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WO2017111503A1 - Procédé et appareil de collecte de dioxyde de carbone présent dans un produit secondaire gazeux d'élaboration de l'acier, et de récupération d'hydrogène - Google Patents

Procédé et appareil de collecte de dioxyde de carbone présent dans un produit secondaire gazeux d'élaboration de l'acier, et de récupération d'hydrogène Download PDF

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Publication number
WO2017111503A1
WO2017111503A1 PCT/KR2016/015112 KR2016015112W WO2017111503A1 WO 2017111503 A1 WO2017111503 A1 WO 2017111503A1 KR 2016015112 W KR2016015112 W KR 2016015112W WO 2017111503 A1 WO2017111503 A1 WO 2017111503A1
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WIPO (PCT)
Prior art keywords
absorbent
carbon dioxide
gas
hollow fiber
module
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Ceased
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PCT/KR2016/015112
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English (en)
Korean (ko)
Inventor
이평수
박유인
남승은
박호식
박아름이
김성중
장종산
박용기
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Korea Research Institute of Chemical Technology KRICT
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Korea Research Institute of Chemical Technology KRICT
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Publication of WO2017111503A1 publication Critical patent/WO2017111503A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/031—Two or more types of hollow fibres within one bundle or within one potting or tube-sheet
    • 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B7/00—Blast furnaces
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • the present invention relates to a method for capturing carbon dioxide from a steel by-product gas, a method for recovering hydrogen, and more particularly, to recovering hydrogen and recovering hydrogen by contacting the iron by-product gas supplied into the hollow fiber membrane with an absorbent to remove carbon dioxide.
  • a method and apparatus for capturing absorbed carbon dioxide is a method and apparatus for capturing absorbed carbon dioxide.
  • BFG Blast furnace gas
  • LDG Linz-Donawitz Converter Gas
  • CO 2 carbon dioxide
  • CO carbon monoxide
  • the absorption method using the ammonia-based absorbent has a disadvantage in that it consumes much energy because it depends largely on the thermodynamic equilibrium.
  • the amount of the adsorbent and other facilities are ideally used to treat a large flow rate of the by-product by-product gas. It is hard to realize it realistically because it enters.
  • the membrane method significantly reduces energy consumption and enables a compact structure, but in the case of a membrane material using a polymer membrane, it is difficult to use due to the low separation rate of hydrogen / carbon dioxide ( ⁇ 2), and an inorganic particle (zeolite, In the case of carbon, metal-organic framework (MOF), etc.), the separation efficiency is very low as 10 or less.
  • the present inventors have developed a method and apparatus for recovering hydrogen by selectively absorbing carbon dioxide having high solubility from by-product gas by contacting gas-liquid contact, seasonal by-product gas and absorber through an absorbent circulating the porous hollow fiber membrane.
  • the present invention has been completed.
  • An object of the present invention is to provide a method and apparatus for collecting carbon dioxide and recovering hydrogen from steel by-product gas with improved energy efficiency.
  • step 2 Injecting seasonal by-product gas containing hydrogen (H 2 ) and carbon dioxide (CO 2 ) into the hollow fiber of the hollow fiber separator (step 2);
  • It provides a method for capturing carbon dioxide and recovering hydrogen from the iron and steel by-product gas comprising the step of separating and discharging the gas inside the hollow fiber containing the carbon dioxide dissolved absorbent and hydrogen not dissolved in the absorbent (step 4).
  • a hollow fiber separator mounted in the housing; And an absorbent filler space defined by an outer side of the hollow fiber membrane and an inner side of the housing constituting the hollow fiber membrane.
  • An absorbent supply unit for supplying an absorbent to the absorbent filling space of the absorbent module
  • a gas supply unit for supplying iron and steel by-product gas including hydrogen (H 2 ) and carbon dioxide (CO 2 ) into the hollow fiber of the hollow fiber membrane of the absorption module;
  • It provides a carbon dioxide capture and hydrogen recovery apparatus from the iron and steel by-product gas, including; a discharge port for discharging the gas containing hydrogen not dissolved in the absorber to the outside of the absorption module.
  • the method and apparatus for capturing carbon dioxide and recovering hydrogen from steelmaking by-product gas according to the present invention have advantages such as simpler, smaller size, lower installation cost, and lower running cost than the prior art through hollow fiber membranes and absorbents.
  • carbon dioxide in the case of a gas containing water and other impurities after the water gas reaction (WGS), carbon dioxide can be stably separated, and hydrogen can be recovered, thereby reducing the burden of pretreatment and having high energy efficiency.
  • FIG. 1 is a diagram showing the gas composition of blast furnace gas (BFG) and converter gas (LDG), which are seasonal by-product gases, and the gas composition when the gases undergo a water gas conversion process and a water removal process;
  • BFG blast furnace gas
  • LDG converter gas
  • FIG. 2 is a schematic diagram schematically showing an example of an absorption module in a carbon dioxide capture and hydrogen recovery apparatus from steelmaking by-product gas according to the present invention
  • FIG. 3 is a schematic diagram schematically showing an example of an absorption module and a degassing module in a carbon dioxide capture and hydrogen recovery apparatus from the steelmaking by-product gas according to the present invention
  • FIG. 4 is a schematic diagram schematically showing an example of an absorption module, a degassing module and an absorbent degassing tank in the carbon dioxide capture and hydrogen recovery apparatus from the steelmaking by-product gas according to the present invention
  • Example 5 is a graph showing the hydrogen recovery and carbon dioxide removal rate of Example 1 and Example 2 according to the present invention.
  • a carbon dioxide capture and hydrogen recovery system was constructed from the steel production by-product gas, in which the average pore size of the hollow fiber membrane of the absorption module 100 was 0.2 ⁇ m, and the effective membrane area was 0.2 m 2 .
  • Polypropylene was used.
  • two absorption modules were provided in series.
  • As the steel by-product gas a gas having a composition of H 2 (20.6%), N 2 (44.4%), and CO 2 (35%) that was subjected to water gas conversion (WGS) was used.
  • Step 1 Water was used as the absorbent and fed into the absorbent filling space at a flow rate of 500 ml / min.
  • Step 2 The iron by-product gas was supplied into the hollow fiber membrane of the absorption module at a flow rate of 200 ml / min.
  • Step 3 The absorbent in the absorbent module was maintained at a pressure of 3 atm, and the seasonal by-product gas at a pressure of 2.5 atm.
  • Step 4 The gas containing hydrogen, which is the seasonal by-product gas passed through the absorption module, and the absorbent in which carbon dioxide was dissolved were discharged.
  • the absorbent water was allowed to be continuously supplied from an external device.
  • a carbon dioxide capture and hydrogen recovery system was constructed from steel by-product gas, in which the average pore size of the hollow fiber membrane of the absorption module 100 was 0.2 ⁇ m, and the effective membrane area was 0.2 m 2 .
  • Polypropylene was used.
  • two absorption modules were provided in series.
  • As the steel by-product gas a gas having a composition of H 2 (20.6%), N 2 (44.4%), and CO 2 (35%) that was subjected to water gas conversion (WGS) was used.
  • Step 1 Water was used as the absorbent and fed into the absorbent filling space at a flow rate of 500 ml / min.
  • Step 2 The iron by-product gas was supplied into the hollow fiber membrane of the absorption module at a flow rate of 200 ml / min.
  • Step 3 The absorbent in the absorbent module was maintained at a pressure of 3 atm, and the seasonal by-product gas at a pressure of 2.5 atm.
  • Step 4 The gas containing hydrogen, which is the seasonal by-product gas passed through the absorption module, and the absorbent in which carbon dioxide was dissolved were discharged.
  • the degassing module 300 and the absorbent degassing tank 500 for separating the gas containing hydrogen and the carbon dioxide dissolved absorbent, the gas containing hydrogen as the seasonal by-product gas passed through the absorbent module 100, the carbon dioxide dissolved in the absorbent ) was further added to degas the carbon dioxide.
  • the average pore size of the hollow fiber membrane 301 of the degassing module 300 is 0.2 ⁇ m
  • the effective membrane area is 0.2 m 2
  • the material was polypropylene.
  • two degassing modules were provided in series.
  • the absorbent in which carbon dioxide was dissolved in the step 4 was supplied to the absorbent degassing tank 500, and degassed partially dissolved carbon dioxide by depressurizing to a pressure of 0.8 atm.
  • Step a The absorbent supplied from the absorbent degassing tank was supplied to the absorbent filling space 302 of the degassing module 300.
  • Step b The gas inside the hollow fiber membrane 301 of the degassing module 300 was discharged to the outside.
  • Step c The gas inside the hollow fiber membrane was depressurized to 0.02 atm using the first pressure reducing pump 400 so that the carbon dioxide dissolved in the absorbent of step a could be degassed into the hollow fiber membrane 301.
  • Step d The carbon dioxide degassed absorbent and the degassed carbon dioxide in the hollow fiber membrane 301 of the degassing module 300 was separated and discharged.
  • Example 1 having a carbon dioxide capture and hydrogen recovery apparatus from the steelmaking by-product gas according to the present invention showed a hydrogen recovery rate of about 90% and a carbon dioxide removal rate, and Example 2 of about 95% or more of hydrogen. It was confirmed that the recovery rate and the carbon dioxide removal rate were shown. Therefore, the degassing module 300 and the absorbent degassing tank 500 were further provided, and it was confirmed that Example 2, which has undergone the step of degassing the carbon dioxide dissolved in the absorbent, has a high hydrogen recovery rate and a carbon dioxide removal rate.
  • the present invention is a.
  • step 1 Supplying an absorbent to the absorbent filling space 102 of the absorbent module 100 (step 1);
  • step 2 Injecting the seasonal by-product gas containing hydrogen (H 2 ) and carbon dioxide (CO 2 ) into the hollow fiber of the hollow fiber separator 101 (step 2);
  • It provides a method for capturing carbon dioxide and recovering hydrogen from the iron and steel by-product gas comprising the step of separating and discharging the gas inside the hollow fiber containing the carbon dioxide dissolved absorbent and hydrogen not dissolved in the absorbent (step 4).
  • FIG. 2 to 4 schematically illustrate an example of a hydrogen recovery apparatus and method according to the present invention through a schematic diagram.
  • step 1 is a step of supplying an absorbent to the absorbent filling space 102 of the absorption module 100.
  • the absorbent is supplied to the absorbent filling space 102 of the absorbent module 100 so that the steelmaking by-product gas and the absorbent may have gas-liquid contact.
  • the absorbent is supplied from the absorbent degassing tank 500 to the absorbent filling space through the absorbent supply unit 200, where the flow rate of the absorbent is supplied in correspondence with the flow rate of the steel-produced by-product gas supplied to the pump in the absorbent supply unit. It is desirable to change the flow rate through.
  • the flow rate supplied with the absorbent may be 100 ml / min to 1000 ml / min when one absorption module is provided, and may be 200 ml / min to 800 ml / min, but can be in effective contact with the seasonal by-product gas If the flow rate is not limited to this, it can be changed by further comprising an additional absorption module.
  • the absorbent is supplied from the lower end of the absorbent module 100 and flows through the absorbent filling space 102, and then is discharged through the outlet 104 to the upper end of the absorbent module, but the absorbent module is designed horizontally, Absorbents passing through the absorbent module may be supplied and discharged in the opposite direction, but are not limited thereto.
  • the absorbent does not pass through the hollow fiber membrane 101 of the absorption module, it may be in contact only with the gas inside the hollow fiber membrane.
  • step 2 includes the hollow fiber of the hollow fiber membrane 101 of the steel by-product by-product containing hydrogen (H 2 ) and carbon dioxide (CO 2 ). Injecting it into the inside.
  • step 2 a steel by-product gas containing hydrogen and carbon dioxide is supplied into the hollow fiber of the hollow fiber membrane 101 so as to be in gas-liquid contact with the absorbent supplied in step 1.
  • the steelmaking by-product gas of step 2 may be supplied through the gas supply part 700, and the flow rate supplied may be adjusted through the gas supply part.
  • the flow rate of the supplied steel by-product gas may be 50 ml / min to 1000 ml / min, preferably 100 ml / min to 500 ml / min, the flow rate that the iron and steel by-product gas can effectively contact the absorbent If not limited to this.
  • the supplied iron by-product gas is supplied into the hollow fiber membrane 101 through the gas supply unit 700, the iron by-product gas is diffused into the pores of the hollow fiber membrane, and is introduced into the absorbent filler space 102 In contact with the absorbent, most of the carbon dioxide of the seasonal by-product gas is selectively dissolved. The remaining gas which is not dissolved is discharged through the outlet 103 to the outside of the absorption module 100.
  • Steelmaking by-product gas of step 2 may include 0.1% by volume to 80% by volume of hydrogen, preferably 0.3% by volume to 45% by volume of hydrogen.
  • the seasonal by-product gas of step 2 may include 0.1% to 80% by volume of carbon dioxide, preferably 3% to 50% by volume of carbon dioxide.
  • the seasonal by-product gas may further include nitrogen, carbon monoxide, water, oxygen and the like.
  • the steel by-product gas of step 2 may be used as the steel by-product gas is a water-gas shift (WGS; Water-Gas Shift) process, wherein the steel by-product gas is water conversion 15% by volume to 50 It may comprise volume percent hydrogen, preferably from 15 volume percent to 40 volume percent hydrogen.
  • WGS Water-Gas Shift
  • the method for capturing carbon dioxide and recovering hydrogen from the steel by-product by-product according to the present invention can efficiently perform the carbon dioxide separation step to be described later, even if the steel-containing by-product is included in the water, so that the water gas conversion process must be performed. It is not necessary.
  • the steel by-product gas subjected to the water gas conversion process may include 20% by volume to 50% by volume of carbon dioxide, preferably 20% by volume to 40% by volume of carbon dioxide.
  • the water gas conversion is a process of generating hydrogen by reacting carbon monoxide contained in blast furnace gas (BFG), iron furnace by-product gas, and converter gas (LDG; Linz-Donawitz Converter Gas) with water vapor again. It is as follows.
  • the carbon dioxide capture and hydrogen recovery apparatus from the iron and steel by-product gas according to the present invention is a gas containing water and carbon monoxide. There is also an advantage that carbon capture and hydrogen recovery is possible.
  • a water removal process may be further added to the gas from the water gas shift reaction using an adsorbent.
  • 1 shows an example of the composition of the steel by-product gas, the steel by-product gas in which the water gas conversion is performed, and the steel by-product gas which has undergone the water removal process after the conversion of the water gas.
  • the flow rate ratio of the steel by-product gas and the absorbent may be 0.01 to 1, may be 0.05 to 1, preferably 0.1 to 1, steel production by-product gas and absorbent If the flow rate ratio that can be efficiently contacted is not limited thereto.
  • step 3 is to adjust the pressure in the absorption module 100 so that carbon dioxide in the steel by-product gas can be selectively dissolved in the absorbent. .
  • step 3 the pressure in the absorbent module 100 is adjusted to effectively dissolve the carbon dioxide into the absorbent.
  • the pressure of the steel by-product by-products in the absorption module may be 0.1 atm to 15 atm, preferably 0.5 to 10 atm, but is not limited to this if the pressure of carbon dioxide can be effectively dissolved in the absorbent.
  • the pressure of the absorbent in the absorbent module 100 may be 0.1 atm to 15 atm, preferably 0.5 to 10 atm, but is not limited thereto as long as carbon dioxide can be effectively dissolved in the absorbent.
  • step 4 is a step of discharging a gas containing an absorbent in which carbon dioxide is dissolved and hydrogen not dissolved in the absorbent.
  • step 4 the hydrogen is not dissolved in the absorbent, and the hydrogen-containing gas and the absorbent are separated and discharged to easily recover the hydrogen.
  • step of degassing carbon dioxide from the absorbent in which the carbon dioxide dissolved in step 4 may further include.
  • the absorbent separated and discharged in step 4 may be transferred to and stored in the absorbent degassing tank 500.
  • the pressure in the absorbent degassing tank may be atmospheric pressure or vacuum, but if the pressure in which the carbon dioxide in the absorbent is degassed is limited thereto. It is not.
  • carbon dioxide dissolved in some absorbents may be degassed and supplied to the hollow fiber membrane 101 of the absorbent module 100.
  • the present invention provides a step (step a) of supplying the absorbent dissolved carbon dioxide separated in the absorbent module 100 to the absorbent filling space 302 of the degassing module 300; Discharging the gas inside the hollow fiber separation membrane 301 of the degassing module to the outside (step b); Adjusting the pressure in the degassing module so that carbon dioxide dissolved in the absorbent can be degassed (step c); Separating and discharging the carbon dioxide degassed absorbent and the degassed carbon dioxide (step d); may further include.
  • step a similar to step 1, the absorbent absorbing carbon dioxide through the absorbent module 100 is supplied to the absorbent filling space of the degassing module 300 so that carbon dioxide in the absorbent can be degassed.
  • the absorbent may be supplied from the upper end of the absorbent module 100 to flow through the absorbent filling space 302 of the degassing module 300 and then discharged to the lower end of the degassing module.
  • Absorbents passing through the degassing module may be supplied and discharged in the opposite direction, but are not limited thereto.
  • the absorbent may not pass into the hollow fiber membrane 301 of the degassing module, and may only contact gas inside the hollow fiber membrane.
  • the absorbent having performed step a may be discharged through the outlet 305 to the outside of the degassing module 300, and may be supplied to the absorption module 100 and circulated again.
  • the gas inside the hollow fiber membrane 301 of the degassing module 300 may be adjusted to a normal pressure or a vacuum state so as to be discharged to the outside, but is not limited thereto.
  • Carbon dioxide dissolved in the absorbent may be degassed and supplied to the inner space of the hollow fiber membrane 301 of step b, and the carbon dioxide may be finally separated and discharged through the outlet 304.
  • step c the pressure in the degassing module 300 is adjusted so that the carbon dioxide dissolved in the absorbent can be effectively degassed into the hollow fiber membrane 301 of the degassing module.
  • the pressure of the gas and the absorbent in the degassing module 300 is adjusted through the first decompression pump 400.
  • the pressure of the carbon dioxide which is a gas in the degassing module 300 may be 0.01 atm to 2 atm, preferably 0.1 atm to 1.5 atm, but if the pressure of the carbon dioxide dissolved in the absorbent can be effectively degassed, it is limited thereto. It is not.
  • step d the carbon dioxide desorbed absorbent and the degassed carbon dioxide are separated and discharged (each gas containing degassed carbon dioxide through an outlet 304 and the carbon dioxide desorbed through an outlet 305), and the carbon dioxide degassed.
  • the absorbent may be supplied back to the absorbent module 100 and circulated.
  • the present invention may further comprise the step (step 6) of purifying hydrogen (H 2 ) using a gas separation membrane gas containing hydrogen separated and discharged in the step 4.
  • nitrogen may be separated from the gas containing hydrogen in step 4 through a gas separation membrane, or, most preferably, gas other than hydrogen may be separated to finally purify hydrogen.
  • the gas separation membrane used for the nitrogen separation or gas separation except hydrogen may be one known by a person skilled in the art.
  • An absorbent module (100) including an absorbent filler space (102) defined by an outer side of the hollow fiber separator and the inside of the housing constituting the hollow fiber separator;
  • An absorbent supply unit 200 for supplying an absorbent to the absorbent filling space of the absorbent module
  • the apparatus for capturing carbon dioxide and recovering hydrogen from steelmaking by-product gas includes: a housing preventing and protecting leakage of an internal fluid; A porous hollow fiber membrane 101 mounted in the housing; And an absorbent filler space 102 defined by an outer side of the hollow fiber membrane and an inner side of the housing constituting the hollow fiber membrane.
  • An absorbent supply unit 200 for supplying an absorbent to the absorbent filling space of the absorbent module;
  • a gas supply unit 700 for supplying an iron and steel by-product gas including hydrogen (H 2 ) and carbon dioxide (CO 2 ) into the hollow fiber of the hollow fiber membrane of the absorption module;
  • An outlet 103 for discharging the gas containing hydrogen not dissolved into the absorbent to the outside of the absorbent module.
  • the surface of the hollow fiber separation membrane 101 is in the form of fine pores, the diffusion of the absorbent is impossible, and the steel production by-product gas can pass through.
  • the hollow fiber membrane may be in contact with the absorbent.
  • carbon dioxide has a high solubility in the absorbent at high pressure, but the remaining gases hydrogen, nitrogen and the like are not high in the absorbent. Therefore, the steel by-product gas passing through the hollow fiber membrane is separated by dissolving carbon dioxide at the interface between the hollow fiber membrane and the absorbent, and the remaining undissolved gas is discharged.
  • a gas pressure control unit controlling a pressure of the steel production by-product gas in the absorption module
  • a degassing module 300 connected with the absorbing module and through which the absorbent passes; And a first pressure reducing pump 400 for adjusting a pressure in the degassing module.
  • the degassing module The degassing module,
  • a hollow fiber separator 301 mounted in the housing and into which the separated carbon dioxide is introduced into the hollow fiber;
  • a carbon dioxide degassing space 303 inside the hollow fiber membrane constituting the hollow fiber membrane.
  • the degassing module 300 may use a hollow fiber membrane similar to the absorbent module 100.
  • the absorbent is circulated and supplied as described above, and thus the same as that of the absorbent module.
  • the absorbent that has passed through the absorbent module has a large amount of carbon dioxide dissolved therein, it is possible to degas the carbon dioxide dissolved in the absorbent in the degassing module.
  • the absorbent supplied to the outside of the hollow fiber membrane 301 of the degassing module is in contact with the gas present in the carbon dioxide degassing space 303 inside the hollow fiber membrane and the hollow fiber membrane, the carbon dioxide dissolved in the absorber carbon dioxide degassing space It is degassed and discharged separately from the absorbent in which the degassing is performed.
  • An absorbent degassing tank 500 connected to the absorbing module 100 and the degassing module 300; And a second pressure reducing pump 600 for adjusting a pressure in the absorbent degassing tank.
  • the absorbent degassing tank 500 stores the absorbent circulating through the absorbent module 100 and the degassing module 300. At this time, the second pressure reducing pump to adjust the pressure inside the absorbent degassing tank may be reduced to a pressure of 0.5 atm to 0.9 atm, wherein the carbon dioxide dissolved in the absorbent may be partially separated, the partial separated Carbon dioxide may be transferred into the hollow fiber membrane 101 of the absorption module.
  • It may further include a gas separation membrane connected to the absorption module and configured to purify hydrogen (H 2 ) from the gas discharged from the absorption module.
  • a gas separation membrane connected to the absorption module and configured to purify hydrogen (H 2 ) from the gas discharged from the absorption module.
  • Hydrogen may be finally purified by separating nitrogen from a gas containing hydrogen that has passed through the absorption module through the gas separation membrane, or by separating gas other than hydrogen.
  • a gas separation membrane used for nitrogen separation or gas separation except hydrogen may be one known by a person skilled in the art.
  • the hollow fiber membranes of the absorption module and the degassing module are polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), perfluoroalkoxy alkanes ), Fluorinated ethylene propylene, ethylene tetrafluoroethylene (ETFE), ethylene fluorinated ethylene propylene (EFEP) and polyphenylene may be used. It can be, if the material to prevent the diffusion of the absorbent and to form a hollow fiber membrane having a fine pore is not limited thereto.
  • the average pore size of the hollow fiber membranes of the absorption module and the degassing module may be 0.001 ⁇ m to 2 ⁇ m, and may be 0.001 ⁇ m to 1 ⁇ m, but gas-liquid contact may be made through the hollow fiber membranes of the absorption module and the degassing module.
  • the pore size that can be effectively achieved is not limited thereto.
  • the porosity of the hollow fiber membranes of the absorption module and the degassing module may be 10% to 90%, and may be 20% to 80%, but gas-liquid contact is effectively achieved through the hollow fiber membranes of the absorption module and the degassing module. If possible porosity is not limited to this.
  • the absorbent of the absorption module and the degassing module may be water, polypropylene carbonate (PC) and polyethylene glycol dimethyl ether (PEGDME) and the like, preferably water may be used, but can selectively absorb carbon dioxide and hollow fiber membrane If the fluid does not pass through it is not limited thereto.
  • PC polypropylene carbonate
  • PEGDME polyethylene glycol dimethyl ether
  • At least one absorption module or degassing module may be connected in series or in parallel, or in series and parallel mixing.
  • the outlet of the absorption module is provided with an outlet 104 for separating and discharging the absorbent selectively absorbing carbon dioxide from the seasonal by-product gas and an outlet 103 for separating and discharging the gas (gas containing hydrogen) from which carbon dioxide has been removed.
  • the discharge port may be organically connected to the absorption module or may be directly installed in the absorption module.
  • the degassing module like the absorption module,
  • the outlet of the degassing module is provided with a discharge port 304 for degassing carbon dioxide from the absorbent and finally discharging and discharging the gas containing carbon dioxide and a discharge port 305 for discharging the absorbent after carbon dioxide is degassed.
  • the outlet may be organically connected to the degassing module or may be installed directly in the degassing module.
  • each module described above may be circulated such that it can be organically connected or reused with a subsequent device that allows further processing of the gas or absorbent discharged from the module.
  • a carbon dioxide capture and hydrogen recovery system was constructed from the steel production by-product gas, in which the average pore size of the hollow fiber membrane of the absorption module 100 was 0.2 ⁇ m, and the effective membrane area was 0.2 m 2 .
  • Polypropylene was used.
  • two absorption modules were provided in series.
  • As the steel by-product gas a gas having a composition of H 2 (20.6%), N 2 (44.4%), and CO 2 (35%) that was subjected to water gas conversion (WGS) was used.
  • Step 1 Water was used as the absorbent and fed into the absorbent filling space at a flow rate of 500 ml / min.
  • Step 2 The iron by-product gas was supplied into the hollow fiber membrane of the absorption module at a flow rate of 200 ml / min.
  • Step 3 The absorbent in the absorbent module was maintained at a pressure of 3 atm, and the seasonal by-product gas at a pressure of 2.5 atm.
  • Step 4 The gas containing hydrogen, which is the seasonal by-product gas passed through the absorption module, and the absorbent in which carbon dioxide was dissolved were discharged.
  • the absorbent water was allowed to be continuously supplied from an external device.
  • a carbon dioxide capture and hydrogen recovery system was constructed from steel by-product gas, in which the average pore size of the hollow fiber membrane of the absorption module 100 was 0.2 ⁇ m, and the effective membrane area was 0.2 m 2 .
  • Polypropylene was used.
  • two absorption modules were provided in series.
  • As the steel by-product gas a gas having a composition of H 2 (20.6%), N 2 (44.4%), and CO 2 (35%) that was subjected to water gas conversion (WGS) was used.
  • Step 1 Water was used as the absorbent and fed into the absorbent filling space at a flow rate of 500 ml / min.
  • Step 2 The iron by-product gas was supplied into the hollow fiber membrane of the absorption module at a flow rate of 200 ml / min.
  • Step 3 The absorbent in the absorbent module was maintained at a pressure of 3 atm, and the seasonal by-product gas at a pressure of 2.5 atm.
  • Step 4 The gas containing hydrogen, which is the seasonal by-product gas passed through the absorption module, and the absorbent in which carbon dioxide was dissolved were discharged.
  • the degassing module 300 and the absorbent degassing tank 500 for separating the gas containing hydrogen and the carbon dioxide dissolved absorbent, the gas containing hydrogen as the seasonal by-product gas passed through the absorbent module 100, the carbon dioxide dissolved in the absorbent ) was further added to degas the carbon dioxide.
  • the average pore size of the hollow fiber membrane 301 of the degassing module 300 is 0.2 ⁇ m
  • the effective membrane area is 0.2 m 2
  • the material was polypropylene.
  • two degassing modules were provided in series.
  • the absorbent in which carbon dioxide was dissolved in the step 4 was supplied to the absorbent degassing tank 500, and degassed partially dissolved carbon dioxide by depressurizing to a pressure of 0.8 atm.
  • Step a The absorbent supplied from the absorbent degassing tank was supplied to the absorbent filling space 302 of the degassing module 300.
  • Step b The gas inside the hollow fiber membrane 301 of the degassing module 300 was discharged to the outside.
  • Step c The gas inside the hollow fiber membrane was depressurized to 0.02 atm using the first pressure reducing pump 400 so that the carbon dioxide dissolved in the absorbent of step a could be degassed into the hollow fiber membrane 301.
  • Step d The carbon dioxide degassed absorbent and the degassed carbon dioxide in the hollow fiber membrane 301 of the degassing module 300 was separated and discharged.
  • Example 1 having a carbon dioxide capture and hydrogen recovery apparatus from the steelmaking by-product gas according to the present invention showed a hydrogen recovery rate of about 90% and a carbon dioxide removal rate, and Example 2 of about 95% or more of hydrogen. It was confirmed that the recovery rate and the carbon dioxide removal rate were shown. Therefore, the degassing module 300 and the absorbent degassing tank 500 were further provided, and it was confirmed that Example 2, which has undergone the step of degassing the carbon dioxide dissolved in the absorbent, has a high hydrogen recovery rate and a carbon dioxide removal rate.
  • the method and apparatus for capturing carbon dioxide and recovering hydrogen from steelmaking by-product gas according to the present invention have advantages such as simpler, smaller size, lower installation cost, and lower running cost than the prior art through hollow fiber membranes and absorbents.
  • carbon dioxide in the case of a gas containing water and other impurities after the water gas reaction (WGS), carbon dioxide can be stably separated, and hydrogen can be recovered, thereby reducing the burden of pretreatment and having high energy efficiency.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Analytical Chemistry (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Combustion & Propulsion (AREA)
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  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

La présente invention concerne un procédé de collecte de dioxyde de carbone présent dans un produit secondaire gazeux d'élaboration de l'acier, et de récupération d'hydrogène. Un procédé et un appareil de collecte de dioxyde de carbone présent dans un produit secondaire gazeux d'élaboration de l'acier, et de récupération d'hydrogène selon la présente invention présentent les avantages en ce que le procédé est plus simple que la technologie de l'état de la technique mise en œuvre par l'intermédiaire d'une membrane de séparation à fibres creuses et d'un absorbant, l'appareil peut être de taille réduite, l'appareil présente de faibles coûts d'installation et de fonctionnement, etc. De plus, même dans le cas d'un gaz qui n'a pas subi de réaction du gaz à l'eau (WGS) et qui contient de l'humidité et d'autres impuretés, du dioxyde de carbone peut être séparé de manière stable et de l'hydrogène peut être récupéré, fournissant ainsi les avantages en ce que la charge se rapportant au prétraitement est faible et l'efficacité énergétique est élevée.
PCT/KR2016/015112 2015-12-22 2016-12-22 Procédé et appareil de collecte de dioxyde de carbone présent dans un produit secondaire gazeux d'élaboration de l'acier, et de récupération d'hydrogène Ceased WO2017111503A1 (fr)

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KR10-2015-0183578 2015-12-22
KR1020150183578A KR101759101B1 (ko) 2015-12-22 2015-12-22 제철 부생가스로부터 이산화탄소 포집, 수소 회수 방법 및 장치

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KR101986632B1 (ko) * 2017-08-10 2019-06-07 울산과학기술원 고로가스 운영시스템
KR102032417B1 (ko) * 2017-12-20 2019-10-16 재단법인 포항산업과학연구원 다단 분리막을 이용한 제철 부생가스로부터의 고농도 유효가스의 분리 방법 및 장치
KR102622341B1 (ko) * 2018-12-28 2024-01-11 주식회사 금강씨엔티 이산화탄소 포집과 수소생산 동시 수행을 위한 수소분리/이산화탄소 흡수 하이브리드 장치 및 공정
KR102350033B1 (ko) * 2019-12-16 2022-01-11 주식회사 포스코 Finex 부생가스로부터 수소를 회수하는 방법 및 장치
KR102503631B1 (ko) 2020-12-18 2023-02-24 주식회사 포스코 가스 처리 장치 및 수소 가스 제조 방법
KR102548309B1 (ko) * 2020-12-18 2023-06-26 주식회사 포스코 이산화탄소 배출 저감형 용철 제조장치 및 그 제조방법
KR102578044B1 (ko) 2021-05-25 2023-09-15 한국화학연구원 제철 부생가스로부터 이산화탄소, 수소 및 일산화탄소를 분리하는 방법
CN113522007B (zh) * 2021-07-30 2023-03-21 哈尔滨工业大学 沼气提纯双膜曝气膜生物膜反应器及其使用方法
KR102579471B1 (ko) * 2021-09-15 2023-09-14 경북대학교 산학협력단 이산화탄소 건식 흡수제를 이용한 일산화탄소 및 합성가스 생성 공정 및 시스템
EP4610244A1 (fr) 2022-10-25 2025-09-03 Korea Research Institute of Chemical Technology Procédé de préparation de matière première pour matières plastiques à l'aide de sous-produit gazeux d'acier

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040042656A (ko) * 2002-11-15 2004-05-20 한국화학연구원 중공사막 접촉기용 이산화탄소 흡수제
JP2007254229A (ja) * 2006-03-24 2007-10-04 Sekiyu Combinat Kodo Togo Unei Gijutsu Kenkyu Kumiai 水素製造方法および水素製造装置
KR20100105908A (ko) * 2008-03-18 2010-09-30 제이에프이 스틸 가부시키가이샤 고로가스의 분리방법
KR20140049702A (ko) * 2012-10-18 2014-04-28 한국화학연구원 미세 다공성 중공사막을 이용한 바이오 가스로부터의 메탄 가스 고순도 정제 방법 및 장치

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040042656A (ko) * 2002-11-15 2004-05-20 한국화학연구원 중공사막 접촉기용 이산화탄소 흡수제
JP2007254229A (ja) * 2006-03-24 2007-10-04 Sekiyu Combinat Kodo Togo Unei Gijutsu Kenkyu Kumiai 水素製造方法および水素製造装置
KR20100105908A (ko) * 2008-03-18 2010-09-30 제이에프이 스틸 가부시키가이샤 고로가스의 분리방법
KR20140049702A (ko) * 2012-10-18 2014-04-28 한국화학연구원 미세 다공성 중공사막을 이용한 바이오 가스로부터의 메탄 가스 고순도 정제 방법 및 장치

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEN, WEI-HSIN ET AL.: "An Evaluation of Hydrogen Production from the Perspective of Using Blast Furnace Gas and Coke Oven Gas as Feedstocks", INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, vol. 36, no. 18, 2011, pages 11727 - 11737, XP028271006 *

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