WO2012153808A1 - 二酸化炭素分離システム - Google Patents

二酸化炭素分離システム Download PDF

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Publication number
WO2012153808A1
WO2012153808A1 PCT/JP2012/062029 JP2012062029W WO2012153808A1 WO 2012153808 A1 WO2012153808 A1 WO 2012153808A1 JP 2012062029 W JP2012062029 W JP 2012062029W WO 2012153808 A1 WO2012153808 A1 WO 2012153808A1
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Prior art keywords
carbon dioxide
gas
zeolite membrane
separation
concentration
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PCT/JP2012/062029
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English (en)
French (fr)
Japanese (ja)
Inventor
健一 澤村
高木　義信
祥広 浅利
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Kanadevia Corp
Original Assignee
Hitachi Zosen Corp
Hitachi Shipbuilding and Engineering Co Ltd
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Priority to CN201280022241.5A priority Critical patent/CN103596663B/zh
Priority to US14/116,739 priority patent/US9205382B2/en
Publication of WO2012153808A1 publication Critical patent/WO2012153808A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/028—Molecular sieves
    • B01D71/0281—Zeolites
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • 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
    • 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)
    • 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
    • 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
    • C10L3/104—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—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
    • B01D53/14—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
    • B01D53/1475—Removing carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates to a carbon dioxide separation system for recovering carbon dioxide (CO 2 ) in a mixed gas having a carbon dioxide concentration of 3 to 75%.
  • Carbon dioxide a typical global warming gas
  • power plants cement plants, steel plants, and chemical plants.
  • carbon dioxide recovery technology Development is an urgent need.
  • Carbon dioxide is also contained in natural gas mainly composed of methane, and it is necessary to recover and remove carbon dioxide from methane from the viewpoint of preventing pipeline corrosion.
  • coal gasification combined power generation finely pulverized coal is pyrolyzed and gasified, undergoes a shift reaction, generates a gas mainly composed of hydrogen and carbon dioxide, and then separates carbon dioxide into hydrogen. Attempts have been made to use rich gas as fuel gas.
  • the membrane separation method using a zeolite membrane is capable of continuous operation and does not require regeneration of an absorbing solution or an adsorbent, and thus is expected as a highly efficient carbon dioxide recovery technology.
  • Non-Patent Document 1 describes an example of performing carbon dioxide separation or nitrogen separation from natural gas mainly composed of methane using membrane separation by a zeolite membrane.
  • the pressure difference through the zeolite membrane becomes the driving force for gas permeation, so the carbon dioxide concentration on the non-permeate side of the zeolite membrane is reduced along with the removal and recovery of carbon dioxide.
  • the fact is that the separation efficiency decreases in the carbon concentration range.
  • Patent Document 1 in order to separate and recover carbon dioxide in exhaust gas, carbon dioxide is firstly concentrated in a membrane separator and further concentrated in an adsorption separator.
  • a hybrid process of a separation zeolite membrane and a pressure swing adsorption method (PSA) is proposed, and high concentration carbon dioxide is recovered.
  • PSA pressure swing adsorption method
  • a mixed gas having a wide range of carbon dioxide concentration and pressure is separated into a high concentration carbon dioxide gas having a carbon dioxide concentration of 80% or more and a carbon dioxide removal gas having a carbon dioxide concentration of 2% or less.
  • a carbon dioxide removal gas having a carbon dioxide concentration of 2% or less there was a problem that the equipment had to be inefficient.
  • An object of the present invention is to provide a carbon dioxide separation system capable of efficiently separating a mixed gas having a wide range of carbon dioxide concentrations and pressures into a high concentration carbon dioxide gas and a carbon dioxide removal gas. is there.
  • the present inventors have conducted a membrane separation method comprising a zeolite membrane for carbon dioxide separation containing a zeolite membrane layer, an amine absorption method or a pressure swing adsorption method (PSA).
  • a membrane separation method comprising a zeolite membrane for carbon dioxide separation containing a zeolite membrane layer, an amine absorption method or a pressure swing adsorption method (PSA).
  • PSA pressure swing adsorption method
  • the invention of the carbon dioxide separation system according to claim 1 is characterized in that a mixed gas (1) having a carbon dioxide concentration of 3 to 75% is mixed with a primary dioxide dioxide comprising a zeolite membrane (5) for carbon dioxide separation. Introduced into the carbon separator (4) to produce a primary permeate gas (6) having a carbon dioxide concentration of 80% or more on the permeate side of the zeolite membrane for carbon dioxide separation (5), and a zeolite membrane for carbon dioxide separation (5) The carbon dioxide concentration of the primary non-permeate side gas (7) is reduced to 3 to 15%, and then the primary non-permeate side gas (7) is converted into secondary dioxide by the amine absorption method or the pressure swing adsorption method (PSA).
  • PSA pressure swing adsorption method
  • acid It is characterized by causing a carbon removal gas (10).
  • the invention of the carbon dioxide separation system of claim 2 introduces a mixed gas (1) having a carbon dioxide concentration of 3 to 75% into a primary carbon dioxide separator (4) comprising a zeolite membrane (5) for carbon dioxide separation.
  • the primary permeation gas (6) containing the permeated carbon dioxide is generated on the permeation side of the zeolite membrane for carbon dioxide separation (5), and the primary non-permeation side gas (7) for the zeolite membrane for carbon dioxide separation (5).
  • the primary non-permeate side gas (7) is introduced into the secondary carbon dioxide separator (8) by the amine absorption method or the pressure swing adsorption method (PSA).
  • PSA pressure swing adsorption method
  • the invention of claim 3 is the carbon dioxide separation system according to claim 1 or 2, wherein the mixed gas (1) having a carbon dioxide concentration of 3 to 75% contains carbon dioxide (CO 2 ), and hydrogen ( H 2 ), nitrogen (N 2 ), oxygen (O 2 ), and at least one gas selected from the group consisting of methane, water (H 2 O), hydrogen sulfide (H 2 S), A gas containing at least one impurity selected from the group consisting of nitrogen oxides (NOx), sulfur oxides (SOx), and hydrocarbons other than methane, and comprising a zeolite membrane for carbon dioxide separation (5) An impurity remover (2) for removing the impurities is provided in a stage preceding the primary carbon dioxide separator (4).
  • the mixed gas (1) having a carbon dioxide concentration of 3 to 75% contains carbon dioxide (CO 2 ), and hydrogen ( H 2 ), nitrogen (N 2 ), oxygen (O 2 ), and at least one gas selected from the group consisting of methane, water (H 2 O), hydrogen sulfide
  • the invention of claim 4 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) is a faujasite (FAU) type zeolite membrane. It is characterized by including a layer.
  • FAU faujasite
  • the invention of claim 5 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) is a chabasite (CHA) type zeolite membrane layer. It is characterized by including.
  • CHA chabasite
  • the invention of claim 6 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) is a ZSM-5 (MFI) type zeolite membrane. It is characterized by containing a layer.
  • MFI ZSM-5
  • the invention of claim 7 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) contains a DDR type zeolite membrane layer. It is characterized by.
  • the invention of claim 8 is the carbon dioxide separation system according to any one of claims 1 to 7, wherein the zeolite membrane layer of the zeolite membrane for carbon dioxide separation (4) has a temperature for drying. It is characterized by being heat-treated at 100 to 600 ° C. to be dehydrated and then kept in a dry state.
  • a ninth aspect of the present invention is the carbon dioxide separation system according to any one of the first to eighth aspects, wherein the carbon dioxide separation system is installed in a coal gasification combined power plant, and the CO2 from the gas after the exhaust gas shift reaction.
  • the carbon dioxide separation system Used for carbon removal or installed in a natural gas refining plant of a natural gas field and used for carbon dioxide removal from natural gas, the above coal gasification combined power plant or natural gas refining plant After the closure, the carbon dioxide separation system is characterized in that it can be moved on land or at sea.
  • the invention of the carbon dioxide separation system according to claim 1 introduces a mixed gas (1) having a carbon dioxide concentration of 3 to 75% into a primary carbon dioxide separator (4) having a zeolite membrane (5) for carbon dioxide separation.
  • the primary permeation gas (6) having a carbon dioxide concentration of 80% or more is generated on the permeation side of the zeolite membrane for carbon dioxide separation (5), and the primary non-permeation side gas (7) of the zeolite membrane for carbon dioxide separation (5).
  • the primary non-permeate side gas (7) is introduced into the secondary carbon dioxide separator (8) by the amine absorption method or the pressure swing adsorption method (PSA).
  • PSA pressure swing adsorption method
  • the mixed gas having a wide range of carbon dioxide concentration and pressure can be efficiently separated into the high concentration carbon dioxide gas and the carbon dioxide removal gas. There is an effect that can be done.
  • a mixed gas (1) having a carbon dioxide concentration of 3 to 75% is introduced into a primary carbon dioxide separator (4) having a zeolite membrane (5) for carbon dioxide separation,
  • a primary permeate gas (6) containing carbon dioxide that has permeated is generated on the permeate side of the zeolite membrane for carbon separation (5), and the carbon dioxide of the primary non-permeate side gas (7) of the zeolite membrane for carbon dioxide separation (5).
  • the carbon concentration is reduced to 3 to 15%, and then this primary non-permeate side gas (7) is introduced into a secondary carbon dioxide separator (8) by an amine absorption method or a pressure swing adsorption method (PSA).
  • PSA pressure swing adsorption method
  • a secondary separation gas (9) containing carbon dioxide separated by a secondary carbon dioxide separator (8) is produced, and a carbon dioxide removal gas (10) having a carbon dioxide concentration of 2% or less is produced.
  • a wide range of carbon dioxide concentrations and pressures are set. The mixed gas is efficiently separated into the high-concentration carbon dioxide gas and the carbon dioxide removal gas.
  • the invention of claim 3 is the carbon dioxide separation system according to claim 1 or 2, wherein the mixed gas (1) having a carbon dioxide concentration of 3 to 75% contains carbon dioxide (CO 2 ), and hydrogen ( H 2 ), nitrogen (N 2 ), oxygen (O 2 ), and at least one gas selected from the group consisting of methane, water (H 2 O), hydrogen sulfide (H 2 S), A gas containing at least one impurity selected from the group consisting of nitrogen oxides (NOx), sulfur oxides (SOx), and hydrocarbons other than methane, and comprising a zeolite membrane for carbon dioxide separation (5)
  • the primary carbon dioxide separator (4) is provided with an impurity remover (2) for removing the impurities before the primary carbon dioxide separator (4). Carbon separator (4) and two An effect that contamination and deterioration due to the impurity of the carbon separation zeolite membrane (5) can be prevented.
  • the invention of claim 4 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) is a faujasite (FAU) type zeolite membrane.
  • FAU faujasite
  • hydrogen (H 2 ), methane, nitrogen (N 2 ), and oxygen by the strong adsorption action of the FAU type zeolite membrane and carbon dioxide, There is an effect that carbon dioxide can be permeated and separated with high selectivity from a gas such as O 2 ).
  • the invention of claim 5 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) is chabasite (CHA) such as SAPO-34. ) Type zeolite membrane layer.
  • CHA chabasite
  • methane which is a large molecule
  • methane is formed by the uniform and rigid pore structure having a diameter of 0.38 mm, which CHA type zeolite has. From the diameter of 0.38 nm, carbon dioxide (0.33 nm in diameter), which is a small molecule, can be permeated and removed with high selectivity in a molecular sieve manner.
  • the invention of claim 6 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) is a ZSM-5 (MFI) type zeolite membrane. According to the invention of claim 6, although the carbon dioxide permeation separation performance is inferior to that of the FAU type zeolite membrane, there is an effect that high durability is obtained.
  • MFI ZSM-5
  • the invention of claim 7 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) contains a DDR type zeolite membrane layer.
  • the hydrophobicity of the DDR type zeolite membrane prevents carbon dioxide from permeating through the membrane, and the DDR type zeolite membrane layer has a pore structure. Due to the difference in diffusivity, carbon dioxide can be selectively permeated and separated from methane.
  • the invention of claim 8 is the carbon dioxide separation system according to any one of claims 1 to 7, wherein the zeolite membrane layer of the zeolite membrane for carbon dioxide separation (4) has a temperature for drying. It is characterized in that it is heat-treated at 100 to 600 ° C., dehydrated, and thereafter kept in a dry state. According to the invention of claim 8, water of crystallization in the zeolite pores is removed. Thus, the effect of obtaining high carbon dioxide permeability can be obtained.
  • a ninth aspect of the present invention is the carbon dioxide separation system according to any one of the first to eighth aspects, wherein the carbon dioxide separation system is installed in a coal gasification combined power plant, and the CO2 from the gas after the exhaust gas shift reaction. Used for carbon removal or installed in a natural gas refining plant of a natural gas field and used for carbon dioxide removal from natural gas, the above coal gasification combined power plant or natural gas refining plant After the closure of the carbon dioxide separation system, the carbon dioxide separation system is made movable on land or at sea.
  • the carbon dioxide separation system according to the present invention is, for example, In a combined gasification combined cycle power plant, when used to remove carbon dioxide from the gas after the exhaust gas shift reaction, after the closed coal gasification combined cycle plant is closed, other coal gasification An effect that can be used and transferred to if the power plant.
  • the carbon dioxide separation system according to the present invention when used for removing carbon dioxide from natural gas, for example, when the adaptive gas field is depleted, it can be transferred to another gas field and used. It has the effect of being easily applied to natural gas fields.
  • FIG. 1 is a flow sheet showing a first embodiment of a carbon dioxide separation system according to the present invention. It is a flow sheet which shows 2nd Embodiment of the carbon dioxide separation system by this invention.
  • FIG. 1 is a flow sheet showing a first embodiment of a carbon dioxide separation and recovery system based on a hybrid of a zeolite membrane and an amine absorption method or a pressure swing adsorption method (PSA) according to the present invention.
  • PSA pressure swing adsorption method
  • the inventors of the present invention performed a specific method of separating a membrane separation method including a zeolite membrane for carbon dioxide separation containing a zeolite membrane layer, an amine absorption method or a pressure swing adsorption method (PSA).
  • a hybrid system combined with operating conditions can efficiently separate a carbon dioxide-containing mixed gas into a high-concentration carbon dioxide gas having a carbon dioxide concentration of 80% or more and a carbon dioxide removal gas having a carbon dioxide concentration of 2% or less.
  • the present inventors have found out what can be done and have completed the present invention.
  • the invention of the carbon dioxide separation system is a primary carbon dioxide separator (1) comprising a mixed gas (1) having a carbon dioxide concentration of 3 to 75% and a zeolite membrane (5) for carbon dioxide separation. 4), a primary permeation gas (6) having a carbon dioxide concentration of 80% or more is generated on the permeation side of the carbon dioxide separation zeolite membrane (5), and the primary non-permeation of the carbon dioxide separation zeolite membrane (5).
  • the carbon dioxide concentration of the side gas (7) is reduced to 3 to 15%, and then the primary non-permeate side gas (7) is separated into a secondary carbon dioxide separator (PSA) by an amine absorption method or a pressure swing adsorption method (PSA) ( 8), and a secondary separation gas (9) having a carbon dioxide concentration of 80% or more separated by the secondary carbon dioxide separator (8) is produced, and carbon dioxide concentration with a carbon dioxide concentration of 2% or less is removed.
  • PSA secondary carbon dioxide separator
  • PSA pressure swing adsorption method
  • a secondary separation gas (9) having a carbon dioxide concentration of 80% or more separated by the secondary carbon dioxide separator (8) is produced, and carbon dioxide concentration with a carbon dioxide concentration of 2% or less is removed.
  • a mixed gas having a wide range of carbon dioxide concentrations and pressures can be efficiently separated into a high concentration carbon dioxide gas and a carbon dioxide removal gas. can do.
  • the zeolite membrane for carbon dioxide separation containing the above zeolite either a tubular or hollow fiber porous substrate made of zeolite can be used. From the viewpoint of pressure resistance of the element, a tubular shape is preferable.
  • the driving force for membrane permeation includes self-pressure of the mixed gas (1), pressurization of the membrane separator supply gas (3) by a compressor (not shown), or pressure reduction on the membrane permeation side by a vacuum pump (not shown). Is available.
  • a carbon dioxide separation system according to the present invention is applied to an amine absorption method or a pressure swing adsorption method (PSA) in which the equipment scale, equipment cost, and energy consumption increase in proportion to an increase in the concentration of carbon dioxide as a processing gas.
  • PSA pressure swing adsorption method
  • FIG. 2 is a flow sheet showing a second embodiment of the carbon dioxide separation system according to the present invention.
  • the invention of the carbon dioxide separation system is a primary carbon dioxide separator (1) comprising a mixed gas (1) having a carbon dioxide concentration of 3 to 75% and a zeolite membrane (5) for carbon dioxide separation. 4) is introduced into the permeation side of the carbon dioxide separation zeolite membrane (5), and the primary permeation gas (6) containing the permeated carbon dioxide is generated and the primary non-permeation of the carbon dioxide separation zeolite membrane (5).
  • the carbon dioxide concentration of the side gas (7) is reduced to 3 to 15%, and then the primary non-permeate side gas (7) is separated into a secondary carbon dioxide separator (PSA) by an amine absorption method or a pressure swing adsorption method (PSA) ( 8) and a secondary separation gas (9) containing carbon dioxide separated by the secondary carbon dioxide separator (8) is produced, and a carbon dioxide removal gas (1) having a carbon dioxide concentration of 2% or less. ), And a primary permeate gas (6) containing carbon dioxide discharged from the zeolite membrane for carbon dioxide separation (5) and a secondary containing carbon dioxide discharged from the secondary carbon dioxide separator (8).
  • PSA secondary carbon dioxide separator
  • PSA pressure swing adsorption method
  • the separation gas (9) is mixed to produce a carbon dioxide enriched gas (11) having a carbon dioxide concentration of 80% or more. According to the present invention, similarly, a wide range of carbon dioxide concentrations , And a mixed gas having pressure can be efficiently separated into high-concentration carbon dioxide gas and carbon dioxide-removed gas.
  • the zeolite membrane for carbon dioxide separation (4) preferably includes a faujasite (FAU) type zeolite membrane layer.
  • FAU faujasite
  • carbon dioxide is selectively permeated and separated from gases such as hydrogen (H 2 ), methane, nitrogen (N 2 ), and oxygen (O 2 ) by the strong adsorption action of the FAU type zeolite membrane and carbon dioxide.
  • the FAU type zeolite membrane is not particularly limited, but for example, a FAU type zeolite membrane (trade name, NaY type zeolite membrane, manufactured by Hitachi Zosen Corporation) can be used.
  • the invention of claim 5 is the carbon dioxide separation system according to any one of claims 1 to 3, wherein the zeolite membrane for carbon dioxide separation (4) Preferably, it contains a chabasite (CHA) type zeolite membrane layer such as SAPO-34.
  • CHA chabasite
  • the CHA-type zeolite membrane is not particularly limited.
  • the CHA-type zeolite membrane was prepared to have a composition of Al 2 O 3 : P 2 O 3 : 0.32SiO 2 : TEAOH: 1.6DPA: 150H 2 O.
  • the SAPO-34 seed crystal densely coated on the porous support in the reaction solution can be synthesized by a method of hydrothermal synthesis at 220 ° C. for 6 hours (for example, Non-patent Document 2: S. Li et al., “Scale-up of SAPO-34 membrane for CO 2 / CH 4 separation” Journal of Membrane Science 352 (2010) 7-13.
  • the zeolite membrane for carbon dioxide separation (4) contains a ZSM-5 (MFI) type zeolite membrane layer.
  • the ZSM-5 type zeolite membrane is not particularly limited.
  • the ZSM-5 type zeolite membrane is porous in a reaction solution prepared to 10Na 2 O: 0.15Al 2 O 3 : 36SiO 2 : 1200H 2 O.
  • ZSM-5 seed crystals coated tightly on a porous support can be synthesized by a method of hydrothermal synthesis at 180 ° C. for 12 hours (for example, Non-Patent Document 3: K. Sawamura et al., “Reverse-Selective Microporous Membrane for Gas Separation” Chem. Asian J. 4 (2009) 1070-1077.).
  • the zeolite membrane for carbon dioxide separation (4) preferably contains a DDR type zeolite membrane layer.
  • the hydrophobicity of the DDR type zeolite membrane prevents the carbon dioxide from permeating through the membrane, and the DDR type zeolite membrane layer has a high selection of carbon dioxide from the diffusivity in the pore structure of the DDR type zeolite membrane layer. There is an advantage that transmission and separation can be performed.
  • the DDR type zeolite membrane is not particularly limited.
  • (1-adamantanamine / silica) 0.125
  • (ethylenediamine / 1-adamantanamine) 16
  • the DDR seed crystal densely coated on the porous support can be synthesized by a method of hydrothermal synthesis at 160 ° C. for 48 hours ( For example, refer to Japanese Patent No. 4204273).
  • the zeolite membrane layer of the zeolite membrane for carbon dioxide separation (4) is dehydrated by heat treatment at a temperature of 100 to 600 ° C. for drying, and then remains in a dry state. It is preferable that it is held.
  • the membrane separator feed gas is dried by the impurity remover (2), and the zeolite membrane is heated to a temperature of 100 to 600 ° C., preferably by a heater (not shown) provided in the primary carbon dioxide separator (4).
  • a heater not shown
  • the inside of the zeolite membrane pores can be kept dry.
  • the carbon dioxide separation system according to the present invention is installed in a coal gasification combined power plant and is used for removing carbon dioxide from a gas after an exhaust gas shift reaction, or in a natural gas purification plant of a natural gas field. Installed and used to remove carbon dioxide from natural gas, and after the coal gasification combined power plant or natural gas refining plant is closed, the carbon dioxide separation system is movable on land or sea It is preferable that
  • the carbon dioxide separation system according to the present invention when used for removing carbon dioxide from the gas after the exhaust gas shift reaction, for example, in a coal gasification combined power plant, after the coal gasification combined power plant is closed, There is an advantage that it can be transferred to other coal gasification combined power plants.
  • the carbon dioxide separation system according to the present invention when used for removing carbon dioxide from natural gas, for example, when the adaptive gas field is depleted, it can be used by moving to another gas field. It has the advantage of being easy to apply to natural gas fields.
  • the carbon dioxide separation and recovery system of the present invention was implemented using the flow sheet shown in FIG.
  • a mixed gas (1) having a carbon dioxide concentration of 20% made of a gas containing impurities (NOx) and sulfur oxides (SOx) is first provided with an adsorbent such as zeolite for removing the impurities.
  • an adsorbent such as zeolite for removing the impurities.
  • the membrane separator supply gas (3) was introduced into the primary carbon dioxide separator (4) equipped with a zeolite membrane for carbon dioxide separation (5).
  • a zeolite membrane for carbon dioxide separation (5) a tubular FAU type zeolite membrane (trade name, NaY type zeolite membrane, manufactured by Hitachi Zosen Corporation) was used.
  • a primary permeate gas (6) having a carbon dioxide concentration of 95% is generated on the permeate side of the zeolite membrane for carbon dioxide separation (5), and a primary non-permeate gas (7) for the zeolite membrane for carbon dioxide separation (5).
  • the carbon dioxide concentration was reduced to 10%.
  • this primary non-permeate side gas (7) is introduced into a secondary carbon dioxide separator (8) by an amine absorption method or pressure swing adsorption method (PSA) made of alkanolamine, and the secondary carbon dioxide separator (8).
  • PSA pressure swing adsorption method
  • Example 1 it was possible to efficiently separate a mixed gas having a wide range of carbon dioxide concentration and pressure into a high concentration carbon dioxide gas and a carbon dioxide removal gas.
  • the carbon dioxide separation system according to the first embodiment of the present invention is a simple method using only the amine absorption method in which the equipment scale, equipment cost, and energy consumption increase in proportion to the increase in the concentration of carbon dioxide as the processing gas.
  • the use of zeolite membrane separation in a high-concentration carbon dioxide region can reduce the equipment scale, equipment cost, and energy consumption.
  • the FAU type zeolite membrane for the carbon dioxide separation zeolite membrane, the membrane deterioration such as that seen in the conventional organic polymer membrane such as plasticization of the membrane by high pressure carbon dioxide does not occur.
  • Example 2 The carbon dioxide separation and recovery system of the present invention was implemented using the flow sheet shown in FIG.
  • the difference from the case of Example 1 is that the pressure non-permeation side gas (7) of the zeolite membrane for carbon dioxide separation (5) is used as a carbon dioxide recovery / separation material and a pressure swing adsorption method comprising zeolite 13X.
  • PSA is introduced into the secondary carbon dioxide separator (8) to produce a secondary separation gas (9) containing carbon dioxide separated by the secondary carbon dioxide separator (8), and a carbon dioxide concentration of 2 % Of carbon dioxide-removing gas (10) or less, from the primary permeate gas (6) containing carbon dioxide discharged from the zeolite membrane for carbon dioxide separation (5), and the secondary carbon dioxide separator (8)
  • the secondary separation gas (9) containing carbon dioxide to be discharged is mixed to produce a carbon dioxide enriched gas (11) having a carbon dioxide concentration of 96%.
  • Example 2 similarly, a mixed gas having a wide range of carbon dioxide concentrations and pressures could be efficiently separated into a high concentration carbon dioxide gas and a carbon dioxide removal gas.
  • the carbon dioxide separation system according to Example 2 of the present invention is a pressure swing adsorption method (PSA) in which the equipment scale, equipment cost, and energy consumption increase in proportion to the increase in the concentration of carbon dioxide as the processing gas.
  • PSA pressure swing adsorption method
  • the pressure swing adsorption method is used in the low concentration carbon dioxide region, so that it is highly selective. Carbon dioxide can be separated.
  • the FAU type zeolite membrane for the carbon dioxide separation zeolite membrane, the membrane deterioration such as that seen in the conventional organic polymer membrane such as plasticization of the membrane by high pressure carbon dioxide does not occur.

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  • Separation Using Semi-Permeable Membranes (AREA)
  • Carbon And Carbon Compounds (AREA)
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  • Gas Separation By Absorption (AREA)
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