltd.) to a thickness of 1 to 5 ⁇ m.
  • the prepared gas separation membrane was an area of 330 cm 2 . It was prepared.
  • a gas separation membrane was prepared by coating a thin film of methyl rubber (LG Chem. Korea) with a thickness of 1 to 5 ⁇ m on a porous polyimide support fabricated by itself, and preparing the gas separation membrane with an area of 330 cm 2 . It was prepared.
  • Butyl rubber (Buthyl rubber, LG Chem Co., Ltd.) on the self-made porous polyimide support to perform a thin film coating to a thickness of 1 to 5 ⁇ m thickness to prepare a gas separation membrane, the prepared gas separation membrane having a size of 330 cm 2 area It was prepared.
  • a gas separation membrane was formed by coating a thin film of poly (4-methylpentene-1) (PMP, Korea Daelim Industrial Co., Ltd.) with a thickness of 1 to 5 ⁇ m on a self-made porous polyimide support.
  • the prepared gas separation membrane was prepared in an area of 330 cm 2 .
  • a gas separation membrane was prepared by performing a thin film coating of ethyl cellulose (EC, East membrane Kodak, USA) on a self-made porous polyimide support with a thickness of 1 to 5 ⁇ m, and the prepared gas separation membrane having an area of 330 cm. Prepared to the size of 2 .
  • EC ethyl cellulose
  • Polyaryletherketone (PEK, BASF Co., Ltd., USA) thin film coating was performed on a self-made porous polyimide support to prepare a gas separation membrane, and the prepared gas separation membrane had an area of 330 cm 2. Prepared to the size of.
  • a gas separation membrane was prepared by performing a thin film coating of polyphenylene oxide (PEO, LG Chem, Korea) with a thickness of 1 to 5 ⁇ m on a self-made porous polyimide support, and preparing the gas separation membrane with an area of 330 cm. Prepared to the size of 2 .
  • PEO polyphenylene oxide
  • Polybenzimidizole (PBI, PBI advanced materials, Inc.) was produced by coating a thin film with a thickness of 1 to 5 ⁇ m on a porous polyimide support fabricated by itself to prepare a gas separation membrane, and the prepared gas separation membrane had an area of 330 cm. Prepared to the size of 2 .
  • Poly (methyl methacrylate; PMMA, LG Chem Co., Ltd., Korea) was a thin film coating to a thickness of 1 to 5 ⁇ m on the porous polyimide support itself prepared to prepare a gas separation membrane, the prepared gas separation membrane It was prepared to a size of area 330 cm 2 .
  • PVDC Polyvinylidene chloride
  • the nitrous oxide permeation rate is excellent from 49.2 GPU to 643.3 GPU per company,
  • the calculated separation coefficient ⁇ (P N 2 O / P N 2 ) is 40.5 to 45.2, that is, it can be confirmed that exhibiting excellent separation characteristics to 40 or more.
  • the gas separation membrane according to the present invention can be used to separate or concentrate nitrous oxide from a nitrous oxide-containing gas mixture generated in the chemical industry at a high concentration.
  • it can be used to separate high-purity nitrous oxide from the gas mixture produced during the production of nitrous oxide by pyrolysis of ammonium nitrate, and also contains nitrous oxide-containing exhaust gases from adipic acid, nitric acid and caprolactam manufacturing processes. It is expected to be useful for the membrane separation process for recovering nitrous oxide for medical and semiconductor, LCD, and OLED.
  • the nitrous oxide selective gas separation membrane according to the present invention is useful for efficiently and economically separating or concentrating nitrous oxide from a gas mixture containing nitrous oxide, nitrogen or oxygen or other gas as a main component.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne une membrane de séparation de gaz sélective d'oxyde nitreux qui comprend une couche de séparation de gaz contenant un matériau polymère qui est un polymère à base de polysulfone ou un polymère à base de polyimide. La membrane de séparation de gaz sélective d'oxyde nitreux présente une propriété de séparation d'oxyde nitreux. La membrane de séparation de gaz sélective d'oxyde nitreux selon la présente invention est efficace dans la séparation d'oxyde nitreux de haute pureté à partir d'un mélange gazeux contenant du suboxyde de carbone produit dans un procédé de fabrication d'oxyde nitreux par pyrolyse de nitrate d'ammonium contenant de l'oxyde nitreux, de l'azote ou de l'oxygène ou d'autres gaz comme ingrédients principaux. La membrane peut aussi à partir d'un mélange de gaz d'échappement contenant de l'oxyde nitreux déchargé de procédés industriels tels que des procédés de fabrication de l'acide adipique, l'acide nitrique et le caprolactame, effectuer une séparation efficace de l'oxyde nitreux. Cette présente invention permet d'effectuer de manière économique une séparation et une concentration.
PCT/KR2017/007000 2016-06-30 2017-06-30 Membrane de séparation de gaz sélective d'oxyde nitreux et procédé de purification d'oxyde nitreux l'utilisant WO2018004314A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0082598 2016-06-30
KR1020160082598A KR101748609B1 (ko) 2016-06-30 2016-06-30 아산화질소 선택성 기체 분리막 및 이를 이용한 아산화질소 정제방법

Publications (1)

Publication Number Publication Date
WO2018004314A1 true WO2018004314A1 (fr) 2018-01-04

Family

ID=59281596

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2017/007000 WO2018004314A1 (fr) 2016-06-30 2017-06-30 Membrane de séparation de gaz sélective d'oxyde nitreux et procédé de purification d'oxyde nitreux l'utilisant

Country Status (2)

Country Link
KR (1) KR101748609B1 (fr)
WO (1) WO2018004314A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108704493A (zh) * 2018-06-26 2018-10-26 黑龙江大学 一种免冲洗pvdf管式微孔膜的制备方法
CN112320941A (zh) * 2020-10-21 2021-02-05 西安建筑科技大学 一种利用分离膜填料驯化产n2o反硝化菌的装置及方法
EP3858786A4 (fr) * 2018-09-28 2022-06-22 Showa Denko K.K. Procédé de purification d'oxyde nitreux

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101951780B1 (ko) * 2017-08-31 2019-02-25 한국화학연구원 가변운전이 가능한 아산화질소 회수 방법 및 장치
KR101952945B1 (ko) * 2017-08-31 2019-02-27 한국화학연구원 아산화질소 회수 방법
KR101951773B1 (ko) * 2017-08-31 2019-02-25 한국화학연구원 가변운전이 가능한 하이브리드 아산화질소 회수 방법 및 장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4230463A (en) * 1977-09-13 1980-10-28 Monsanto Company Multicomponent membranes for gas separations
US5409524A (en) * 1992-12-01 1995-04-25 The Dow Chemical Company Membranes having improved selectivity and recovery, and process for making same
JP2003038942A (ja) * 2001-07-31 2003-02-12 Dainippon Ink & Chem Inc 分離膜
KR20060085845A (ko) * 2005-01-25 2006-07-28 한양대학교 산학협력단 다공성 유기 고분자, 이의 제조방법 및 이를 이용한 기체분리막
KR20110130486A (ko) * 2009-03-27 2011-12-05 유오피 엘엘씨 열 처리 및 ｕｖ 가교에 의해 방향족 폴리이미드 막으로부터 제조된 고분자 막

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4230463A (en) * 1977-09-13 1980-10-28 Monsanto Company Multicomponent membranes for gas separations
US5409524A (en) * 1992-12-01 1995-04-25 The Dow Chemical Company Membranes having improved selectivity and recovery, and process for making same
JP2003038942A (ja) * 2001-07-31 2003-02-12 Dainippon Ink & Chem Inc 分離膜
KR20060085845A (ko) * 2005-01-25 2006-07-28 한양대학교 산학협력단 다공성 유기 고분자, 이의 제조방법 및 이를 이용한 기체분리막
KR20110130486A (ko) * 2009-03-27 2011-12-05 유오피 엘엘씨 열 처리 및 ｕｖ 가교에 의해 방향족 폴리이미드 막으로부터 제조된 고분자 막

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108704493A (zh) * 2018-06-26 2018-10-26 黑龙江大学 一种免冲洗pvdf管式微孔膜的制备方法
EP3858786A4 (fr) * 2018-09-28 2022-06-22 Showa Denko K.K. Procédé de purification d'oxyde nitreux
CN112320941A (zh) * 2020-10-21 2021-02-05 西安建筑科技大学 一种利用分离膜填料驯化产n2o反硝化菌的装置及方法
CN112320941B (zh) * 2020-10-21 2022-10-11 西安建筑科技大学 一种利用分离膜填料驯化产n2o反硝化菌的装置及方法

Also Published As

Publication number Publication date
KR101748609B1 (ko) 2017-06-21

Similar Documents

Publication Publication Date Title
WO2018004314A1 (fr) Membrane de séparation de gaz sélective d'oxyde nitreux et procédé de purification d'oxyde nitreux l'utilisant
AU2012354175B2 (en) Stabilization of porous morphologies for high performance carbon molecular sieve hollow fiber membranes
WO2013180517A1 (fr) Membrane d'osmose inverse hautement perméable comprenant un composé à base de carbodiimide, et procédé de réalisation de celle-ci
WO2018084553A1 (fr) Procédé de séparation et de récupération de monoxyde de carbone à partir de gaz de sous-produits de l'industrie sidérurgique
US6660062B2 (en) Chemical modification of polyimides
WO2018016750A1 (fr) Procédé de récupération et de purification d'oxyde nitreux à partir d'un mélange gazeux contenant de l'oxyde nitreux
WO2014196835A1 (fr) Membrane de séparation de traitement d'eau à base de polyamide ayant une excellente résistance à l'oxydation et une excellente résistance au chlore, et procédé de fabrication de celle-ci
WO2014204220A1 (fr) Procédé de préparation d'une membrane à osmose inverse à base de polyamide possédant un rejet de sel et un flux de perméation remarquables, et membrane à osmose inverse préparée par ledit procédé de préparation
WO2019209010A1 (fr) Technique de fabrication d'un séparateur utilisant un hydrocarbure aromatique et ayant une excellente efficacité d'élimination de soluté
WO2020256450A1 (fr) Adsorbant en fibres à réseau organométallique structuré pour la capture de dioxyde de carbone et son procédé de fabrication
WO2018147602A1 (fr) Film de polyamide-imide
WO2015137678A1 (fr) Film composite comprenant une couche de revêtement d'oxyde de graphène, support polymère poreux le comprenant, et procédé pour les préparer
WO2014137049A1 (fr) Membrane de traitement d'eau à base de polyamide présentant une remarquable résistance à la contamination et son procédé de préparation
WO2015016683A1 (fr) Membrane de séparation de traitement d'eau à base de polyamide ayant une excellente durabilité, et son procédé de fabrication
TW349031B (en) Process and system for separation and recovery of perfluorocompound gases
WO2013103257A1 (fr) Membrane d'osmose inverse remarquablement résistante à la contamination et son procédé de fabrication
DK85789D0 (da) Fremgangsmaade til udtraekning af organiske forbindelser fra luft/permanentgasblandinger
WO2017146457A2 (fr) Membrane composite à film ultramince à base de copolymère de poly (benzoxazole-imide) thermiquement réarrangé, et procédé de production associé
WO2018147618A1 (fr) Procédé de préparation d'un film de polyamide-imide
WO2011105828A2 (fr) Membrane en fibres creuses hautement poreuses et procédé de préparation de cette membrane
WO2022124554A1 (fr) Membrane d'osmose inverse en polyamide présentant d'excellentes propriétés de durabilité et antisalissure, et son procédé de fabrication
WO2017171474A1 (fr) Composition pour la polymérisation interfaciale d'un polyamide et procédé de fabrication d'une membrane d'osmose inverse l'utilisant
US20200276542A1 (en) Carbon molecular sieve membranes containing a group 13 metal and method to make them
WO2018012684A1 (fr) Filtre composite et procédé de fabrication associé
KR940008735A (ko) 다중 정제 막분리 방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17820590

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17820590

Country of ref document: EP

Kind code of ref document: A1