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WO2006103812A1 - Procede de purification du gaz, appareil correspondant et liquide absorbant les gaz acides utilise lors de la purification - Google Patents

Procede de purification du gaz, appareil correspondant et liquide absorbant les gaz acides utilise lors de la purification Download PDF

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Publication number
WO2006103812A1
WO2006103812A1 PCT/JP2005/022523 JP2005022523W WO2006103812A1 WO 2006103812 A1 WO2006103812 A1 WO 2006103812A1 JP 2005022523 W JP2005022523 W JP 2005022523W WO 2006103812 A1 WO2006103812 A1 WO 2006103812A1
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WO
WIPO (PCT)
Prior art keywords
gas
liquid
absorption
pressure
absorption tower
Prior art date
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Ceased
Application number
PCT/JP2005/022523
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English (en)
Japanese (ja)
Inventor
Wenbin Dai
Ryohei Mori
Kenjun Den
Kazuaki Ota
Akio Umemura
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Publication date
Priority claimed from JP2005094450A external-priority patent/JP4687184B2/ja
Priority claimed from JP2005212054A external-priority patent/JP4826156B2/ja
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Publication of WO2006103812A1 publication Critical patent/WO2006103812A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/229—Integrated processes (Diffusion and at least one other process, e.g. adsorption, absorption)
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • B01D53/526—Mixtures of hydrogen sulfide and carbon dioxide
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C01B17/167—Separation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/50—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0662—Treatment of gaseous reactants or gaseous residues, e.g. cleaning
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/066—Integration with other chemical processes with fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

Definitions

  • an ionic liquid or an organic solvent is used to absorb CO 2, H 2 S, CO
  • Acid gases such as S, SO, SO, NO, CS, HCN, NH, mercaptan, and H, CH
  • the present invention relates to a gas purification method and apparatus for separating and recovering the acid gas from the gas, and an acid gas absorption liquid used for the separation and recovery of the acid gas. More specifically, acid gas contained in synthesis gas, natural gas, etc. by fossil fuel gasification, reforming or partial oxidation, and acidity contained in exhaust gas from thermal power plants, cement plants, steel plants, chemical plants, etc.
  • the present invention relates to a gas purification method and apparatus for separating and recovering gas directly in a liquid state, and an acid gas absorbing solution used therefor. It also relates to the purification of hydrogen gas supplied to hydrogen stations and fuel cell vehicles, and the separation and recovery of liquid CO.
  • the acidic gas of 2 is separated and recovered, and this separation and recovery method includes a method of absorbing the acidic gas, a method of distilling the mixed gas, a method of adsorbing the acidic gas, a method of separating the mixed gas by membrane separation, and these methods.
  • the method which combined these is mentioned.
  • the lectisol process and the methyljetylamine process (hereinafter referred to as the MDEA process) are methods that are often used industrially (for example, see Non-Patent Document 1).
  • the lectisol process is a physical absorption process, using methanol as an absorbent, and CO contained in various gases such as synthesis gas by fossil fuel gasification, reforming or partial oxidation, ammonia synthesis gas, and natural gas. It is a method of absorbing and separating acid gases such as. Na
  • the absorption temperature of acid gas is set in the range of -10 to -75 ° C, and the absorption pressure is set in the range of 7 to 8MPa.
  • This lectizol process (physical absorption process) requires less regeneration energy than the MDEA process (chemical absorption process)! Have signs.
  • the absorption mechanism is based on the dissolution of gas in the absorption liquid, so the amount of acid gas dissolved is proportional to the acid gas partial pressure in the absorption tower. For this reason, the acid gas in the mixed gas is separated by the difference in the partial pressure of the acid gas in the absorption tower and the regeneration tower.
  • methanol is inexpensive and the absorption capacity for acid gas is 3 to 6 times the absorption capacity for acid gas in other physical absorption processes, so that a large amount of acid gas can be processed under high pressure by physical absorption! /
  • MDEA process is a chemical absorption process, some methyl oxygenate chill ⁇ Min aqueous tertiary Amin of 30 weight 0/0 as an absorbing liquid alone, when used in conjunction with active agent, the exhaust gas from the combustion of fossil fuels
  • This is a method for absorbing and separating acidic gas contained in various gases such as natural gas.
  • the absorption temperature of acid gas is set in the range of 30-60 ° C, and the absorption pressure is set in the range of 2-3MPa.
  • the absorption mechanism is a reversible reaction between an acid gas and an absorption liquid, and a compound is formed at low temperature and high pressure (the absorption liquid proceeds in the direction of absorbing the acid gas in the absorption tower). Decomposes into acid gas and absorption liquid at low pressure (advanced in the direction of releasing acid gas in the regeneration tower;).
  • the MDEA process is characterized by the fact that the regenerative energy of the absorbing solution is less than 1Z7 ⁇ : LZ2 of other chemical absorption processes and has a high ability to absorb acid gases.
  • Non-Patent Document 1 Editor: Japan Petroleum Institute, edited by Kodansha Scientific, Inc., “Oil Refinery Process”, Kodansha Co., Ltd., May 1998, p. 360-361)
  • the lectisol process shown in the above-mentioned conventional non-patent document 1 has a methanol loss.
  • the absorption temperature In order to suppress loss and increase the amount of acid gas absorbed per unit volume of the absorbent, the absorption temperature must be set low, a refrigerator is required, and the absorbent has vapor pressure.
  • the specific gravity is almost the same as the specific gravity of liquid CO.
  • the lectizol process and the MDEA process leave a small amount of absorbing liquid in the separated and collected acid gas.
  • the acid gas is CO used for food addition. If there is, high purity 99.99% by volume or more high purity CO
  • the first object of the present invention is to separate and recover acidic gas with high efficiency and low cost, and to increase the amount of acidic gas absorbed per unit volume of the absorbing liquid, and to further reduce the circulating amount of the absorbing liquid.
  • Another object of the present invention is to provide a gas purification method and apparatus capable of saving circulating energy.
  • the second object of the present invention is to use an absorption liquid having a low vapor pressure, so that the absorption liquid can be regenerated relatively easily and at a low cost, and the absorption liquid can be regenerated at a temperature lower than that of the conventional method.
  • Another object of the present invention is to provide a gas purification method and apparatus capable of reducing the regeneration energy.
  • the third object of the present invention is to reduce the evaporation port of the absorbing solution by using the absorbing solution having a low vapor pressure, and the absorbing solution does not remain in the separated and recovered CO gas.
  • the fourth object of the present invention is to efficiently recover CO in a liquid state, which makes the process easier than before.
  • Another object of the present invention is to provide a gas purification method and an apparatus therefor.
  • the fifth object of the present invention is to absorb acidic gas at a temperature higher than room temperature, thereby eliminating the need for a refrigerator and refrigeration energy, reducing costs, saving energy, and reducing the size of the gas. It is to provide a purification apparatus.
  • An ionic liquid is an organic salt that is melted without crystallization even at room temperature.
  • Ionic liquids have high heat resistance with low vapor pressure despite being liquid (thermally stable even at 400 ° C or higher), and have a wide temperature range of liquid – 100 to 300 ° C), low viscosity
  • it is highly polar and has unique properties such as being chemically stable and nonflammable.
  • the inventors of the present invention have the ability to absorb acidic gas such as CO per unit volume of ionic liquid under pressure.
  • an absorption liquid mainly composed of an ionic liquid is supplied to the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively.
  • a mixed gas containing an acidic gas and a non-acidic gas is supplied to the lower part of the gas, and the mixed gas is brought into contact with the absorbing liquid, thereby absorbing the acidic gas into the absorbing liquid and separating the non-acidic gas from the acidic gas.
  • the acidic gas is recovered from the step of recovering the acidic gas from the absorption tower 13 and the upper part of the regeneration tower 16 maintained at a temperature equal to or higher than the temperature in the absorption tower 13 and lower than the pressure in the absorption tower 13.
  • an absorption liquid mainly composed of an ionic liquid is supplied to the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively.
  • non-acidic gas and acidic gas can be combined with the mixed gas power. Efficient separation and recovery.
  • the invention according to claim 2 is an absorption liquid mainly composed of one or both of an organic solvent and water at the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure.
  • a mixed gas containing an acidic gas and a non-acidic gas is supplied to the lower part of the absorption tower 13, and the mixed gas is brought into contact with the absorbing liquid 42 so that the absorbing gas 42 absorbs the acidic gas and the non-acidic gas is absorbed.
  • the liquid acid gas 41 is separated from the liquid 42 by the mutual insolubility and specific gravity difference between the liquid liquid 41 and the liquid 42.
  • a process to recover from the regenerator 46 and to regenerate the absorbent 42 And a method of purifying a mixed gas containing an acidic gas, including the step of supplying the regenerated absorbing liquid 42 to the upper portion of the absorption tower 13.
  • the organic solvent or water is used as the main component at the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively.
  • the absorbing liquid 42 is supplied and a mixed gas containing acidic gas and non-acidic gas is supplied to the lower part of the absorption tower 13, the mixed gas comes into contact with the absorbing liquid 42 and the acidic gas is absorbed by the absorbing liquid 42. Separated into non-acid gas and acid gas, the non-acid gas is recovered from the absorption tower 13.
  • the absorption liquid 42 that has absorbed the acid gas is supplied to the separation regenerator 46 that is maintained at the same level, the acid gas is liquefied in the separation regenerator 46, and the mutual insolubility between the liquid acid gas 41 and the absorption liquid 42 and The liquid acid gas 41 is separated from the absorbent 42 by the difference in specific gravity and recovered from the separation regenerator 46, and the absorbent 42 is regenerated and reused.
  • the solubility in acidic gas becomes very large under pressure and in a predetermined temperature range.
  • the acidic gas is liquefied in a temperature range lower than the predetermined temperature range, and the liquid acidic gas
  • the acidic gas 41 is recovered as a gas and then cooled by cooling to form a liquid.
  • the mixed gas force non-acidic gas and liquid acidic gas 41 can be separated and recovered efficiently.
  • an absorption liquid 42 mainly composed of an ionic liquid is supplied to the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively.
  • a mixed gas containing an acidic gas and a non-acidic gas is supplied to the lower part of 13 and bringing the mixed liquid into contact with the absorbing liquid 42 ⁇ .
  • the absorbing gas 42 absorbs the acidic gas and the non-acidic gas and the acidic gas
  • the non-acidic gas is recovered from the absorption tower 13 and the separation regenerator 46 maintained at a predetermined pressure and lower than the temperature in the absorption tower 13 is supplied with the absorbing liquid that has absorbed the acidic gas.
  • the acid gas is liquefied, and the liquid acid gas 41 is separated from the absorbing liquid 42 by the mutual insolubility and the specific gravity difference between the liquid acid gas 41 and the absorbing liquid 42 and recovered from the separation regenerator 46 and absorbed.
  • Step of regenerating liquid 42 and the regenerated absorbent And a step of supplying 42 to the upper part of the absorption tower 13.
  • the absorption liquid 42 mainly composed of an ionic liquid is supplied to the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively. If a mixed gas containing an acidic gas and a non-acidic gas is supplied to the lower part of the absorption tower 13, the mixed gas comes into contact with the absorbent 42 and the acidic gas is absorbed by the absorbent 42. The non-acidic gas is recovered from the absorption tower 13. Maintain the same pressure as that in the absorption tower 13, a pressure slightly higher than the pressure in the absorption tower 13, or a pressure slightly lower than the pressure in the absorption tower 13 and a temperature lower than the temperature in the absorption tower 13.
  • the separation / regenerator 46 When the absorption liquid that has absorbed the acid gas is supplied to the maintained separation / regenerator 46, the separation / regenerator 46 liquefies the acid gas, and the mutual insolubility and specific gravity difference between the liquid acid gas 41 and the absorption liquid 42 are reduced.
  • the liquid acid gas 41 is separated from the absorbing liquid 42 and recovered from the separation regenerator 46, and the absorbing liquid 42 is regenerated and reused. That is, the solubility in acidic gas becomes very large under pressure and in a predetermined temperature range, and the acidic gas is liquefied under pressure and in a temperature range lower than the predetermined temperature range.
  • the acid gas 41 is recovered in the liquid state directly rather than being pressurized and cooled after being recovered as a gas. Since the recovery is performed, the non-acidic gas and the liquid acidic gas 41 can be efficiently separated and recovered by using the mixed gas power.
  • a liquid membrane 51 in which a porous membrane is impregnated with an absorption liquid mainly composed of an ionic liquid is stretched in a membrane separator 52.
  • the membrane separator 52 is divided into a first chamber 52a and a second chamber 52b, the first chamber 52a is set to a pressure higher than that of the second chamber 52b, and the first chamber 52a is a mixed gas containing acidic gas and non-acidic gas.
  • the non-acid gas remains in the first chamber 52a, passes through the liquid film 51 and moves to the low-pressure second chamber 52b, and recovers the non-acid gas from the first chamber 52a.
  • it is a gas purification method for recovering acid gas from the second chamber 52b.
  • the invention according to claim 8 is the invention according to any one of claims 1, 3, or 4, and is characterized in that the absorbing liquid containing an ionic liquid as a main component is neutral or alkaline. And In the gas purification method described in claim 8, since the absorbing solution is neutral or alkaline, the acidic gas is easily dissolved in the absorbing solution, and the solubility thereof is larger than that of the acidic absorbing solution.
  • the invention according to claim 9 is the invention according to claim 1 or 3, further comprising a step of dehumidifying the mixed gas before supplying the mixed gas to the absorption tower 13, as shown in FIG. It is a feature.
  • the invention according to claim 10 is the invention according to claim 4, further comprising a step of dehumidifying the mixed gas before introducing the mixed gas into the membrane separator 52, as shown in FIG. It is a feature.
  • the acid gas is absorbed into the absorption liquid.
  • the solubility of the acidic gas in the absorbing liquid or the permeability to the liquid film 51 is increased.
  • the absorption liquid force that absorbed the acid gas is lower than 0 ° C. in order to separate the acid gas in a liquid state, the acid gas that does not freeze water is quickly separated from the absorption liquid.
  • the invention according to claim 13 is the invention according to claim 2 or 3, and as shown in FIG. 2 or 3, the temperature discharged from the absorption tower 13 and lower than the temperature in the absorption tower 13. Before the absorption liquid 42 containing the acidic gas cooled to the separation regenerator 46 is supplied to the separation regenerator 46, it further includes a step of centrifugation or stirring.
  • the acidic gas in the absorbing liquid 42 is liquefied by cooling the absorbing liquid 42 containing the acidic gas to a temperature lower than the temperature in the absorber 13.
  • the absorption liquid 42 including the liquid acid gas 41 is obtained by centrifuging or stirring before being supplied to the separation regenerator 46.
  • the separator / regenerator 46 the liquid acid gas and the absorbing liquid are quickly separated into phases.
  • the invention according to claim 14 is the invention according to claim 2 or 3, wherein, as shown in FIG. 7 or FIG. 8, the absorbing liquid 42 has magnetism, and a magnet 61 is provided below the separation regenerator 46. It is provided.
  • the pressure is almost the same as the pressure in the absorption tower 13, that is, the same pressure as the pressure in the absorption tower 13, a pressure slightly higher than the pressure in the absorption tower 13,
  • the absorption liquid 42 containing the liquid acidic gas 41 is supplied to the separation regenerator 46 which is maintained at a pressure slightly lower than the pressure in the absorption tower 13 and maintained at a temperature lower than the temperature in the absorption tower 13.
  • the liquid acid gas 41 and the absorption liquid 42 are quickly separated into the absorption liquid 42 and the liquid acid gas 41 by the mutual insolubility and the specific gravity difference between the liquid acid gas 41 and the absorption liquid 42 and the attractive force of the magnetic absorption liquid 42 by the magnet 61.
  • the invention according to claim 15 is the invention according to any one of claims 1 to 3, and further includes water, alcohols, ethers and phenols as shown in FIG. 9 or FIG.
  • One or two or more additives 71 selected from the group consisting of these are added to the absorbent 42.
  • the viscosity of the absorbing liquid 42 can be reduced by adding the additive 71 to the absorbing liquid 42.
  • the additive-containing absorption liquid 75 is supplied to the absorption tower 13, so that the absorption gas can be absorbed by the absorption tower 13 without substantially reducing the ability of the additive-containing absorption liquid 75 to absorb the acid gas.
  • the contained absorbent 75 flows smoothly, and the additive-containing absorbent 75 can be handled easily.
  • the invention according to claim 16 is the invention according to claim 2 or 3, further comprising one or two selected from the group consisting of water, alcohols and ethers as shown in FIG. 11 or FIG.
  • the specific gravity of the liquid acidic gas 41 and the additive-containing absorbent 75 in the separation regenerator 46 is adjusted.
  • the additive-containing absorption liquid 75 discharged from the separation / regenerator 46 is supplied to the distillation separator 83 and the inside of the distillation separator 83 is heated to a predetermined temperature to absorb the additive-containing absorption. And a step of distilling and separating the additive 71 in the liquid 75 from the absorbing liquid 42.
  • the additive 71 is separated into the separation regenerator 46 together with the absorbing liquid 42 containing the liquid acidic gas 41 in a state where the pressure and temperature in the separation regenerator 46 are adjusted.
  • the mutual insolubility and specific gravity difference between the liquid acid gas 41 and the absorbing liquid 42 and the additive having the mutual solubility in the absorbing liquid 42 and the mutual insolubility in the liquid acidic gas 41 71 By replacing the liquid acidic gas 41 dispersed in the absorbent 42 by the additive 71 with the additive 71, the liquid acidic gas 41 and the additive-containing absorbent 75 are quickly separated.
  • the additive-containing absorbent 75 discharged from the separator / regenerator 46 is supplied to the distillation separator 83 while the inside of the distillation separator 83 is heated to a predetermined temperature, the additive in the additive-containing absorbent 75 is added. 71 is distilled off from the absorbent 42. As a result, the absorption liquid 42 from which the additive 71 has been removed is supplied to the absorption tower 13, so that the absorption gas 13 can absorb the acid gas without reducing the ability of the absorption liquid 42 to absorb the acid gas.
  • the invention according to claim 17 is the invention according to claim 2 or 3, characterized in that a flocculant is further added to the absorbing liquid containing liquid acidic gas in the separation regenerator.
  • the liquid acid gas dispersed in the absorption liquid by adding the flocculant to the absorption liquid containing the liquid acid gas in the separation regenerator. Since the (dispersed liquid) can be agglomerated, it is quickly separated into the aggregating agent-containing absorbing liquid and the liquid acidic gas due to the difference in specific gravity between the aggregating agent-containing absorbing liquid and the liquid acid gas in the separation regenerator. Thereafter, if the flocculant-containing absorbing liquid is separated by distillation, the flocculant and the absorbing liquid are further separated.
  • the invention according to claim 18 is the invention according to claim 2 or 3, wherein the acidic gas is CO gas and the separation regenerator is maintained at a pressure of 4 to 25 MPa as shown in FIG. 13 or FIG. Four
  • Water is supplied into the absorption liquid 42 containing liquid CO 41 in 6.
  • the separation regenerator 46 is kept in the absorbing liquid 42 containing the liquid CO 41 in the separation regenerator 46 while the inside of the separation regenerator 46 is kept at a high pressure of 4 to 25 MPa.
  • the invention according to claim 19 includes a compressor 12 for compressing a mixed gas containing an acidic gas and a non-acidic gas, a compressed mixed gas supplied at the lower part, and an organic solvent or water at the upper part.
  • the absorbing liquid 42 containing either or both of the main components is supplied, and the mixed gas is brought into contact with the absorbing liquid 42 to absorb the acidic gas into the absorbing liquid 42 to separate and recover the non-acidic gas from the acidic gas.
  • Absorption tower 13 cooler 47 that cools the absorption liquid that has absorbed the acid gas, and absorption liquid that has been cooled and absorbed the acid gas are supplied, and due to the mutual insolubility and specific gravity difference between liquid acid gas 41 and absorption liquid 42 Separating and recovering the liquid acid gas 41 from the absorbing liquid 42 and regenerating and reusing the absorbing liquid 42, the separating regenerator 46 and the absorbing liquid 42 discharged from the separating regenerator 46, And a circulation pump 17 for supplying to the upper part.
  • it is a purification apparatus for a mixed gas containing acid gas.
  • an absorption liquid mainly composed of one or both of an organic solvent and water is provided above the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively.
  • a mixed gas containing acidic gas and non-acidic gas is compressed and supplied to the lower part of the absorption tower 13 with the compressor 12, the mixed gas comes into contact with the absorbing liquid 42 and the acidic gas is absorbed into the absorbing liquid 42. Therefore, the non-acid gas is separated from the acid gas column and recovered from the absorption tower 13.
  • the separation regenerator 46 From the same pressure as in the absorption tower 13 above, the pressure in the absorption tower 13 If the absorption liquid that has absorbed the acid gas is supplied to the separation regenerator 46 maintained at a slightly lower pressure or slightly higher than the pressure in the absorption tower 13 after being cooled by the cooler 47, the separation regenerator 46 Thus, the acid gas is liquidized, and the liquid acid gas 41 is separated from the absorbing liquid 42 by the mutual insolubility and the specific gravity difference between the liquid acid gas 41 and the absorbing liquid 42 and collected from the separation regenerator 46. In addition, the absorbing liquid 42 regenerated by removing the liquid acid gas is supplied to the upper portion of the absorption tower 13 by the circulation pump 17 and reused.
  • the invention according to claim 20 includes a dehumidifier 11 for dehumidifying a mixed gas containing an acidic gas and a non-acidic gas, a compressor 12 for compressing the dehumidified mixed gas, and a lower portion of the compressed gas.
  • the mixed liquid is supplied, and the upper part is supplied with an absorbing liquid 42 containing an ionic liquid as a main component, and the mixed gas is brought into contact with the absorbing liquid 42 to absorb the acidic gas into the absorbing liquid 42 to thereby remove the non-acidic gas.
  • Absorption tower 13 that separates and recovers acid gas from the tank, cooler 47 that cools the absorption liquid that has absorbed the acid gas, and liquid insoluble gas 41 and absorption liquid 42 that are supplied with cooled absorption liquid 42 are mutually insoluble.
  • the liquid acid gas 41 is separated and recovered from the absorbent 42 due to the difference in specific gravity, and at the same time, the separator / regenerator 46 that regenerates and reuses the absorbent 42 and the absorbent 42 discharged from the separator / regenerator 46 remain at high pressure And a circulation pump 17 to be supplied to the upper part of the absorption tower 13. And an apparatus for purifying gases.
  • an absorption liquid 42 containing an ionic liquid as a main component is supplied to the upper part of the absorption tower 13 maintained at a predetermined temperature and a predetermined pressure, respectively.
  • a mixed gas containing acidic gas and non-acidic gas dehumidified by the dehumidifier 11 is compressed and supplied to the lower part of the dehumidifier 11 by the compressor 12, the mixed gas comes into contact with the absorbing liquid 42 and the acidic gas becomes the absorbing liquid 42. As it is absorbed, the non-acid gas is separated from the acid gas column and recovered in the absorption tower.
  • Acid gas is fed to the separation regenerator 46 maintained at the same pressure as the pressure in the absorption tower 13 or slightly lower than the pressure in the absorption tower 13 or slightly higher than the pressure in the absorption tower 13.
  • the acidic gas is liquefied by the separator / regenerator 46.
  • the absorption liquid 42 Liquid acid gas 41 is separated and recovered from separation regenerator 46.
  • the absorbent 42 regenerated by removing the liquid acid gas is supplied to the upper part of the absorption tower 13 by the circulation pump 17 and reused.
  • the invention according to claim 21 is the invention according to claim 19 or 20, further comprising an absorption tower 13, a cooler 47, and a separation regenerator 46 as shown in FIG. 4 or FIG. It is characterized by that.
  • the apparatus can be miniaturized.
  • the invention according to claim 22 is the invention according to any one of claims 19 to 21, and further between the cooler 47 and the separation regenerator 46 as shown in FIG. 2 or FIG. A centrifuge 48 or a stirrer is provided in the interior.
  • the acidic gas in the absorbing liquid 42 is cooled by cooling the absorbing liquid containing acidic gas to a temperature lower than the temperature in the absorption tower 13 by the cooler 47.
  • this liquid acid gas 41 is dispersed in the absorbing liquid, the liquid acid gas 41 is centrifuged or stirred with a centrifuge 48 or a stirrer before being supplied to the separation regenerator 46.
  • the absorbing liquid 42 contained in the acidic gas 41 is quickly phase-separated into the liquid acidic gas 41 and the absorbing liquid 42 in the separation regenerator 46.
  • the invention according to claim 23 is the invention according to any one of claims 19 to 22, and as shown in FIG. 7 or FIG. 8, the absorbing liquid 42 has magnetism, and the separation regenerator 46 A magnet 61 is provided in the lower part.
  • the pressure is almost the same as the pressure in the absorption tower 13, that is, the same pressure as the pressure in the absorption tower 13, a pressure slightly higher than the pressure in the absorption tower 13,
  • the absorption liquid 42 containing the liquid acidic gas 41 is supplied to the separation regenerator 46 which is maintained at a pressure slightly lower than the pressure in the absorption tower 13 and maintained at a temperature lower than the temperature in the absorption tower 13.
  • the liquid acid gas 41 and the absorption liquid 42 are quickly separated into the absorption liquid 42 and the liquid acid gas 41 by the mutual insolubility and the specific gravity difference between the liquid acid gas 41 and the absorption liquid 42 and the attractive force of the magnetic absorption liquid 42 by the magnet 61.
  • the invention according to claim 24 is the invention according to any one of claims 19 to 23, and further includes water, alcohols, ethers and phenols as shown in FIG. 9 or FIG.
  • Absorbing liquid 42 to which one or two or more additives 71 selected from the group are added is stored, and an absorbing liquid storage tank 72 is provided for supplying the additive-containing absorbing liquid 75 to the absorption tower 13. It is characterized by that.
  • the viscosity of the absorbent 42 can be reduced.
  • the additive-containing absorption liquid 75 is supplied to the absorption tower 13, so that the absorption gas 13 can absorb the acid gas without substantially reducing the ability of the additive-containing absorption liquid 75 to absorb the acid gas.
  • the additive-containing absorbent 75 flows smoothly, and the additive-containing absorbent 75 can be handled easily.
  • the invention according to claim 25 is the invention according to any one of claims 19 to 23, and is further selected from the group consisting of water, alcohols and ethers as shown in FIG. 11 or FIG.
  • One or two or more additives 71 are stored and the additive storage tank 81 connected to the upper part of the separation regenerator 46, and pressure adjusting means for adjusting the pressure in the separation regenerator 46 provided in the separation regenerator 46 82, a distillation separator 83 for storing an additive-containing absorbent 75 that is connected to the lower part of the separation regenerator 46, separated by specific gravity in the separation regenerator 46, and transferred to the lower phase thereof, and a distillation separator 83.
  • a heating means 84 for heating the inside of the distillation separator 83 to a predetermined temperature is further provided.
  • the additive is used together with the absorbing liquid 42 containing the liquid acidic gas 41 in a state where the temperature and pressure in the separation regenerator 46 are adjusted by the cooler 47 and the pressure adjusting means 82.
  • the separator / regenerator 46 When 71 is supplied to the separator / regenerator 46, the mutual insolubility and specific gravity difference between the liquid acid gas 41 and the absorbing liquid 42 and the mutual solubility with respect to the absorbing liquid 42 and the liquid acid gas 41 are mutually exclusive.
  • the liquid acid gas 41 is transferred to the upper phase of the separation regenerator 46 and The additive-containing absorbent 75 is transferred to the lower phase of the separation regenerator 46, and the liquid acidic gas 41 and the additive-containing absorbent 75 are quickly separated.
  • the distillation separator 83 is heated to a predetermined temperature by the heating means 84, the additive-containing absorbing liquid 75 from which the lower force of the separation regenerator 46 is discharged is supplied to the distillation separator 83.
  • the additive 71 in the absorbent 75 is separated from the absorbent 42 by distillation.
  • the invention according to claim 26 is the invention according to any one of claims 19 to 23, further characterized in that a flocculant tank for storing the flocculant is connected to the separation regenerator. .
  • the flocculant stored in the flocculant tank is dispersed in the absorbent by adding it to the absorbent containing the liquid acidic gas in the separation regenerator.
  • the liquid acid gas (dispersed liquid) can be agglomerated, so that it is quickly separated into the flocculant-containing absorption liquid and the liquid acid gas due to the difference in specific gravity between the flocculant-containing absorption liquid and the liquid acid gas. The Thereafter, if the flocculant-containing absorbing liquid is separated by distillation, the flocculant and the absorbing liquid are further separated.
  • the invention according to claim 27 is the invention according to any one of claims 19 to 23, and further, as shown in FIG. 13 or FIG. 14, the acidic gas is CO gas, Pressure
  • a pressure adjusting means 82 for keeping the force at 4 to 25 MPa is provided in the separation regenerator 46, and a water storage tank 91 in which water is stored is connected to the lower part of the separation regenerator 46.
  • water is separated from the water storage tank 91 in the separation regenerator 46 while the pressure in the separation regenerator 46 is maintained at a high pressure of 4 to 25 MPa by the pressure adjusting means 82.
  • the pressure in the separation regenerator 46 is maintained at a high pressure of 4 to 25 MPa by the pressure adjusting means 82.
  • the invention according to claim 29 is, as shown in FIG. 15, one or more selected from the group consisting of desulfurized gasoline, naphtha, kerosene, methanol, dimethyl ether, liquefied petroleum gas and natural gas. After reforming the fuel, transforming CO and removing CO to make a mixed gas of H and CO
  • gas purification apparatus described in claim 1 using the mixed gas purification method described in claim 1 or the gas purifying method described in claim 19 or claim 1 is used. Is used to separate and collect H and CO, and this separated and collected H is supplied to the hydrogen station.
  • high pressure H is not produced from various fuels.
  • the invention according to claim 30 is an on-vehicle reforming type using a fuel cell as a drive source. Installed in vehicles, desulfurized gasoline, naphtha, kerosene, methanol, dimethyl ether, liquid oil, natural gas, and one or more fuels selected from the group consisting of reforming, CO conversion and CO After removing it to make a mixed gas of H and CO, this mixed gas is charged.
  • the system described in claim 30 can be miniaturized to such an extent that it can be mounted on a vehicle, and liquid CO can be efficiently recovered while producing high-pressure H with various fuel forces.
  • an absorption liquid mainly composed of an ionic liquid is supplied to the upper part of the absorption tower maintained at a predetermined temperature and a predetermined pressure, and acidic gas and non-acidic gas are supplied to the lower part of the absorption tower.
  • the mixed gas is supplied, the mixed gas is brought into contact with the absorbing liquid, and the acidic gas is absorbed into the absorbing liquid, and is maintained at a temperature equal to or higher than the temperature in the absorbing tower and lower than the pressure in the absorbing tower. Since the absorption liquid that has absorbed the acid gas is supplied to the upper part of the regeneration tower that is maintained at the above, the non-acid gas can be separated from the acid gas column by the absorption tower and recovered, and the acid gas can be recovered by the regeneration tower.
  • the absorption liquid force can be separated by separating and recovered, and the regeneration tower force can be recovered.
  • the absorption liquid can be regenerated, and by supplying the regenerated absorption liquid to the upper part of the absorption tower, the absorption liquid can be reused.
  • non-acidic gas and acidic gas can be combined with the mixed gas power.
  • the absorption amount of the acidic gas per unit volume of the absorption liquid can be increased, the circulation volume of the absorption liquid can be reduced, and the circulation energy can be saved.
  • the regeneration tower can be made relatively simple, and the absorption liquid can be regenerated relatively easily and at a low cost. This can reduce the regeneration energy of the absorbing liquid.
  • the absorption liquid Evaporation loss can be eliminated, and there is no absorption liquid remaining in the separated and collected acid gas, making it possible to easily produce high-purity acid gas.
  • an absorption liquid mainly composed of one or both of an organic solvent and water is supplied to the upper part of the absorption tower maintained at a predetermined temperature and a predetermined pressure, and an acid gas is supplied to the lower part of the absorption tower.
  • a mixed gas containing non-acidic gas is supplied, and the mixed gas is brought into contact with the absorbing liquid so that the absorbing gas absorbs the acidic gas, and is maintained at a predetermined pressure and maintained at a temperature lower than the temperature in the absorption tower.
  • the non-acid gas can be separated from the acid gas column in the absorption tower and recovered from the absorption tower, and the liquid acid gas and the absorption liquid can be separated by the separation regenerator.
  • the liquid acid gas can be separated from the absorption liquid by the mutual insolubility and specific gravity difference and recovered from the separator / regenerator, and the absorption liquid can be regenerated.
  • the regenerated absorption liquid is supplied to the upper part of the absorption tower with high pressure. By doing so, the absorbent can be reused.
  • the solubility in acidic gas becomes very large under pressure and in a predetermined temperature range, and acidic gas is liquefied under pressure and in a temperature range lower than the predetermined temperature range.
  • the acid gas is recovered directly in the liquid state rather than being recovered by pressurization and cooling after the acid gas is recovered as a gas. Therefore, the non-acidic gas and the liquid acidic gas can be separated and recovered efficiently and at low cost in addition to the mixed gas power.
  • the process can be simplified compared to the conventional method, and there is no significant fluctuation in temperature and pressure throughout the process, and the regenerative energy of the absorbent is eliminated, and the recompression energy when returning the regenerated absorbent to the absorption tower is unnecessary. Energy saving can be achieved.
  • an absorption liquid mainly composed of an ionic liquid is supplied to the upper part of the absorption tower maintained at a predetermined temperature and a predetermined pressure, and acidic gas and non-acidic gas are contained in the lower part of the absorption tower.
  • a separation / regenerator that supplies the mixed gas to the absorbent and contacts the mixed gas so that the acidic gas is absorbed by the absorbent, and is maintained at a predetermined pressure and lower than the temperature in the absorption tower.
  • the non-acidic gas can be separated from the acidic gas by the absorption tower and recovered from the absorption tower, and the separation regenerator can be used due to the mutual insolubility and specific gravity difference between the liquid acidic gas and the absorbing liquid.
  • Absorbing liquid power Separation and regenerator power can be recovered by separating liquid acid gas
  • the absorbing solution can be regenerated, and the regenerated absorbing solution can be reused by supplying the regenerated absorbing solution to the upper part of the absorption tower with high pressure.
  • the solubility in acidic gas becomes very large under pressure and in a predetermined temperature range, and the acidic gas is liquefied under pressure and in a temperature range lower than the predetermined temperature range.
  • the acidic gas is directly in a liquid state rather than being recovered by pressurization and cooling after being collected as a gas.
  • the non-acid gas and the liquid acid gas can be separated and recovered from the mixed gas efficiently and at low cost.
  • the process can be simplified compared to the conventional method, and there is no significant fluctuation in temperature and pressure during the entire process, and the regeneration energy of the absorption liquid is eliminated, and the recompression energy is not required when returning the regenerated absorption liquid to the absorption tower. Energy saving can be achieved.
  • a liquid membrane impregnated with a porous membrane impregnated with an absorption liquid mainly composed of an ionic liquid is stretched in the membrane separator to partition the membrane separator into a first chamber and a second chamber. If one chamber is set to a pressure higher than that of the second chamber and a mixed gas containing acidic gas and non-acidic gas is introduced into the first chamber, the acidic gas will leave the liquid film while the non-acidic gas remains in the first chamber. Since it permeates and flows into the low pressure second chamber, the mixed gas can be separated into acidic gas and non-acidic gas and recovered from the membrane separator.
  • the absorbing liquid mainly composed of an ionic liquid is neutral or alkaline, the acidic gas is easily dissolved in the absorbing liquid, and the solubility is higher than that of the acidic absorbing liquid.
  • the solubility of the acidic gas in the absorbing liquid can be increased, and the mixed gas is removed before the mixed gas is introduced into the membrane separator.
  • the permeability of the acid gas to the liquid film can be increased.
  • the absorption liquid containing the acid gas discharged and cooled to a temperature lower than the temperature in the absorption tower is centrifuged or stirred before being supplied to the separation / regenerator, the absorption liquid can be contained in the absorption liquid. Since the dispersed liquid acid gas is almost separated into the liquid acid gas and the absorbing liquid before being supplied to the separation / regenerator, the liquid acid gas and the absorbing liquid can be quickly separated into the liquid acid gas and the absorbing liquid in the separation / regenerator. As a result, the phase separation time between the liquid acidic gas and the absorbing liquid can be shortened, and the liquid acidic gas can be efficiently recovered.
  • the pressure in the absorption tower If the absorption liquid has magnetism and a magnet is provided at the bottom of the separation regenerator, the pressure in the absorption tower If an absorption liquid containing liquid acidic gas is supplied to a separation regenerator that is maintained at the same pressure as that of the absorption tower and lower than the temperature in the absorption tower, the mutual insolubility and specific gravity difference between the liquid acidic gas and the absorption liquid And the absorption force of the magnetic absorption liquid by the magnets cause rapid separation into the absorption liquid and the liquid acidic gas. As a result, the liquid acid gas can be quickly recovered from the separation regenerator, and the absorbing liquid can be quickly regenerated and reused.
  • the viscosity of the absorbing solution can be reduced by adding one or more additives selected from the group consisting of water, alcohols, ethers and phenols to the absorbing solution.
  • the additive-containing absorption liquid is supplied to the absorption tower, so that the additive-containing absorption liquid can absorb the acid gas in the absorption tower without substantially reducing the ability to absorb the acid gas, and the additive-containing absorption liquid
  • the absorption liquid flows smoothly and handling of the additive-containing absorption liquid becomes easy.
  • the additive-containing absorbent discharged from the separator / regenerator is supplied to the distillation separator to absorb the additive in the additive-containing absorbent. If the liquid is separated by distillation, the additive and the absorbent can be recovered in a separated state. As a result, the absorption liquid from which the additive has been removed is supplied to the absorption tower, and the additive from which the absorption liquid has been removed is supplied to the additive storage tank, so that the absorption liquid and the additive can be reused immediately.
  • the absorption gas can be absorbed by the absorption tower without reducing the ability of the absorption liquid to absorb the acid gas.
  • the liquid acidic gas (dispersed liquid) dispersed in the absorbing liquid can be aggregated.
  • the specific gravity difference between the liquid acidic gas and the flocculant-containing absorbent can be rapidly advanced in the separation regenerator, and then the flocculant-containing absorbent is separated by distillation. Liquid and Can be further separated.
  • the acid gas is CO gas, and the liquid in the separation regenerator is kept at a pressure of 4-25 MPa.
  • o can be separated by absorbing fluid force.
  • the above mixed gas is compressed by a compressor and supplied to the lower part of the absorption tower, and an absorption liquid mainly composed of one or both of an organic solvent and water is supplied from the upper part of the absorption tower to the absorption liquid.
  • the absorbing gas absorbs the acidic gas
  • the absorbing liquid that has absorbed the acidic gas is cooled by a cooler and supplied to the separation / regenerator. It can be separated and recovered from the absorption tower, and it can be separated and regenerated by separating the regenerator power in a state where the acid gas is liquefied in the separation regenerator. If the acidic gas is absorbed at the temperature of, a refrigerator can be eliminated.
  • the mixed gas is dehumidified by a dehumidifier and compressed by a compressor and supplied to the lower part of the absorption tower, and the absorbing liquid is supplied from the upper part of the absorbing tower, and the mixed gas is brought into contact with the absorbing liquid.
  • the absorption gas can be recovered by separating the non-acid gas from the acid gas in the absorption tower.
  • the separation regenerator the absorption liquid force can be separated and recovered from the separation regenerator while it is in the liquid state, and the absorption liquid can be regenerated and reused to absorb the acid gas at a temperature above room temperature. , Refrigerator can be eliminated.
  • the apparatus can be reduced in size. Also, there is a centrifuge between the cooler and the separator / regenerator! If a stirrer is provided, the absorption liquid containing acid gas is cooled to a temperature lower than the temperature in the absorption tower with a cooler, so that the acid gas in the absorption liquid becomes liquid and the absorption liquid Therefore, the absorption liquid containing the liquid acid gas is separated into the liquid acid gas and the absorption liquid before being supplied to the separation regenerator by centrifuging or stirring with a centrifuge or a stirrer. The As a result, liquid acid gas and absorption liquid can be phase-separated quickly in the separation regenerator, so that the liquid acid gas and absorption liquid And the liquid acid gas can be efficiently recovered.
  • the separation is maintained at a pressure substantially the same as the pressure in the absorption tower and lower than the temperature in the absorption tower.
  • an absorption liquid containing liquid acid gas is supplied to the regenerator, the absorption liquid and liquid acid gas are caused by the mutual insolubility and specific gravity difference between the liquid acid gas and the absorption liquid and the suction force of the magnetic absorption liquid by the magnet.
  • the liquid acid gas can be quickly recovered from the separation regenerator, and the regenerated absorption liquid after the liquid acid gas is removed is supplied to the upper part of the absorption tower by the circulation pump and can be reused quickly. .
  • an absorption liquid containing one or more additives selected from the group consisting of water, alcohols, ethers and phenols is stored, and this additive-containing absorption liquid is supplied to the absorption tower.
  • an absorption liquid tank is provided, the viscosity of the absorption liquid can be reduced by adding an additive to the absorption liquid in the absorption liquid tank.
  • the additive-containing absorption liquid can absorb the acid gas in the absorption tower with almost no decrease in the ability to absorb the acid gas, and the additive-containing absorption liquid flows smoothly and the additive-containing absorption liquid is handled. Becomes easier.
  • the additive storage tank in which the additive is stored is connected to the upper part of the separation regenerator, and a pressure adjusting means for adjusting the pressure in the separation regenerator is provided in the separation regenerator.
  • a pressure adjusting means for adjusting the pressure in the separation regenerator is provided in the separation regenerator.
  • the additive-containing absorbent that has also been discharged from the lower force of the separation regenerator is supplied to the distillation separator while the inside of the distillation separator is heated to a predetermined temperature by the heating means, the additive in the additive-containing absorbent is removed.
  • Absorption fluid power Is separated.
  • the absorption liquid from which the additive has been removed is supplied to the absorption tower, and the additive from which the absorption liquid has been removed is supplied to the additive storage tank.
  • the absorption liquid and the additive can be reused immediately after being supplied, and the absorption gas can be absorbed in the absorption tower without reducing the ability of the absorption liquid to absorb the acid gas at all.
  • the flocculant tank for storing the flocculant is connected to the separation regenerator, the flocculant stored in the flocculant tank is added to the absorbent containing the liquid acidic gas in the separation regenerator,
  • the liquid acidic gas (dispersed liquid) can be agglomerated by being dispersed in the absorbing liquid.
  • the specific gravity difference between the liquid acidic gas and the flocculant-containing absorbing liquid can be rapidly advanced in the separation regenerator, and then the flocculant-containing absorbing liquid can be separated by distillation. And can be further separated.
  • the acid gas is CO gas
  • the pressure is adjusted to maintain the pressure in the separation regenerator at 4 to 25 MPa.
  • the regulating means is installed in the separation regenerator and the water storage tank in which water is stored is connected to the lower part of the separation regenerator, the water is stored in the state where the pressure in the separation regenerator is kept at a high pressure of 4 to 25 MPa.
  • liquid C When water is supplied from the tank to the absorption liquid containing liquid CO in the regenerator, liquid C
  • this is a system installed in an on-vehicle reforming vehicle that uses a fuel cell as a drive source.
  • the fuel is reformed on the vehicle, converted to CO and removed to form a mixed gas of H and CO.
  • FIG. 1 is a cross-sectional configuration diagram of a gas purification method and apparatus according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional configuration diagram corresponding to FIG. 1 showing a second embodiment of the present invention.
  • FIG. 3 is a cross-sectional configuration diagram corresponding to FIG. 2 showing a third embodiment of the present invention.
  • FIG. 4 is a cross-sectional configuration diagram corresponding to FIG. 2 showing a fourth embodiment of the present invention.
  • FIG. 5 is a cross-sectional configuration diagram corresponding to FIG. 4 showing a fifth embodiment of the present invention.
  • FIG. 6 is a cross-sectional configuration diagram corresponding to FIG. 1 showing a sixth embodiment of the present invention.
  • FIG. 7 is a cross-sectional configuration diagram corresponding to FIG. 2 showing a seventh embodiment of the present invention.
  • FIG. 8 is a cross-sectional configuration diagram corresponding to FIG. 7 showing an eighth embodiment of the present invention.
  • FIG. 9 is a cross-sectional configuration diagram corresponding to FIG. 2 showing a ninth embodiment of the present invention.
  • FIG. 10 is a cross-sectional configuration diagram corresponding to FIG. 9 showing a tenth embodiment of the present invention.
  • FIG. 11 is a cross-sectional configuration diagram corresponding to FIG. 9 showing an eleventh embodiment of the present invention.
  • FIG. 12 is a cross-sectional configuration diagram corresponding to FIG. 11 showing a twelfth embodiment of the present invention.
  • FIG. 13 is a cross-sectional configuration diagram corresponding to FIG. 11 showing a thirteenth embodiment of the present invention.
  • FIG. 14 is a cross-sectional configuration diagram corresponding to FIG. 13 showing a fourteenth embodiment of the present invention.
  • FIG. 15 is a block diagram showing a system according to a fifteenth embodiment of the present invention.
  • FIG. 16 is a configuration diagram showing a system according to a sixteenth embodiment of the present invention.
  • Fig. 17 shows the solubility of CO gas in the absorbent of Example 1 at a measurement temperature of 35 ° C.
  • FIG. 18 shows H 2 S gas and COS in the absorption liquid of Example 1 at a measurement temperature of 35 ° C.
  • Fig. 19 shows the H gas, CH gas, and the like in the absorption liquid of Example 1 at a measurement temperature of 35 ° C.
  • Fig.20 shows the phase separation between the absorbing liquid (polyethylene glycol) and liquid CO FIG.
  • Fig. 21 shows the solubility of CO in the absorbents of Examples 2 to 5 at a measurement temperature of 35 ° C.
  • FIG. 2 is a diagram showing changes associated with pressure changes.
  • Fig. 22 shows the solubility of CO in the absorbing solutions of Examples 2 to 5 at a measurement temperature of 45 ° C.
  • FIG. 2 is a diagram showing changes associated with pressure changes.
  • FIG. 23 shows the solubility of CO in the absorbing solutions of Examples 2 to 5 at a measurement temperature of 55 ° C.
  • FIG. 2 is a diagram showing changes associated with pressure changes.
  • FIG. 24 is a graph showing a change in the solubility of the non-acidic gas in the absorbing liquid of Example 2 at a measurement temperature of 35 ° C. with a change in pressure.
  • FIG. 25 shows CO 2, H 2 S and CO into the absorption liquid of Example 2 at a measurement temperature of 35 ° C.
  • FIG. 26 is a photographic diagram showing the state of phase separation between the absorbing liquid (ionic liquid) and liquid CO.
  • the refining device is provided with a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas, a compressor 12 for compressing the dehumidified mixed gas, and extending in the vertical direction. Absorbed by supplying the gas mixture compressed in the lower part and absorbing liquid in the upper part, bringing the mixed gas into contact with the absorbing liquid to absorb the acidic gas into the absorbing liquid and separating the non-acidic gas by the acidic gas force The tower 13 and the absorbing liquid that has absorbed the acid gas are expanded and depressurized. The expansion turbine 14 is supplied with the expanded and depressurized absorbing liquid. In addition, a regeneration tower 16 that regenerates the absorption liquid and a circulation pump 17 that supplies the regenerated absorption liquid to the upper part of the absorption tower 13 are provided.
  • the mixed gas is a fuel gas such as a synthetic gas obtained by gasification, reforming or partial oxidation of fossil fuel, natural gas, or an exhaust gas discharged from a thermal power plant, a cement plant, a steel plant, a chemical plant, etc.
  • Acid gas is CO, H S, COS, SO, SO, NO, CS, HCN,
  • Gas is a group consisting of ⁇ , CH, CO, ⁇ , ⁇ , and hydrocarbon compounds with 2 to 10 carbon atoms.
  • hydrocarbon compound having 2 to L0 carbon atoms examples include C H, C H, C H, C H, C H, and C H. Also
  • the absorbing liquid is an ionic liquid or a composition containing the same as the main component. Has on and key-on.
  • the cation is [R, R, -NCH] ( ⁇ , ⁇ , -dialkylimid
  • R and R in the cation are alkyl groups having 1 to 18 carbon atoms or hydrogen, and X in the cation is 1) To 3), preferably [R, R'-NCH] + (+, ⁇ , -alkyl having an alkyl group of 1 to 10 carbon atoms)
  • Anions are also PF-, BF-, NO-, EtSO-, A1C1- and AlBr "
  • a gas supply pipe 18 that connects the compressor 12 and the absorption tower 13 in communication is provided with a precooler 19, and the mixed gas is brought to a predetermined temperature and a predetermined pressure by the compressor 12 and the precooler 19.
  • Each is maintained and supplied to the lower part of the absorption tower 13.
  • the temperature of the mixed gas supplied to the absorption tower 13, that is, the temperature in the absorption tower 13 is set to 0 to: L00 ° C., preferably 30 to 50 ° C., and is supplied to the absorption tower 13.
  • the pressure of the mixed gas, that is, the pressure in the absorption tower 13 is set to 1 to 25 MPa, preferably 4 to 10 MPa.
  • the temperature in the absorption tower 13 is limited to the range of 0 to L00 ° C.
  • a refrigerator is required if the temperature is less than 0 ° C, and if it exceeds 100 ° C, the energy required for raising the temperature is increased.
  • the pressure in the absorption tower 13 is limited to the range of l to 25MPa because the absorption amount of the acid gas absorption solution is less than IMPa, and if it exceeds 25MPa, the absorption tower 13 with high pressure resistance is required. This is because the cost increases.
  • the absorption tower 13 may be an absorption drum, it is desirable to use a multistage absorption tower 13 in order to improve the absorption efficiency of acid gas.
  • the regeneration tower 16 may be a regeneration drum, but it improves the regeneration efficiency of the absorption liquid. Therefore, it is desirable to use a multistage regeneration tower 16.
  • the first communication pipe 21 that connects the lower end of the absorption tower 13 and the expansion turbine 14 is provided with a pressure reducing valve 23, a flash drum 24, and a heat exchanger 26 in order from the absorption tower 13 side.
  • the absorbing liquid containing the acidic gas discharged from the lower end force of the absorption tower 13 by the pressure reducing valve 2 3 and the flash drum 24 is depressurized by a predetermined pressure, for example, 0.1 to 0.5 MPa from the pressure in the absorption tower 13.
  • the This dissipates only non-acidic gases such as H, CH, CO, O, and N contained in the absorbent.
  • the heat exchanger 26 is configured such that the high-temperature absorbent discharged from the lower end of the regeneration tower 16 gives heat to the low-temperature absorbent containing the acid gas discharged from the lower end of the flash drum 24. That is, the heat exchanger 26 is configured to heat the absorbing liquid containing the acidic gas from which the lower end force of the flash drum 24 is also discharged and to cool the high temperature absorbing liquid from which the lower end force of the regeneration tower 16 is also discharged. Is done.
  • the second communication pipe 22 that connects the expansion turbine 14 and the regeneration tower 16 to each other is provided with a heater 28, and the expansion turbine 14 and the heater 28 allow the absorption liquid containing the acid gas to be absorbed in the absorption tower 13. It is supplied to the upper part of the regeneration tower 16 while being maintained at a temperature equal to or higher than the temperature in the absorption tower 13 and maintained at a pressure lower than the pressure in the absorption tower 13. Specifically, the absorption liquid supplied to the regeneration tower 16 is set to a temperature of 30 to 200 ° C., preferably 30 to 100 ° C. The pressure of the liquid, that is, the pressure in the regeneration tower 16 is set to 0.1 to 5 MPa, preferably 0.1 to 3 MPa.
  • the temperature in the regeneration tower 16 is limited to the range of 30 to 200 ° C.
  • the temperature is lower than 30 ° C, it is disadvantageous for acid gas emission, and when it exceeds 200 ° C, the temperature rise energy increases.
  • the pressure in the regenerator 16 is limited to the range of 0.1 to 5 MPa because the pressure in the regenerator 16 becomes negative and the equipment becomes complicated if it is less than IMPa. This is because it is disadvantageous for the emission of acid gas.
  • the absorbing solution is preferably neutral or alkaline. This is because if the absorbing liquid is acidic, the amount of acidic gas absorbed per unit volume, that is, the solubility of the acidic gas is reduced. In order to make the absorption liquid alkaline, an alkaline ionic liquid is used, or alkali is added to the absorption liquid. [0041] A method for purifying a gas using the thus configured purifying apparatus will be described.
  • the circulation pump 17 and the auxiliary compressor 27 are operated in advance, and a refrigerant such as water, air, or ammonia is allowed to flow through the precooler 19 and the aftercooler 29, and the heater 28
  • the heater is energized to circulate the absorption liquid, and the temperature of the absorption liquid supplied to the absorption tower 13 and the regeneration tower 16 is set to a predetermined temperature.
  • the mixed gas is dehumidified by the dehumidifier 11. As a result, water that reduces the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas column, and the solubility of the acid gas in the absorbing liquid can be increased.
  • the dehumidified mixed gas is heated or cooled to a predetermined temperature by the compressor 12 and the precooler 19 and supplied to the lower part of the absorption tower 13 in a state where the pressure is increased to a predetermined pressure.
  • the mixed gas comes into contact with the absorbing solution and the acidic gas is absorbed into the absorbing solution, so that the non-acidic gas is separated from the acidic gas column and recovered from the upper end column of the absorption tower 13.
  • the above non-acid gas mixed gas of H, CH, CO, O, N, etc.
  • the non-acidic gas is once depressurized using an expansion turbine or an adiabatic expansion valve.
  • this low-temperature non-acidic gas can be used as the refrigerant of the precooler 19 or the aftercooler 29.
  • an expansion turbine is used for decompression of the non-acidic gas, power can be generated by this expansion turbine, so that the electric power can be used for consumption in the V where the refining device of this embodiment is installed.
  • the absorbing liquid containing a large amount of acidic gas and a small amount of non-acidic gas discharged from the lower end of the absorption tower 13 is depressurized by a predetermined pressure by the pressure reducing valve 23 and the flash drum 24.
  • the pressure reducing valve 23 and the flash drum 24 As a result, only non-acidic gases such as H, CH, CO, O, and N contained in the absorbing solution are diffused and
  • the dissipated non-acid gas also discharges the upper end force of the flash drum 24 and is further pressurized by the auxiliary compressor 27 and returned to the absorption tower 13 again.
  • the absorption liquid containing the acid gas discharged from the lower end force of the flash drum 24 is heated by the regenerated absorption liquid by heat exchange, then expanded and depressurized by the expansion turbine 14, and further heated to a predetermined temperature by the heater 28. , Supplied to the upper part of the regeneration tower 16. That is, the absorption liquid heated by the heat exchanger 26 is equal to the temperature in the absorption tower 13 by the expansion turbine 14 and the heater 28.
  • the regeneration tower 16 is supplied to the upper portion of the regeneration tower 16 while maintaining a temperature higher than the temperature in the absorption tower 13 and maintaining a pressure lower than the pressure in the absorption tower 13.
  • the absorption liquid is set to such a pressure and temperature
  • the acid gas contained in the absorption liquid is released in the second communication pipe 22 or the regeneration tower 16, so that the acid gas is separated by the absorption liquid force and the regeneration tower 16 The upper end force of is recovered.
  • the regenerated absorption liquid that does not contain the acidic gas discharged from the bottom end of the regeneration tower 16 is conveyed by the circulation pump 17 and cooled to a predetermined temperature by the heat exchanger 26 and the after cooler 29. , Supplied to the upper part of the absorption tower 13 and reused.
  • Acid gas is CO gas
  • the refining device is supplied with a compressor 12 that compresses a mixed gas containing acidic gas and non-acidic gas, and a mixed gas that extends in the vertical direction and is compressed in the lower part.
  • the absorption liquid 42 is supplied to the absorption liquid 42, and the mixed gas is brought into contact with the absorption liquid 42 to absorb the acidic gas into the absorption liquid 42, and the non-acidic gas is separated and recovered, and the absorption tower 13 absorbs the acidic gas.
  • the cooler 47 that cools the absorbed liquid 42 and the cooled absorbent 42 are supplied to separate the liquid acidic gas 41 from the absorbent 42 due to the mutual insolubility and specific gravity difference between the liquid acidic gas 41 and the absorbent 42.
  • a regenerator 46 that regenerates and reuses the absorbing liquid 42 and a circulation pump 17 that supplies the regenerated absorbing liquid 42 to the upper portion of the absorption tower 13 with high pressure.
  • the mixed gas is the same as the mixed gas of the first embodiment.
  • the absorbing liquid is a liquid excluding an ionic liquid, and specifically, a liquid composed of one or both of an organic solvent and water, or an organic solvent or water, or one or both of them as a main component. It is a liquid.
  • the organic solvent use a polar organic solvent that has a large absorption capacity for acid gas and does not dissolve in liquid acid gas (liquid CO, etc.) with high density and low vapor pressure.
  • the organic solvent is preferably one or two or more polymers selected from the group consisting of polyethylene glycol, polybutyl alcohol, polyether, polyester, polyalkane and polyolefin ion.
  • water is acid It has a relatively large absorption capacity for chemical gases, and does not dissolve much with liquid acid gases (liquid CO, etc.) with relatively high density and relatively low vapor pressure.
  • a gas supply pipe 18 that connects the compressor 12 and the absorption tower 13 in communication is provided with a precooler 19, and the mixed gas is brought to a predetermined temperature and a predetermined pressure by the compressor 12 and the precooler 19.
  • Each is maintained and supplied to the lower part of the absorption tower 13.
  • the temperature of the mixed gas supplied to the absorption tower 13, that is, the temperature in the absorption tower 13 is set to 0 to: L00 ° C., preferably 30 to 50 ° C., and is supplied to the absorption tower 13.
  • the pressure of the mixed gas, that is, the pressure in the absorption tower 13 is set to 4 to 25 MPa, preferably 6 to 10 MPa.
  • the temperature in the absorption tower 13 is limited to the range of 0 to L00 ° C.
  • a refrigerator is required if the temperature is less than 0 ° C, and if it exceeds 100 ° C, the energy required for raising the temperature is increased.
  • the pressure in the absorption tower 13 is limited to the range of 4 to 25 MPa. If the pressure is less than 4 MPa, the amount of absorption by the absorbing solution of the acidic gas decreases, and if it exceeds 25 MPa, the absorption tower 13 with high pressure resistance is required. This is because the cost increases.
  • the absorption tower 13 may be an absorption drum, it is desirable to use a multistage absorption tower 13 in order to improve the absorption efficiency of acid gas.
  • the first communication pipe 21 that connects the lower end of the absorption tower 13 and the cooler 47 is provided with a pressure reducing valve 23, a flash drum 24, and a heat exchanger 26 in order from the absorption tower 13 side.
  • the absorbing solution containing the acidic gas discharged from the lower end force of the absorption tower 13 by the pressure reducing valve 23 and the flash drum 24 is depressurized by a predetermined pressure, for example, 0.1 to 0.5 MPa from the pressure in the absorption tower 13. This is because of the H, CH, CO, O, N, and carbon compounds from 2 to L0 contained in the absorbent.
  • the heat exchanger 26 is configured such that the high-temperature absorption liquid discharged from the lower end of the separation regenerator 46 gives heat to the low-temperature absorption liquid containing acid gas discharged from the lower end of the flash drum 24. The That is, the heat exchanger 26 heats the absorption liquid containing the acid gas discharged from the lower end of the flash drum 24 and cools the high-temperature absorption liquid discharged from the lower end force of the separation regenerator 46. Configured.
  • the cooler 47 causes the absorption liquid 42 containing acid gas to be almost the same as the pressure in the absorption tower 13. And supplied to the separation regenerator 46 while being cooled to a temperature lower than that in the absorption tower 13. Specifically, the pressure of the absorption liquid 42 supplied to the separation regenerator 46, that is, the pressure in the separation regenerator 46 is the same as the pressure in the absorption tower 13, which is slightly higher than the pressure in the absorption tower 13.
  • Pressure or slightly lower than the pressure in the absorption tower 13 4 to 25 MPa, preferably 6 to:
  • the temperature of is lower than the temperature in the absorption tower 13-30 to 30 ° C, preferably 0 to 20 ° C.
  • the pressure in the separation regenerator 46 is the same as the pressure in the absorption tower 13, a pressure slightly higher than the pressure in the absorption tower 13, or a pressure slightly lower than the pressure in the absorption tower 13 to 4 to 25 MPa.
  • the reason for limiting to this range is to liquefy the acid gas and to reduce the consumption of circulating energy of the absorbing liquid.
  • the reason why the temperature in the separation regenerator 46 is limited to the range of 30 to 30 ° C is that the cooling energy increases when the temperature is lower than 30 ° C, and the acidic gas such as CO becomes liquid when the temperature exceeds 30 ° C. Because it becomes difficult. Note that the separation regenerator 46
  • the pressure difference is within the range of 0.1 to 3MPa, where the acidic gas can be liquefied by the above temperature drop.
  • the pressure difference is preferably in the range of 0.1 to 3 MPa at which the acidic gas can be liquefied by the temperature drop.
  • liquid acid gas 41 is liquid CO, and
  • the specific gravity of the absorbing liquid is 1.2 to 1.6
  • the specific gravity of liquid CO is 0.8.
  • the heat exchanger 26 is configured such that the lower temperature absorbent 42 discharged from the lower end force of the separation regenerator 46 takes heat away from the low temperature absorbent containing the acid gas from which the lower end force of the flash drum 24 is also discharged. Is done. That is, the heat exchanger 26 further cools the absorbing liquid 42 containing the acid gas discharged from the lower end of the flash drum 24 and the lower temperature absorbing liquid discharged from the lower end force of the separation regenerator 46. Configured to heat 42.
  • a centrifuge 48 is provided in the second communication pipe 22 between the cooler 47 and the separation regenerator 46.
  • the lower end of the separator / regenerator 46 is connected to the upper portion of the absorption tower 13 by a second return pipe 32, and the circulating pump 17 is provided in the second return pipe 32.
  • a stirrer may be installed in the centrifuge.
  • the circulation pump 17 and the auxiliary compressor 27 are operated in advance, and a refrigerant such as water, air, or ammonia is allowed to flow through the pre-cooler 19 and the cooler 47. 48 is rotated to circulate the absorption liquid, and the temperature of the absorption liquid 42 supplied to the absorption tower 13 and the separation regenerator 46 is set to a predetermined temperature.
  • the mixed gas is heated or cooled to a predetermined temperature by the compressor 12 and the precooler 19 and supplied to the lower part of the absorption tower 13 in a state where the pressure is increased to a predetermined pressure.
  • the mixed gas comes into contact with the absorbing liquid 42 and the acidic gas is absorbed by the absorbing liquid 42, so that the non-acidic gas is separated from the acidic gas and the upper end force of the absorption tower 13 is also recovered. If the pressure of the recovered non-acid gas is higher than the pressure required on the user side, for example, the non-acid gas (H, CH, CO, O, N
  • the absorbing liquid containing a large amount of acidic gas and a small amount of non-acidic gas discharged from the lower end of the absorption tower 13 is depressurized by a predetermined pressure by the pressure reducing valve 23 and the flash drum 24.
  • H, CH, CO, O, N, carbon number 2 ⁇ hydrocarbon compounds up to L0 contained in the absorption liquid
  • the dissipated non-acid gas also discharges the upper end force of the flash drum 24 and is further pressurized by the auxiliary compressor 27 and returned to the absorption tower 13 again.
  • the lower end force of the flash drum 24 The discharged absorbing liquid 42 containing acid gas is cooled by the regenerated absorbing liquid by heat exchange 26, and further cooled by a cooler 47. At this time, the acidic gas in the absorbing liquid is liquidated and dispersed in the absorbing liquid 42. .
  • the absorption liquid 42 containing the liquid acid gas 41 is substantially separated into the liquid acid gas 41 and the absorption liquid 42 by the centrifugal separator 48 due to the specific gravity difference between the liquid acid gas 41 and the absorption liquid 42, and is then supplied to the separation regenerator 46. Supplied.
  • the liquid acid gas 41 has a lower specific gravity than the absorption liquid 42, so the liquid acid gas 41 moves in a direction away from the rotation center force of the centrifuge 48, and the absorption liquid 42 moves to the rotation center of the centrifuge 48. Move in the direction you approach.
  • the absorption liquid 42 is kept almost the same as the pressure in the absorption tower 13 by the heat exchanger 26 and the cooler 47 and is made lower than the temperature in the absorption tower 13, so that the gas in the absorption liquid 42 becomes liquid. Then, the liquid is further separated into the liquid acid gas 41 and the absorbing liquid 42 by the centrifuge 48, and then supplied to the separation regenerator 46.
  • the absorption liquid 42 containing the liquid acid gas 41 supplied to the separation regenerator 46 in a state of being substantially separated into the liquid acid gas 41 and the absorption liquid 42 is the mutual insolubility and specific gravity of the liquid acid gas 41 and the absorption liquid 42. Due to the difference, the liquid acid gas 41 and the absorbing liquid 42 are rapidly phase-separated.
  • the specific gravity of the liquid acid gas 41 is smaller than that of the absorbing liquid 42, so that the liquid acidic gas 41 quickly floats and shifts to the upper phase, and the absorbing liquid 42 quickly sinks and shifts to the lower phase.
  • the liquid acid gas 41 is separated from the absorbing liquid 42 and the upper force of the separation regenerator 46 is efficiently recovered in a relatively short time.
  • the regenerated absorbent 42 containing no acid gas discharged from the lower end force of the separation regenerator 46 is transported by the circulation pump 17 and heated to a predetermined temperature by heat exchange 26, and then It is supplied to the upper part and reused.
  • the liquid acidic gas 41 is liquid CO
  • part or all of the recovered liquid CO is opened in the pressure reducing valve.
  • FIG. 3 shows a third embodiment.
  • the same reference numerals as those in FIG. 2 denote the same parts.
  • an ionic liquid or a liquid mainly composed of an ionic liquid is used as an absorbing liquid, and a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas is provided in front of the compressor 12.
  • the configuration is the same as that of the second embodiment except for the above.
  • the mixed gas is dehumidified by the dehumidifier 11 and an ionic liquid is used as the absorbing liquid 42. Since the operation other than the above is substantially the same as the operation of the first embodiment, repeated description will be omitted.
  • dehumidifying the mixed gas with the dehumidifier 11 In addition, moisture that decreases the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas column, and the solubility of the acid gas in the absorbing liquid can be increased.
  • FIG. 4 shows a fourth embodiment.
  • the same reference numerals as those in FIG. 2 denote the same parts.
  • the pressure reducing valve, the flash drum, the auxiliary compressor, and the heat exchanger of the second embodiment are not used, and the absorption tower 13, the cooler 47, the centrifuge 48, and the separation regenerator 46 are the same.
  • the upward force is also provided integrally in a state of being aligned vertically in the downward direction.
  • the absorbing liquid 42 a liquid having either or both of an organic solvent and water, or a liquid mainly containing either or both of the organic solvent and water is used.
  • the configuration other than the above is the same as that of the second embodiment.
  • the absorption tower 13, the cooler 47, the centrifuge 48, and the separation regenerator 46 are integrally provided, so that the apparatus can be downsized. Since the operation other than the above is substantially the same as the operation of the second embodiment, repeated description will be omitted.
  • the liquid acidic gas 41 is liquid CO, part or all of the recovered liquid CO is opened in the pressure reducing valve.
  • FIG. 5 shows a fifth embodiment.
  • the same reference numerals as those in FIG. 4 denote the same parts.
  • an ionic liquid or a liquid mainly composed of an ionic liquid is used as an absorbing liquid, and a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas is provided in front of the compressor 12.
  • the configuration is the same as that of the fourth embodiment except for the above.
  • the mixed gas is dehumidified by the dehumidifier 11 and an ionic liquid is used as the absorbing liquid 42. Since the operation other than the above is substantially the same as the operation of the fourth embodiment, the repeated description is omitted.
  • dehumidifying the mixed gas with the dehumidifier 11 moisture that decreases the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas tank, and the solubility of the acidic gas in the absorbing liquid is increased. can do.
  • FIG. 6 shows a sixth embodiment.
  • a porous membrane is impregnated with an ionic liquid or an absorption liquid containing the ionic liquid as a main component to form a liquid membrane 51.
  • the liquid membrane 51 is stretched in a membrane separator 52 to form a membrane fraction.
  • the separator 52 is divided into a first chamber 52a and a second chamber 52b, the first chamber 52a is set to a pressure higher than that of the second chamber 52b, and a mixed gas containing acidic gas and non-acidic gas in the first chamber 52a. Is configured to be introduced.
  • the gas supply pipe 18 is provided with a compressor 12 and a precooler 19. A method for purifying a gas using the purification apparatus configured as described above will be described.
  • the mixed gas is introduced into the first chamber 52a of the membrane separator 52 while being pressurized to a predetermined pressure by the compressor 12 and the precooler 19.
  • the non-acidic gas remains in the first chamber 52a, and the acidic gas passes through the liquid film 51 and flows into the second chamber 52b, so that the mixed gas is separated into acidic gas and non-acidic gas.
  • FIG. 7 shows a seventh embodiment.
  • the absorbing liquid 42 which is a liquid composed mainly of one or both of an organic solvent and water, or a liquid mainly composed of one or both of the organic solvent and water, has magnetism.
  • a magnet 61 is provided at the lower part of the separation regenerator 46.
  • the absorbing liquid 42 having magnetism include a low-temperature molten salt (normal temperature molten salt) containing Fe element in the ion.
  • the magnet 61 is provided on the lower inner surface of the separation regenerator 46.
  • the separation regenerator 46 is preferably formed of a nonmagnetic material so as not to be affected by the magnet 61.
  • the configuration other than the above is the same as that of the second embodiment.
  • the absorption liquid 42 containing the liquid acidic gas 41 When the absorption liquid 42 containing the liquid acidic gas 41 is supplied to the separation regenerator 46 maintained at a pressure almost the same as the pressure in the absorption tower 13 and maintained at a temperature lower than the temperature in the absorption tower 13, the absorption The liquid acid gas 41 has a lower specific gravity than the liquid 42. Therefore, the liquid acid gas 41 and the absorbing liquid 42 are absorbed by the mutual insolubility and specific gravity difference of the liquid acid gas 41 and the magnet 61 of the absorbing liquid 42 having magnetism. It is quickly separated into liquid 42 and liquid acid gas 41. That is, the liquid acidic gas 41 quickly moves to the upper phase, and the absorbing liquid 42 quickly moves to the lower phase.
  • the liquid acid gas 41 can be quickly recovered from the separator / regenerator 46, and the regenerated absorbent 42 after the liquid acid gas 41 is removed is supplied to the upper portion of the absorption tower 13 by the circulation pump 17. Can be reused promptly. Since the operation other than the above is substantially the same as the operation of the second embodiment, repeated description will be omitted.
  • FIG. 8 shows an eighth embodiment.
  • the same reference numerals as those in FIG. 7 denote the same parts.
  • an ionic liquid or a liquid mainly composed of an ionic liquid is used as an absorbing liquid, and a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas is provided in front of the compressor 12. Except for this, the configuration is the same as that of the seventh embodiment.
  • the mixed gas is dehumidified by the dehumidifier 11 and an ionic liquid is used as the absorbing liquid 42. Since the operation other than the above is substantially the same as the operation of the seventh embodiment, repeated description will be omitted.
  • dehumidifying the mixed gas with the dehumidifier 11 moisture that decreases the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas tank, and the solubility of the acidic gas in the absorbing liquid is increased. can do.
  • FIG. 9 shows a ninth embodiment.
  • an absorption liquid storage tank 72 in which the absorption liquid 42 to which the additive 71 is added is stored.
  • the absorbing liquid 42 either an organic solvent or water or a liquid having a bi-directional force, or a liquid mainly containing either or both of an organic solvent and water is used.
  • the additive 71 includes one or more additives selected from the group consisting of water, alcohols, ethers and phenols.
  • the additive 71 may be one or more additives selected from the group consisting of alcohols, ethers and phenols.
  • examples of alcohols include methanol and ethanol
  • examples of ethers include dimethyl ether and ethyl ether
  • examples of phenols include phenol and the like.
  • These additives 71 should hardly interfere with the ability of the absorbent 42 to absorb acid gases.
  • the absorbent 42 in the absorbent reservoir 72 is added with 1 to 50% by weight, preferably 5 to 10% by weight, of the additive with respect to 100% by weight of the absorbent.
  • the additive was limited to the range of 1 to 50% by weight. If the amount is less than 1% by weight, the effect of reducing the viscosity of the absorbent 42 cannot be obtained so much. This is an adverse effect on the absorption performance of acid gas by the absorbent 42.
  • a stirrer 73 is provided in order to uniformly disperse the additive 71 in the absorbing liquid.
  • the lower part of the absorption liquid storage tank 72 is connected to the upper part of the absorption tower 13 by an absorption liquid supply pipe 74.
  • the absorption liquid supply pipe 74 includes an absorption liquid supply pump 76 for supplying the additive-containing absorption liquid 75 in the absorption liquid storage tank 72 to the upper part of the absorption tower 13, and an on-off valve for opening and closing the absorption liquid supply pipe 74 7 7 And force S is provided.
  • the configuration other than the above is the same as that of the second embodiment.
  • the additive 71 is added to the absorbent 42 in the absorbent reservoir 72 and mixed by the stirrer 73, the additive 71 is dispersed in the absorbent 42 and the viscosity of the absorbent 42 decreases.
  • the opening / closing valve 77 is opened, and the additive-containing absorbing liquid 75 is supplied to the upper portion of the absorption tower 13 by the absorbing liquid supply pump 76, and then the opening / closing valve 77 is closed.
  • the additive-containing absorption liquid 75 is circulated between the absorption tower 13 and the separation regenerator 46 by the circulation pump 17.
  • the absorption tower 13 As a result, it is possible to absorb the acid gas in the absorption tower 13 without substantially reducing the ability of the additive-containing absorbing liquid 75 to absorb the acid gas.
  • the low-viscosity additive-containing absorption liquid 75 smoothly circulates between the absorption tower 13 and the separation regenerator 46, so that the absorption liquid can be handled easily. Since the operation other than the above is substantially the same as the operation of the first embodiment, repeated description will be omitted.
  • FIG. 10 shows a tenth embodiment.
  • the same reference numerals as those in FIG. 9 denote the same parts.
  • an ionic liquid or a liquid mainly composed of an ionic liquid is used as an absorbing liquid, and a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas is provided in front of the compressor 12. It is done.
  • Additive 71 includes polar solvents, that is, one or more additives selected from the group consisting of water, alcohols, ethers, and phenols. Specifically, methanol and ethanol are exemplified as alcohols, dimethyl ether and ethyl ether are exemplified as ethers, and phenol and the like are exemplified as phenols.
  • the configuration other than the above is the same as that of the ninth embodiment.
  • the mixed gas is dehumidified by the dehumidifier 11 and an ionic liquid is used as the absorbing liquid 42. Since the operation other than the above is substantially the same as the operation of the fourth embodiment, the repeated description is omitted.
  • dehumidifying the mixed gas with the dehumidifier 11 moisture that decreases the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas tank, and the solubility of the acidic gas in the absorbing liquid is increased. can do.
  • water as the additive 71 is circulated in the absorption tower 13. Therefore, before supplying the water to the absorption tower 13, acid gas containing CO gas is removed by the dehumidifier 11. No need to dehumidify
  • the dehumidifier 11 is not provided, the dehumidifier 11 is provided when the amount of water in the absorbent 42 circulated to the absorption tower 13 increases beyond the range of the additive amount added. Better. As a result, it is possible to prevent a significant decrease in the ability to absorb CO by the absorbent 42.
  • FIG. 11 shows an eleventh embodiment.
  • the same reference numerals as those in FIG. 9 denote the same parts.
  • an additive storage tank 81 in which the additive 71 is stored is connected to the upper part of the separation regenerator 46, the pressure adjusting means 82 is provided in the separation regenerator 46, and a distillation is performed at the lower part of the separation regenerator 82.
  • a separator 83 is connected, and the distillation separator 83 is provided with heating means 84.
  • the absorbing liquid 42 a liquid having either or both of an organic solvent and water, or a liquid mainly containing either or both of the organic solvent and water is used.
  • the additive 71 includes one or more additives selected from the group consisting of water, alcohols and ethers.
  • the additive 71 includes one or both of alcohols and ethers.
  • the lower part of the distillation separator 83 is connected to the suction port of the circulation pump 17 by the second return pipe 32.
  • the pressure in the separation regenerator 46 is adjusted to 4 to 25 MPa, preferably 6 to: LOMPa by the pressure adjusting means 82.
  • the temperature in the distillation separator 83 is adjusted to 50 to 250 ° C, preferably 100 to 150 ° C by the heating means 84.
  • the reason why the pressure in the separation regenerator 46 adjusted by the pressure adjusting means 82 is limited to the range of 4 to 25 MPa is that a gas phase may be generated if the pressure is less than 4 MPa, and if it exceeds 25 MPa, the equipment cost is increased.
  • the temperature in the distillation separator 83 adjusted by the heating means 84 is limited to the range of 50 to 250 ° C. It is difficult to completely separate the additive 71 below 50 ° C. It is because the energy of this is needed.
  • a check valve 86 is provided in the second communication pipe 22 between the centrifuge 48 and the separation regenerator 46.
  • This check valve 86 permits the flow of the additive-containing absorbent 75 from the centrifuge 48 to the separator / regenerator 46, and allows the additive-containing absorbent 75 to flow from the separator / regenerator 46 to the centrifuge 48. Configured to block flow.
  • the phenolic power of the sixth embodiment S The additive power of the seventh embodiment is also excluded because it is separated by a distillation operation where the boiling point of phenols is high ( This is because it cannot be completely separated without heating. Other than the above, the configuration is the same as that of the ninth embodiment.
  • the temperature in the separation regenerator 46 is adjusted to the range of 0 to 30 ° C by the cooler 47, and the pressure in the separation regenerator 46 is adjusted to the range of 4 to 25 MPa by the pressure force adjusting means 82.
  • additive 71 is supplied to separator / regenerator 46 together with absorption liquid 42 containing gas 41, mutual insolubility and specific gravity difference between liquid acid gas 41 and additive-containing absorption liquid 75, and mutual dissolution with respect to absorption liquid 42. And regenerating by replacing the liquid acid gas 41 dispersed in the absorption liquid 42 with the additive 71 with the additive 71, which is soluble and mutually insoluble in the liquid acid gas 41.
  • Liquid acid gas 41 is transferred to the upper phase of the vessel 46, and the additive-containing absorbent 75 is transferred to the lower phase of the separator / regenerator 46, so that the liquid acid gas 41 and the additive-containing absorbent 75 are rapidly separated.
  • the additive-containing absorbent 75 discharged from the lower part of the separator / regenerator 46 while the inside of the distillation separator 83 is heated to a temperature of 50 to 250 ° C., preferably 100 to 150 ° C. by the heating means 84. Is fed to the distillation separator 83, the additive 71 in the additive-containing absorbent 75 is distilled and separated from the absorbent 42.
  • the additive 71 and the absorbing liquid 42 can be recovered in a separated state, the absorbing liquid 42 from which the additive 71 has been removed is supplied to the absorption tower 13, and the additive 71 from which the absorbing liquid 42 has been removed is added.
  • the absorbent 42 and the additive 71 can be reused immediately after being supplied to the agent storage tank 81, and the absorption gas 13 is absorbed in the absorption tower 13 without degrading the ability of the absorbent 42 to absorb the acid gas. can do. Since operations other than those described above are substantially the same as those of the second embodiment, repeated description will be omitted. ⁇ Twelfth Embodiment>
  • FIG. 12 shows a twelfth embodiment.
  • the same reference numerals as those in FIG. 11 denote the same parts.
  • an ionic liquid or a liquid mainly composed of an ionic liquid is used as an absorbing liquid, and a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas is provided in front of the compressor 12. It is done.
  • the additive storage tank 81 stores a polar solvent, that is, one or more additives 71 selected from the group consisting of water, alcohols and ethers. The configuration other than the above is the same as that of the eleventh embodiment.
  • the mixed gas is dehumidified by the dehumidifier 11 and an ionic liquid is used as the absorbing liquid 42. Since the operation other than the above is substantially the same as the operation of the eleventh embodiment, repeated description will be omitted.
  • dehumidifying the mixed gas with the dehumidifier 11 moisture that decreases the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas tank. Solubility can be increased.
  • FIG. 13 shows a thirteenth embodiment.
  • the same reference numerals as those in FIG. 11 denote the same parts.
  • the acidic gas is CO gas
  • the pressure in the separation regenerator 46 is 4 to 2
  • a pressure adjusting means 82 for maintaining LOMPa is provided in the separation regenerator 46, and a water storage tank 91 in which water is stored is connected to the lower part of the separation regenerator 46.
  • a solid-liquid separator 92 is connected to the separation regenerator 46, and a sub-separation regenerator 93 is connected to the upper part of the solid-liquid separator 92.
  • the lower part of the sub separation regenerator 93 is connected to the suction port of the circulation pump 17 by the second return pipe 32.
  • the pressure in the separation regenerator 46 adjusted by the pressure adjusting means 82 is limited to the range of 4 to 25 MPa. If the pressure is less than 4 MPa, CO hydrate is generated.
  • Examples of the solid-liquid separator 92 include a filter and a centrifugal separator.
  • a liquid composed of one or both of an organic solvent and water, or a liquid mainly composed of one or both of the organic solvent and water is used.
  • the configuration other than the above is the same as that of the eleventh embodiment. A method for purifying a gas using the purification apparatus configured as described above will be described.
  • liquid CO and absorption liquid in the solid-liquid separator 92 are sub-separated and regenerated.
  • the liquid CO 41 and the absorbing liquid 42 are insoluble in each other and due to the difference in specific gravity.
  • the liquid CO 41 can be separated from the absorbing liquid 42 more quickly.
  • FIG. 14 shows a fourteenth embodiment.
  • the same reference numerals as those in FIG. 13 denote the same parts.
  • an ionic liquid or a liquid mainly composed of an ionic liquid is used as an absorbing liquid, and a dehumidifier 11 for dehumidifying a mixed gas containing acidic gas and non-acidic gas is provided in front of the compressor 12. Except for this, the configuration is the same as that of the thirteenth embodiment.
  • the mixed gas is dehumidified by the dehumidifier 11 and an ionic liquid is used as the absorbing liquid 42. Since the operation other than the above is substantially the same as the operation of the thirteenth embodiment, the repeated description is omitted.
  • dehumidifying the mixed gas with the dehumidifier 11 moisture that decreases the solubility of the acid gas in the absorbing liquid can be removed in advance from the mixed gas tank. Solubility can be increased.
  • FIG. 15 shows a fifteenth embodiment.
  • the fuel is reformed, CO transformed and CO removed to mix H and CO.
  • this mixed gas is separated and recovered into H and CO using any of the gas purification methods or gas purification apparatuses of the first to fourteenth embodiments described above, and this separation circuit is further recovered.
  • the collected H is supplied to the hydrogen station, and the separated and recovered CO is adiabatically expanded. And configured to produce dry ice (solid CO 2).
  • solid CO 2 dry ice
  • fuels selected from the group consisting of hydrogen, naphtha, kerosene, methanol, dimethyl ether, liquid petroleum gas, and natural gas.
  • This reforming of fuel is steam reforming, partial oxidation, or supercritical water reforming.
  • the remaining CO is removed.
  • the remaining mixed gas of H and CO is the above first to 14th.
  • High pressure H is a hydrogen station
  • part or all of the recovered liquid CO is adiabatic and expanded by opening the pressure reducing valve.
  • CO is in a gaseous state
  • Part or all of CO is sold as a product by adiabatic expansion by opening the pressure reducing valve.
  • FIG. 16 shows a sixteenth embodiment.
  • the fuel is reformed on the vehicle, CO is transformed, and CO is removed to remove H and CO.
  • the mixed gas of 2 2 is obtained, the mixed gas is separated and recovered into H and CO by using either the gas purification method or the gas purification apparatus of the first to fourteenth embodiments, and further this
  • the fuel include one or more fuels selected from the group consisting of desulfurized gasoline, naphtha, kerosene, methanol, dimethyl ether, liquid petroleum gas, and natural gas.
  • the reforming of this fuel is steam reforming, and the fuel is reformed into H and CO by this steam reforming. Also, most of CO is transformed into CO by CO transformation
  • the combined gas is separated into high-pressure H and liquid CO using any of the gas purification methods or gas purification apparatuses of the first to fourteenth embodiments. Furthermore, the high pressure H is supplied to the fuel cell.
  • liquid CO is temporarily stored in the vehicle and later collected. This As a result, liquid CO can be efficiently recovered while producing various types of fuel-powered high-pressure H.
  • One or more additives selected from the group consisting of water, alcohols, ethers and phenols may be added to the absorbent of the purification apparatus shown in the first embodiment.
  • the absorption liquid smoothly flows without reducing the ability of the absorption liquid to absorb the acidic gas, making it easy to handle the absorption liquid and reducing the viscosity due to the additive. Can be separated by distillation.
  • a flocculant to the absorption liquid containing the liquid acidic gas in a separation regenerator.
  • a flocculant tank for storing the flocculant is connected to the separation regenerator.
  • the flocculant stored in the flocculant tank to the absorbent containing the liquid acidic gas in the separation regenerator, the liquid acidic gas (dispersed liquid) dispersed in the absorbent is agglomerated or minutely dispersed.
  • the pressure in the separation regenerator is set to 4 to 25 MPa, and the temperature is set to 0 to 30 ° C, the inside of the separation regenerator Since the specific gravity difference separation between the liquid acid gas and the flocculant-containing absorption liquid proceeds promptly, the liquid acid gas and the flocculant-containing absorption liquid are quickly separated, and the flocculant-containing absorption liquid is supplied to the distillation separator.
  • the lower part of the separation regenerator is connected to a distillation separator with heating means, the lower part of the distillation separator is connected to the inlet of the circulation pump, and the upper part of the distillation separator is further connected to the flocculant tank. Separation of specific gravity between the liquid acidic gas and the flocculant-containing absorbent proceeds rapidly in the regenerator, and the flocculant in the distillation separator is separated from the absorbent by distillation. It is quickly separated from the liquid and only the absorption liquid is supplied to the absorption tower.
  • the refining method or refining apparatus of the second to fifth and seventh to fourteenth embodiments described above is applied to a high-pressure gas source discharged from a petroleum refinery plant or an ammonia plant, steel exhaust gas with high CO (
  • these gas sources may be supplied to the absorption tower of the purification method or purification apparatus of the first to fourteenth embodiments to produce liquid CO or dry ice. 2-5 and 7 above
  • the purification method or purification apparatus of the embodiment of -14 basically uses a physical absorption method. Therefore, it accounts for 70-80% of the running cost of a conventional (existing) liquid CO production plant
  • Example 1 Commercially available primary polyethylene glycol having an average molecular weight of 200 was used as the absorbing solution. This absorbing solution was designated as Example 1.
  • Example 1 The absorption liquid of Example 1 was contacted with high purity CO gas having a purity of 99.99% by volume.
  • the constant temperature was kept constant at 35 ° C, and the pressure was changed stepwise from atmospheric pressure to 0.5 MPa. From the total amount of CO gas that is the raw material gas and the amount of CO gas that has not been absorbed, the absorption of CO gas
  • the purity of S gas was as high as 99.9% by volume. Specifically, using a high-pressure gas-liquid equilibrium measurement device, the solubility of the above HS gas and COS gas in the absorbing solution
  • a gas-liquid equilibrium test with a non-acid gas was carried out separately for each type of gas.
  • the purity of H gas is 99.99% by volume or higher, and the purity of CH gas is 99.97% by volume or higher.
  • the purity of CO gas is 99.97 volume% or more, and the purity of N gas is 99.999 volume
  • the constant temperature was kept constant at 35 ° C, and the pressure was changed stepwise from atmospheric pressure to 0.5 MPa. From the amount of various gases and the amount of various gases that were not absorbed, H gas, CH gas, CO gas, and N
  • the above absorption liquid and liquid CO 2 are placed in a high-pressure container (formed by a transparent member visible from the outside) set at a temperature of 20 ° C and a pressure of 7 MPa.
  • Figure 20 shows the state of the absorbing liquid and liquid CO in the high-pressure vessel after standing still.
  • Example 2 An absorbing solution consisting only of an ionic liquid was used. Specifically, 1-n-decyl-3-methylimidazolium hexafluorophosphate (1-n-decy ⁇ 3-methylimidazo hum
  • Example 2 Heated to 0 ° C. to dry and degas.
  • the water content in the absorbent after deaeration was 0.2% by weight or less. This absorbent was designated as Example 2.
  • An absorbing solution consisting only of an ionic liquid was used. Specifically, 1-n-decyl-3-methylimidazolium tetrafluoroborate ((1-n-decy ⁇ 3-methylimidazolium tetrafluoroborate) [DMIM] [BF] was used as the ionic liquid. This absorbent is 70 in a vacuum of 1 X 10 _4 Pa.
  • Example 3 Dried and degassed by heating to ° C. The water content in the absorbent after deaeration was 0.2% by weight or less. This absorbent was designated as Example 3.
  • Example 4 Dry and degassed. The water content in the absorbing solution after deaeration was 0.2% by weight or less. This absorbent solution was designated as Example 4.
  • N-ethy pyridinium tetrafluoroborate N-ethy ⁇ pyridinium
  • a high-purity CO gas (acid gas) with a purity of 99.99% by volume was contacted with the absorbing solutions of Examples 2 to 5.
  • the resolution was measured.
  • the measurement temperature is constant at 35 ° C, 45 ° C and 55 ° C, respectively, and the pressure is large.
  • the pressure was changed stepwise from atmospheric pressure to lOMPa.
  • the solubility in the collected liquid was measured.
  • the measurement temperature was kept constant at 35 ° C, and the pressure was changed stepwise from atmospheric pressure to 10 MPa.
  • the amount of various gases and the amount of various gases that have not been absorbed also affect the solubility of H gas, CH gas, CO gas, and N gas in the absorbing solution.
  • the absorption liquid contains H gas and CH gas.
  • the degree of solubility was calculated in terms of solubility per unit volume (Nm 3 Zm 3 ), and the results are shown in FIG.
  • the solubility per unit volume increases as the pressure increases, and the solubility of H 2 S gas increases.
  • the largest COS gas has the next highest CO gas solubility.
  • the above absorption liquid and liquid CO were respectively injected into a high-pressure vessel (formed by a transparent member visible from the outside) set at a pressure of 7 MPa at a temperature of 20 ° C. did.
  • the injected absorption liquid (specific gravity 1.37) and liquid CO (specific gravity 0.81) are in phase.
  • Fig. 26 shows the absorption liquid and liquid CO in the high-pressure vessel after standing.
  • the two forces are considered to have been separated into two liquid phases promptly because they are insoluble in each other and the specific gravity difference is large.
  • the liquid level of the two liquid phases before stirring and the liquid level of the two liquid phases after stirring and standing were the same level.

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Abstract

Selon l’invention, un gaz acide est séparé de et récupéré à partir d’un mélange de gaz de manière efficace et à faible coût. La quantité de gaz acide absorbée par unité de volume d’un liquide absorbant est augmentée et la quantité de liquide absorbant en circulation est réduite afin d’économiser l’énergie de circulation. On alimente une partie supérieure d’une colonne d’absorption (13), dont la température et la pression sont maintenues à une température et une pression données, avec un liquide absorbant renfermant un liquide ionique en tant qu’ingrédient principal, tout en alimentant la partie inférieure de la colonne d’absorption (13) avec un mélange de gaz, comprenant un gaz acide et un gaz non acide, afin de mettre en contact le mélange de gaz avec le liquide absorbant. Ainsi, le gaz acide est absorbé par le liquide absorbant et le gaz non acide est séparé du gaz acide et récupéré à partir de la colonne d’absorption (13). Le liquide absorbant contenant le gaz acide qu’il a absorbé est introduit dans une partie supérieure d’une colonne de régénération (16), dont la température est maintenue à une température égale ou supérieure à celle de l’intérieur de la colonne d’absorption (13) et dont la pression est maintenue à une pression inférieure à celle de la colonne d’absorption (13). Ainsi, la libération du gaz acide du liquide absorbant et sa récupération à partir de la colonne de régénération (16) se produisent en même temps que la régénération du liquide absorbant. On alimente la partie supérieure de la colonne d’absorption (13) avec le liquide absorbant régénéré.
PCT/JP2005/022523 2005-03-28 2005-12-08 Procede de purification du gaz, appareil correspondant et liquide absorbant les gaz acides utilise lors de la purification Ceased WO2006103812A1 (fr)

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JP2005-094450 2005-03-29
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JP2008178764A (ja) * 2007-01-23 2008-08-07 Mitsubishi Materials Corp 吸収液と液体二酸化炭素の分離再生装置及びこの分離再生装置を用いたガスの精製装置
WO2008138832A1 (fr) * 2007-05-11 2008-11-20 Basf Se Pompes à chaleur à absorption, machines frigorifiques à absorption et transformateurs à chaleur contenant du dioxyde de soufre en tant que fluide frigorigène
FR2923728A1 (fr) * 2007-11-16 2009-05-22 Inst Francais Du Petrole Procede de liquefaction d'un effluent gazeux
WO2010081657A1 (fr) * 2009-01-15 2010-07-22 Vtu Holding Gmbh Procede d'utilisation d'un liquide ionique dans le stockage d'hydrogene
WO2011061385A1 (fr) * 2009-11-20 2011-05-26 Nokia Corporation Piégeage de nanostructures
WO2012033973A1 (fr) * 2010-09-09 2012-03-15 Exxonmobil Research And Engineering Company Liquides ioniques destinés à l'élimination du dioxyde de carbone
JP2012170842A (ja) * 2011-02-17 2012-09-10 National Institute Of Advanced Industrial Science & Technology 低揮発性二酸化炭素吸収液およびガス分離方法
JP2012245505A (ja) * 2011-05-31 2012-12-13 Jx Nippon Oil & Energy Corp 気体分離ゲル膜
CN104174263A (zh) * 2014-08-18 2014-12-03 南京信息工程大学 一种用于脱除so2的离子液体及其制备方法和应用
WO2015167729A1 (fr) * 2014-05-02 2015-11-05 Exxonmobil Research And Engineering Company Procédé de lavage de dioxyde de carbone
CN109011983A (zh) * 2018-08-24 2018-12-18 郑州釜鼎热能技术有限公司 一种磁性液体净化污染气体的除尘脱污装置
CN109794153A (zh) * 2019-03-14 2019-05-24 中国铝业股份有限公司 一种铝电解槽大修渣无害化处理过程中的气体处置方法
CN111803857A (zh) * 2020-05-28 2020-10-23 南通大学 一种铝灰渣无害化处理回收利用系统及其工作方法
IT202000002353A1 (it) * 2020-02-06 2021-08-06 Eni Spa Processo e impianto di trattamento di miscele di gas contenenti gas acidi
WO2022129974A1 (fr) * 2020-12-17 2022-06-23 Totalenergies Onetech Milieu d'élimination sélective de sulfure d'hydrogène à partir d'un courant gazeux

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JP2008178764A (ja) * 2007-01-23 2008-08-07 Mitsubishi Materials Corp 吸収液と液体二酸化炭素の分離再生装置及びこの分離再生装置を用いたガスの精製装置
WO2008138832A1 (fr) * 2007-05-11 2008-11-20 Basf Se Pompes à chaleur à absorption, machines frigorifiques à absorption et transformateurs à chaleur contenant du dioxyde de soufre en tant que fluide frigorigène
FR2923728A1 (fr) * 2007-11-16 2009-05-22 Inst Francais Du Petrole Procede de liquefaction d'un effluent gazeux
FR2923727A1 (fr) * 2007-11-16 2009-05-22 Inst Francais Du Petrole Procede de liquefaction d'un effluent gazeux
WO2010081657A1 (fr) * 2009-01-15 2010-07-22 Vtu Holding Gmbh Procede d'utilisation d'un liquide ionique dans le stockage d'hydrogene
US9580311B2 (en) 2009-01-15 2017-02-28 Proionic Gmbh Method of use of an ionic liquid for storing hydrogen
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US9028785B2 (en) 2010-09-09 2015-05-12 Exxonmobil Reseach And Engineering Company High CO2 to amine adsorption capacity CO2 scrubbing processes
US9186616B2 (en) 2010-09-09 2015-11-17 Exxonmobil Research And Engineering Company Ionic liquids for removal of carbon dioxide
US9713788B2 (en) 2010-09-09 2017-07-25 Exxonmobil Research And Engineering Company Non-aqueous amine scrubbing for removal of carbon dioxide
WO2012033973A1 (fr) * 2010-09-09 2012-03-15 Exxonmobil Research And Engineering Company Liquides ioniques destinés à l'élimination du dioxyde de carbone
US9034288B2 (en) 2010-09-09 2015-05-19 Exxonmobil Research And Engineering Company Alkanolamine CO2 scrubbing process
US8715397B2 (en) 2010-09-09 2014-05-06 Exxonmobil Research And Engineering Company Mixed amine and non-nucleophilic base CO2 scrubbing process for improved adsorption at increased temperatures
US9186617B2 (en) 2010-09-09 2015-11-17 Exxonmobil Research And Engineering Company Non-aqueous amine scrubbing for removal of carbon dioxide
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JP2012170842A (ja) * 2011-02-17 2012-09-10 National Institute Of Advanced Industrial Science & Technology 低揮発性二酸化炭素吸収液およびガス分離方法
JP2012245505A (ja) * 2011-05-31 2012-12-13 Jx Nippon Oil & Energy Corp 気体分離ゲル膜
WO2015167729A1 (fr) * 2014-05-02 2015-11-05 Exxonmobil Research And Engineering Company Procédé de lavage de dioxyde de carbone
CN104174263A (zh) * 2014-08-18 2014-12-03 南京信息工程大学 一种用于脱除so2的离子液体及其制备方法和应用
CN109011983A (zh) * 2018-08-24 2018-12-18 郑州釜鼎热能技术有限公司 一种磁性液体净化污染气体的除尘脱污装置
CN109794153A (zh) * 2019-03-14 2019-05-24 中国铝业股份有限公司 一种铝电解槽大修渣无害化处理过程中的气体处置方法
IT202000002353A1 (it) * 2020-02-06 2021-08-06 Eni Spa Processo e impianto di trattamento di miscele di gas contenenti gas acidi
WO2021156814A3 (fr) * 2020-02-06 2021-09-23 Eni S.P.A. Procédé et installation de traitement de mélanges de gaz contenant du gaz acide
CN111803857A (zh) * 2020-05-28 2020-10-23 南通大学 一种铝灰渣无害化处理回收利用系统及其工作方法
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