US20160256819A1 - Hybrid membrane and adsorption-based system and process for recovering co2 from flue gas and using combustion air for adsorbent regeneration - Google Patents
Hybrid membrane and adsorption-based system and process for recovering co2 from flue gas and using combustion air for adsorbent regeneration Download PDFInfo
- Publication number
- US20160256819A1 US20160256819A1 US14/638,631 US201514638631A US2016256819A1 US 20160256819 A1 US20160256819 A1 US 20160256819A1 US 201514638631 A US201514638631 A US 201514638631A US 2016256819 A1 US2016256819 A1 US 2016256819A1
- Authority
- US
- United States
- Prior art keywords
- stream
- gas stream
- permeate
- deficient
- vent gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003546 flue gas Substances 0.000 title claims abstract description 79
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 239000003463 adsorbent Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims description 34
- 230000008929 regeneration Effects 0.000 title claims description 20
- 238000011069 regeneration method Methods 0.000 title claims description 20
- 238000002485 combustion reaction Methods 0.000 title abstract description 21
- 238000001179 sorption measurement Methods 0.000 title abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 186
- 239000012466 permeate Substances 0.000 claims abstract description 112
- 239000007788 liquid Substances 0.000 claims abstract description 66
- 238000000926 separation method Methods 0.000 claims abstract description 54
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 15
- 239000000446 fuel Substances 0.000 claims abstract description 9
- 230000002950 deficient Effects 0.000 claims description 85
- 239000000047 product Substances 0.000 claims description 43
- 238000004891 communication Methods 0.000 claims description 30
- 239000012530 fluid Substances 0.000 claims description 30
- 238000004821 distillation Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 13
- 238000005191 phase separation Methods 0.000 claims description 13
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000012546 transfer Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 6
- 230000000153 supplemental effect Effects 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 231
- 229910002092 carbon dioxide Inorganic materials 0.000 description 228
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 229910001868 water Inorganic materials 0.000 description 25
- 238000011084 recovery Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000001301 oxygen Substances 0.000 description 15
- 229910052760 oxygen Inorganic materials 0.000 description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 239000003245 coal Substances 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000001991 steam methane reforming Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- 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
- B01D53/002—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 condensation
-
- 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
-
- C01B31/20—
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0257—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of nitrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/02—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
- F25J3/0228—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
- F25J3/0266—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/066—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of nitrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J3/00—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
- F25J3/06—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation
- F25J3/063—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream
- F25J3/067—Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by partial condensation characterised by the separated product stream separation of 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
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2215/00—Preventing emissions
- F23J2215/50—Carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2219/00—Treatment devices
- F23J2219/70—Condensing contaminants with coolers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2900/00—Special arrangements for conducting or purifying combustion fumes; Treatment of fumes or ashes
- F23J2900/15061—Deep cooling or freezing of flue gas rich of CO2 to deliver CO2-free emissions, or to deliver liquid CO2
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/02—Processes or apparatus using separation by rectification in a single pressure main column system
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2200/00—Processes or apparatus using separation by rectification
- F25J2200/70—Refluxing the column with a condensed part of the feed stream, i.e. fractionator top is stripped or self-rectified
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/02—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum
- F25J2205/04—Processes or apparatus using other separation and/or other processing means using simple phase separation in a vessel or drum in the feed line, i.e. upstream of the fractionation step
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/40—Processes or apparatus using other separation and/or other processing means using hybrid system, i.e. combining cryogenic and non-cryogenic separation techniques
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2205/00—Processes or apparatus using other separation and/or other processing means
- F25J2205/60—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end
- F25J2205/64—Processes or apparatus using other separation and/or other processing means using adsorption on solid adsorbents, e.g. by temperature-swing adsorption [TSA] at the hot or cold end by pressure-swing adsorption [PSA] at the hot end
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/04—Mixing or blending of fluids with the feed stream
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2210/00—Processes characterised by the type or other details of the feed stream
- F25J2210/70—Flue or combustion exhaust gas
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2220/00—Processes or apparatus involving steps for the removal of impurities
- F25J2220/60—Separating impurities from natural gas, e.g. mercury, cyclic hydrocarbons
- F25J2220/62—Separating low boiling components, e.g. He, H2, N2, Air
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2230/00—Processes or apparatus involving steps for increasing the pressure of gaseous process streams
- F25J2230/30—Compression of the feed stream
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2235/00—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams
- F25J2235/80—Processes or apparatus involving steps for increasing the pressure or for conveying of liquid process streams the fluid being carbon dioxide
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/40—Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval
- F25J2240/44—Expansion without extracting work, i.e. isenthalpic throttling, e.g. JT valve, regulating valve or venturi, or isentropic nozzle, e.g. Laval the fluid being nitrogen
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2240/00—Processes or apparatus involving steps for expanding of process streams
- F25J2240/90—Hot gas waste turbine of an indirect heated gas for power generation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2245/00—Processes or apparatus involving steps for recycling of process streams
- F25J2245/02—Recycle of a stream in general, e.g. a by-pass stream
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
- F25J2270/00—Refrigeration techniques used
- F25J2270/04—Internal refrigeration with work-producing gas expansion loop
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/32—Direct CO2 mitigation
-
- 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
Definitions
- the present invention relates to a process and apparatus for the separation of gaseous mixture containing carbon dioxide as main component. It relates in particular to processes and apparatus for purifying carbon dioxide, for example coming from combustion of a carbon containing fuel, such as takes place in an air-fired or oxycombustion fossil fuel or biomass power plant.
- high CO 2 recoveries from feed gases is desirable for a variety of reasons.
- the U.S. Department of Energy (DOE) has set a target recovery for recovering CO 2 from power plants.
- high CO 2 recoveries allow more CO 2 product gas to be sold or used in order to recover the costs associated with the pre-treatment of the flue gas necessary for recovery.
- the driving force across the membrane decreases and approaches a pinch point beyond which additional recovery comes at the expense of high compression energy costs or high membrane surface areas.
- this problem has the potential to increase capital and operating expenses to unsatisfactory levels.
- Membranes are known to be efficient for bulk separation of gases when the driving force is high. They have been used in combination with other, subsequent, gas separation techniques in order to achieve an overall CO 2 recovery. Such hybrid systems are known where a membrane performs a bulk CO 2 separation from natural gas followed by amine treatment of the lower concentration membrane residue stream. Hybrid combinations of solvent (e.g. piperazine) and membrane have also been studied for CO 2 capture from flue gas.
- solvent e.g. piperazine
- Hybrid processes combining adsorption and membranes are also known.
- U.S. Pat. No. 8,591,769 and U.S. Pat. No. 6,183,628 discuss membrane treatment of PSA vent gas to recover H 2 .
- this technique was applied to flue gas, such a scheme would require use of a less optimum adsorbent that is exposed to many impurities Co-adsorption of moisture and other acid gas components in flue gas prevents optimum adsorption of CO 2 .
- WO14009449 A1 proposes to combine membrane and adsorption processes for moisture removal.
- Membranes can be swept with a sweep gas in order to overcome the above-described membrane driving force pinch problem.
- U.S. Pat. No. 8,734,569 discloses that this can be done by diverting a small fraction of gas (that is derived from the low CO 2 concentration residue) to sweep the permeate side of a membrane module.
- a small fraction of gas that is derived from the low CO 2 concentration residue
- the permeate CO 2 concentration decreases marginally but the membrane area can be decreased significantly.
- permeate CO 2 concentrations can decrease significantly.
- Another sweep concept particularly applicable to CO 2 capture from flue gas, utilizes a two step membrane process (Merkel, et al., “Power plant post-combustion carbon dioxide capture: An opportunity for membranes”, Journal of Membrane Science 359 (2010) 126-139).
- the 1 st permeate at relatively high CO 2 purity is sent for further CO 2 purification.
- the 2 nd membrane is swept with an air stream to achieve high CO 2 recovery.
- the air stream is then sent to the boiler island where the recovered CO 2 dilutes the overall stream, imposing a small energy penalty for combustion.
- a method for recovering CO 2 from flue gas that comprises the following steps. Impurities are removed from a flue gas stream to provide a purified flue gas stream.
- the purified flue gas stream is compressed at a first compressor and fed to a gas separation membrane unit comprising one or more gas separation membranes to produce a permeate stream and a non-permeate stream deficient in CO 2 compared to the permeate stream.
- the permeate stream is compressed at a second compressor.
- the permeate stream is cooled to produce a partially condensed permeate stream.
- the partially condensed permeate stream is separated into a CO 2 -deficient vent gas stream deficient in CO 2 compared to partially condensed permeate stream and high purity liquid CO 2 product.
- the CO 2 -deficient vent gas stream is recycled to the gas separation membrane unit.
- the non-permeate stream is fed to a PSA unit comprising one or more adsorbent beds to produce a further CO 2 -depleted vent gas stream depleted in CO 2 compared to the non-permeate stream, a CO 2 blow-down stream enriched in CO 2 compared to the non-permeate stream, and a regeneration product stream.
- the CO 2 blow-down stream is compressed at the second compressor along with the permeate stream.
- the regeneration product stream is combusted at a combustor that produces the flue gas.
- the regeneration product stream is produced by feeding a stream of air to the PSA unit to regenerate one of said one or more adsorbent beds and desorb CO 2 therefrom.
- the regeneration product stream is air enriched with the desorbed CO 2 .
- a system for recovering CO 2 from flue gas comprising: a combustor adapted and configured to combust fuel, oxidant, and supplemental oxidant to produce a flue gas stream; a purification unit in fluid communication with the combustor that is adapted and configured to purify the flue gas stream and produce a purified flue gas stream; a first compressor in fluid communication with the purification unit that is adapted and configured to compress the purified flue gas stream; a gas separation membrane unit in fluid communication with the first compressor that comprising one or more gas separation membranes adapted and configured to receive a feed gas stream from the first compressor and separate the feed gas stream into a permeate gas stream and a non-permeate gas stream that is deficient in CO 2 compared to the permeate gas stream; a second compressor in fluid communication with the gas separation membrane unit that is adapted and configured to receive and compress the permeate gas stream to produce a compressed permeate gas stream; at least one heat exchanger, at least one of the at least one
- the method and/or system may include one or more of the following aspects:
- the compressed purified flue gas stream is cooled at a heat exchanger to a temperature ranging from 20° C. to ⁇ 60° C.
- the further CO 2 -depleted vent gas stream is expanded to lower a temperature thereof, wherein the compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the expanded further CO 2 -depleted vent gas stream.
- the compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the CO 2 -deficient vent gas stream prior to feeding the CO 2 -deficient gas stream to the gas separation membrane unit.
- the CO 2 -deficient vent gas stream is heat exchanged two times with the compressed purified flue gas stream and the CO 2 -deficient vent gas stream is expanded to lower a temperature thereof in between the two times.
- the high purity liquid CO 2 product is vaporized at the heat exchanger to produce a high purity CO 2 product gas, wherein the compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the high purity liquid CO 2 product.
- the non-permeate stream is expanded to lower a temperature thereof prior to being fed to the PSA unit, wherein compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the expanded non-permeate stream.
- the non-permeate stream is heat exchanged two times with the compressed purified flue gas stream and the non-permeate stream is expanded in between the two times.
- said step of separating is performed by separating the partially condensed permeate stream in a phase separator.
- step of separating is performed by: separating the partially condensed permeate stream in a first phase separator into a first CO 2 -deficient vent gas stream deficient in CO 2 compared to partially condensed permeate stream and a first high purity liquid CO 2 stream; expanding the first CO 2 -deficient vent gas stream for partial condensation thereof; separating the partially condensed first CO 2 -deficient vent gas stream into a second CO 2 -deficient vent gas stream deficient in CO 2 compared to partially condensed permeate stream and a second high purity liquid CO 2 stream; and combining the first and second high purity liquid CO 2 streams to produce the high purity liquid CO 2 product.
- said step of separating is performed by: separating the partially condensed permeate stream in a first phase separator into a first CO 2 -deficient vent gas stream deficient in CO 2 compared to partially condensed permeate stream and a first high purity liquid CO 2 stream; expanding the first CO 2 -deficient vent gas stream for partial condensation thereof; separating the partially condensed first CO 2 -deficient vent gas stream into a second CO 2 -deficient vent gas stream deficient in CO 2 compared to partially condensed permeate stream and a second high purity liquid CO 2 stream; expanding each of the first and second high purity liquid CO 2 streams at first and second Joule-Thomson expanders; feeding the expanded high purity liquid CO 2 streams to a distillation column; withdrawing the high purity liquid CO 2 product from a bottom of the distillation column; and withdrawing a CO 2 -deficient vapor stream from a top of the distillation column, wherein the CO 2 -deficient vent gas stream is comprised of the second CO 2 -deficient vent gas stream
- an expander is adapted and configured to expand the further CO 2 -depleted vent gas stream to lower a temperature of the further CO 2 -depleted vent gas stream, wherein at least one of the at least one heat exchanger is in heat transfer relation between, on one hand, the further CO 2 -depleted vent gas stream, and on the other hand, either the feed gas stream or the compressed permeate stream.
- At least one of the at least one heat exchanger is in heat transfer relation between the feed gas stream and the CO 2 -deficient vent gas stream.
- At least one of the at least one heat exchanger is in heat transfer relation between the high purity liquid CO 2 product and the feed gas stream and is further adapted and configured to vaporize the high purity liquid CO 2 product to produce a high purity CO 2 gas product.
- an expander is adapted and configured to expand the non-permeate stream to lower a temperature thereof, wherein at least one of the at least one heat exchanger is in heat transfer relation between the expanded non-permeate stream and the feed gas stream.
- the phase separation unit comprises one phase separator vessel.
- the phase separation unit comprises first and second phase separator vessels and a Joule-Thomson expander;
- the first phase separator vessel is in fluid communication with the second compressor and is adapted and configured to receive the partially condensed permeate stream for phase separation into a first CO 2 -deficient vent gas stream and a first liquid CO 2 stream;
- the Joule-Thomson expander is in fluid communication between the first and second phase separator vessels and is adapted and configured to expand the first CO 2 -deficient vent gas stream for partial condensation thereof;
- the second phase separator vessel is in fluid communication with the Joule-Thomson valve and is adapted and configured to receive the partially condensed first CO 2 -deficient vent gas stream for separation into a second CO 2 -deficient vent gas stream and a second liquid CO 2 stream;
- the high purity liquid CO 2 product is comprised of the first and second high purity liquid CO 2 streams;
- the first compressor is in fluid communication with the second phase separator vessel to receive the second CO 2 -deficient vent gas stream
- the phase separation unit comprises first and second phase separator vessels, first, second, and third Joule-Thomson valves, and a distillation column;
- the first phase separator vessel is in fluid communication with the second compressor and is adapted and configured to receive the partially condensed permeate stream for phase separation into a first CO 2 -deficient vent gas stream and a first liquid CO 2 stream;
- the first Joule-Thomson expander is in fluid communication between the first and second phase separator vessels and is adapted and configured to expand the first CO 2 -deficient vent gas stream for partial condensation thereof;
- the second phase separator vessel is in fluid communication with the first Joule-Thomson valve and is adapted and configured to receive the partially condensed first CO 2 -deficient vent gas stream for separation into a second CO 2 -deficient vent gas stream and a second liquid CO 2 stream;
- the second and third Joule-Thomson valves are in fluid communication between the first and second phase separator vessel, respectively, and the distillation column;
- the flue gas contains 3-90% vol CO 2 .
- a non-CO 2 balance of the flue gas is predominantly N 2 .
- the flue gas is obtained from an air-fired coal combustion plant and contains 8-16% vol CO 2 .
- the flue gas is obtained from an air-fired natural gas combustion plant and contains 3-10% vol CO 2 .
- the flue gas is obtained from an oxycoal combustion plant combusting coal with pure oxygen or synthetic air and contains 60-90% vol CO 2 .
- the flue gas is obtained from a steam methane reformer and contains 15-90% vol CO 2 .
- the flue gas is obtained from a blast furnace and contains 20-90% CO 2 .
- the flue gas comprises 4-30% vol CO 2 .
- FIG. 1 is a schematic of the inventive method and system.
- FIG. 2 is a schematic of an embodiment of the inventive method and system.
- FIG. 3 is a schematic of another embodiment of the inventive method and system.
- FIG. 4 is a schematic of a two-phase separator alternative to the single phase separator of FIG. 2 or FIG. 3 .
- FIG. 5 is a schematic of a two-phase separator plus distillation column alternative to the single phase separator of FIG. 2 or FIG. 3 .
- the method combines the benefits of the gas separation techniques of membranes and adsorption, but integrates the two to maximize efficiencies. For example, a recovery of greater than approximately 90% of the CO 2 from the flue gas of an existing air-fired coal power plant may be possible with a less than approximately 35% increase in the plant's cost of electricity.
- the flue gas may be obtained or derived from suitable combustion processes such as steam methane reforming (SMR), blast furnaces, and air-fired or oxygen-enhanced combustion of fossil fuels (such as in power plants).
- SMR steam methane reforming
- blast furnaces blast furnaces
- oxygen-enhanced combustion of fossil fuels such as in power plants.
- the combustion may be full oxycombustion or partial oxycombustion.
- the primary and secondary oxidants and tertiary and quaternary oxidants, if present
- one or more of the oxidants may be air and one or more of the remaining oxidants may be oxygen or synthetic air (a mixture of oxygen and recycled flue gas), or alternatively, one or more of the oxidants may be oxygen-enriched air.
- Pure oxygen means that the oxidant has a concentration typically found in conventional industrial oxygen production processes such as in cryogenic air separation units.
- the oxygen concentration of synthetic air may range from a concentration at, or above that, of oxygen in air to a concentration less than pure oxygen.
- the flue gas contains 3-90% vol CO 2 .
- Other components that may be contained within the flue gas include but are not limited to other combustion byproducts, such as water, methane, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen.
- the non-CO 2 balance of the flue gas is predominantly N 2 .
- Flue gas obtained from an air-fired coal combustion plant typically contains 8-16% vol CO 2
- flue gas obtained from an air-fired natural gas combustion plant typically contains 3-10% vol CO 2 .
- Flue gas obtained from an oxycoal combustion plant typically contains 60-90% vol CO 2 with a balance of water, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen.
- Flue gas obtained from a steam methane reformer typically contains 15-90% vol CO 2 with a balance of water, methane, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen.
- Flue gas obtained from a blast furnace typically contains 20-90% CO 2 with a balance of water, hydrogen, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen.
- the flue gas comprises 4-30% vol CO 2 .
- a fuel stream 51 , one or more oxidant streams 52 and a supplemental oxidant stream 66 are combusted at a combustor 1 , thereby producing a raw flue gas stream 53 .
- the type of fuel in fuel stream 51 and the type of combustor 1 are not limited, typically the fuel is natural gas or coal and the combustor 1 is a boiler.
- One or more streams of the one or more oxidant streams 52 may be air, oxygen-enriched air, and/or industrially pure oxygen.
- the supplemental oxidant stream 66 is described below. It or they may be fed as primary air with or without secondary air, tertiary air, and quaternary air.
- primary air “secondary air”, “tertiary air”, and “quaternary air” are not meant as being limited to air, but rather encompass oxygen-enriched air and industrially pure oxygen as well.
- Raw stream 53 is fed to a purification unit 2 for removal of impurities.
- Suitable treatment methods include but are not limited to those disclosed in WO 2009010690, WO 2009095581, and U.S. Published Patent Application Nos. US 2009013717, US2009013868, and US2009013871, the treatment methods of which are incorporated herein by reference in their entireties.
- the moisture content of the raw stream 53 should be reduced to a low level for a variety of reasons. First, it is desirable to avoid competition for the adsorbent (in the downstream PSA unit 7 ) by moisture and CO 2 . In the case of sub-ambient membrane operation in gas separation membrane unit 4 , it is desirable to avoid the freezing of moisture on cold surfaces in any heat exchanger present.
- drying materials and adsorbent-based processes include alumina, silica, or molecular sieves. Condensation of moisture through cooling may also be used to lower the moisture content of raw gas stream 53 .
- the purification unit 2 typically removes particulates with filters and acid gases, such as NO x and So x , with scrubbers.
- the purified flue gas stream 54 is then compressed at a compression unit 3 to boost its pressure to about 4-20 bar.
- the compression unit 3 includes one or more compressors. In between multiple compression stages (in the case of a multi-stage compressor), stream 54 may be cooled with water, other non-water coolant, or a coolant gas whereby additional water may be removed from stream 54 through condensation (i.e., knocked out). In the case of a boiler for combustor 1 , stream 54 may be cooled with boiler feed water. In this manner, the boiler feed water may be pre-heated prior to introduction in the boiler combustor 1 and the efficiency of the boiler combustor 1 and compression unit 3 are both increased.
- stream 54 when stream 54 is compressed to 16 bar, sufficient heat is generated to pre-heat boiler feed water to approximately 147° C. In a coal power plant, such pre-heating allows more steam turbine energy to be used for electricity generation.
- Suitable types of compressors include centrifugal, screw, reciprocating, and axial compressors.
- compressed, purified flue gas stream 55 is fed to an inlet of a gas separation membrane unit 4 .
- the membranes of the gas separation membrane unit 4 allow selective permeation to form a low pressure CO 2 enriched permeate stream 57 and a CO 2 depleted stream non-permeate stream 58 .
- the gas separation membranes of unit 4 may be operated at ambient or sub-ambient temperature.
- the upstream water cooling is sufficient to bring stream 55 to ambient temperature.
- the required cold temperature is achieved through heat exchange between stream 56 and non-permeate stream 58 (after expansion of stream 58 ) and/or between stream 56 and PSA vent gas 64 (after expansion of stream 64 ).
- This heat exchange may be accomplished with a conventional heat exchanger, such as a plate fin, shell-in-tube, spiral wound, or brazed aluminum plate heat exchanger, or it may be a falling film evaporator as disclosed in EP 1008826, a heat exchanger derived from an automobile radiator as disclosed in US 2009/211733, or plate heat exchangers manufactured as disclosed in FR 2,930,464, FR 2,930,465, and FR 2,930,466.
- the heat exchangers in the cited patent publications are all incorporated herein by reference in their entireties.
- the heat exchanger is a brazed aluminum plate exchanger having multiple parallel cores allowing it to cool/heat a number of streams. The temperature of stream 54 should be maintained above its water freezing point.
- the permeate stream 57 is fed to a suction inlet of a compression unit 5 where the combined stream is compressed to about 16-30 bar.
- the compression unit 5 contains one or more compressors selected from centrifugal, screw, reciprocating, and axial compressors.
- the compression unit 5 also typically uses boiler feed water for cooling of stream 57 so that further water may be knocked out (or optionally, to avoid flooding of a water removal adsorbent) and the boiler feed water may be preheated.
- the compressed stream 60 is then fed to a liquefaction unit 6 to produce high purity ( ⁇ 95% vol) liquid CO 2 and a vent gas stream 62 .
- the high purity liquid CO 2 is re-gasified to produce gaseous CO 2 product 59 .
- the cold temperature required for liquefaction of the CO 2 is substantially generated through heat exchange with stream 58 (after expansion) and/or stream 64 (after expansion).
- the cold temperature required for liquefaction may optionally also be generated through heat exchange with a portion of the high purity liquid CO 2 so as to cool compressed stream 60 and vaporize the high purity liquid CO 2 .
- the liquefaction unit 6 may also include a pump to boost the pressure of high purity liquid CO 2 prior to re-gasification to produce the CO 2 product 61 .
- the CO 2 -depleted vent gas 62 containing about 20-40% vol CO 2 , is also fed to the gas separation membrane unit 4 . Depending upon the pressure of the CO 2 -depleted vent gas 62 , it can first be expanded to the pressure of stream 55 as necessary.
- the non-permeate stream 58 containing about 4-15% vol CO 2 , is fed to pressure swing adsorption (PSA) unit 7 .
- PSA unit 7 contains a plurality of adsorbent columns.
- CO 2 from stream 58 is selectively adsorbed so that a further CO 2 depleted vent gas 64 is produced that contains anywhere from 10 ppm vol to 4% vol of CO 2 .
- the CO 2 depleted vent gas 64 is expanded at a turbo-expander 8 to recover useful energy and vented to atmosphere as stream 65 .
- the adsorbed CO 2 is partially recovered as a CO 2 blow-down stream 69 .
- the CO 2 concentration of the CO 2 blow-down stream 69 is equal to or higher than that of stream 58 and is fed to the suction inlet of compressor 5 .
- the CO 2 concentration for the CO 2 blow-down stream 69 is lower than that of stream 58 , as shown by the dotted line, it may instead be fed to the suction inlet of compressor 3 .
- the adsorbent in PSA unit 7 is regenerated by an air stream 63 , thereby producing a vent stream 66 that contains air and substantially the remaining desorbed CO 2 .
- the air and desorbed CO 2 -containing stream 66 is fed to combustor 1 as the entirety of, or as a portion of, the primary, secondary, tertiary (if present), and/or quaternary (if present) oxidant that is fed to the combustor.
- Stream 66 may be mixed with a portion of oxidant from one or more of streams 52 or may be fed to combustor 1 separately from streams 52 .
- oxidant injection schemes are known in the field of combustion (especially combustion performed with recycled flue gas) and their details need not be recited herein.
- Some degree of moisture may remain adsorbed on adsorbent in PSA unit 7 after CO 2 desorption.
- a portion of the air of stream 63 may either be dried (e.g. with zeolite 3 A) or pre-heated upstream of PSA unit 7 .
- one embodiment includes sub-ambient membrane separation and expansion of a non-permeate stream downstream of PSA separation.
- Fuel 51 with one or more oxidant streams 52 and supplemental oxidant stream 66 are combusted in combustor 1 which is a boiler.
- the resulting flue gas stream 53 is purified in purification unit 2 for removal of impurities as described above.
- the purification unit 2 may optionally include a blower in order to provide adequate suction pressure for compressor 3 .
- compressor 3 may include one or more compressors which also typically includes water cooling of the compressed CO 2 enriched stream that may be used to preheat boiler feed water and for further water knock-out.
- the compressed, purified flue gas stream 55 after water cooling is dried with an adsorbent-based moisture removal unit 9 that contains one or more adsorbent beds containing adsorbents known in the art for removal of moisture from gases.
- Exchanger 10 may be a multi-stream type heat exchanger adapted and configured to exchange heat between a plurality of streams.
- the multi-stream heat exchanger is a brazed aluminum plate exchanger having multiple parallel cores allowing it to cool/heat the plurality of streams.
- exchanger 10 could be a combination of several smaller heat exchangers not necessarily exchanging heat between each of the streams illustrated. A combination of several smaller heat exchangers is useful for segregation of higher pressure streams from low pressure streams.
- each particular heat exchanger will exchange heat between less than all of the streams illustrated.
- the skilled artisan will recognize that selection of which stream or streams are used to cool another stream or streams at a particular heat exchanger is well within the knowledge of a chemical engineer in the field of industrial gases.
- the cold, dried, compressed, purified flue gas stream 68 is fed to a gas separation membrane unit 4 .
- the membranes of the gas separation membrane unit 4 allow selective permeation to form a low pressure CO 2 enriched permeate stream 57 and a CO 2 depleted stream non-permeate stream 58 .
- the gas separation membranes of unit 4 may be operated at ambient or sub-ambient temperature as described above.
- the CO 2 enriched permeate gas 57 is re-compressed to about 6-30 bar in compressor 5 .
- Compressor 5 also typically includes water cooling of stream 57 where the thus-heated water may be used as preheated boiler feed water.
- the water cooling of stream 57 also allows further water knock-out, but additional adsorbent-based drying may be included, if needed.
- the dried and compressed CO 2 enriched stream 60 having a concentration of >60% vol CO 2 , is cooled in exchanger 10 to partially condense the CO 2 .
- phase separator 12 is a one pot phase separation unit producing a high purity, liquid CO 2 stream 68 and a cold vent stream 62 .
- the pressure of the high purity, liquid CO 2 stream 68 is boosted to about 60-150 bar by a cryo-pump 14 and then warmed/vaporized at exchanger 10 to form high purity (>95% vol CO 2 ) product gas stream 59 .
- the cold vent stream 62 is passed through exchanger 10 and is optionally partially expanded in expander 15 to match the pressure of stream 67 . After heat exchange and optional partial expansion, stream 62 is combined with stream 67 .
- FIG. 2 illustrates a PSA unit with four adsorbent bed columns 71 , 72 , 73 , 74 .
- the PSA unit is not limited to such a configuration. Rather, it may be configured according to any other schemes known in the field of adsorbent-based gas separation taking into consideration capital cost vs. capture efficiency trade-offs.
- the adsorbent bed columns 71 , 72 , 73 , 74 cycle through four modes of operation:
- CO 2 is selectively adsorbed from warmed stream 58 by the adsorbent in column 71 .
- a further CO 2 depleted (10 ppm-4%) vent gas is expanded at expander 75 to provide a cold, expanded, CO 2 -depleted stream 64 .
- the cold, expanded, CO 2 -depleted stream 64 is passed through exchanger 10 to provide the necessary cold energy (i.e., for removal of enthalpy) to cool stream 67 for sub-ambient membrane operation and also to partially condense stream 60 .
- it may be heated at heat exchanger 76 and then further expanded at turbo-expander 8 for energy recovery and vented as inert vent gas 65 .
- CO 2 blow-down stream 69 has a CO 2 concentration equal to or higher than that of stream 58 and is fed to the suction inlet of compressor 5 .
- CO 2 blow-down stream 69 has a CO 2 concentration lower than that of stream 58 , as shown by the dotted line, it may instead be fed to the suction inlet of compressor 3 .
- the CO 2 -enriched air stream 66 is fed to combustor 1 as described above.
- the columns 71 , 72 , 73 , 74 are subsequently operated in the following modes:
- the columns 71 , 72 , 73 , 74 are subsequently operated in the following modes:
- FIG. 3 another embodiment also includes sub-ambient membrane separation and expansion of a non-permeate stream downstream of PSA separation.
- the embodiment of FIG. 3 is the same as FIG. 2 except for the following differences.
- the further CO 2 -depleted vent gas 74 from column 71 is not expanded for purposes of providing the necessary cold energy for cooling the combination of streams 62 and 67 and for partial condensation of stream 60 . Rather, stream 74 is heated at heat exchanger 76 and then further expanded at turbo-expander 8 for energy recovery and vented as inert vent gas 65 .
- the non-permeate stream 58 is expanded at expander 76 .
- the now-cold, expanded non-permeate stream 58 is passed through exchanger 10 in order to provide the necessary cold energy for cooling stream 67 and for partial condensation of stream 60 , prior stream 58 being fed to column 71 .
- the adsorption of CO 2 from stream 58 in column 71 takes place at a lower pressure and temperature than in the embodiment of FIG. 2 .
- FIGS. 2 and 3 show one phase separator 12 for effecting separation of the partially liquefied stream 60 into vent gas stream 62 and CO 2 product 59
- FIG. 4 includes two phase separators 12 a , 12 b .
- the embodiment of FIG. 4 can be thought of as a variation of the embodiment of FIG. 2 or a variation of the embodiment of FIG. 3 where all like-numbered reference characters denote a same apparatus or stream.
- permeate stream 57 is compressed and partially condensed by compressor 5 and exchanger 10 to produce stream 60 .
- stream 60 is received in a first phase separator 12 of two in-series phase separators 12 a , 12 b .
- the gaseous overhead from phase separator 12 a exits as stream 62 a , is partially expanded across a Joule-Thomson valve, further cooled at exchanger 10 , and partially condensed in phase separator 12 b .
- the resulting vent gas stream 62 b from phase separator 12 b is optionally further expanded in expander 13 b to provide vent gas stream 62 .
- the bottom CO 2 -rich liquids exiting phase separators 12 a , 12 b is combined to provide high purity liquid CO 2 stream 68 .
- the pressure of stream 68 is boosted at cryo-pump 14 and then vaporized at exchanger to form gaseous CO 2 product stream 59 .
- FIG. 5 includes two phase separators 12 a , 12 b plus a distillation column.
- the embodiment of FIG. 5 can be thought of as a variation of the embodiment of FIG. 2 or a variation of the embodiment of FIG. 3 where all like-numbered reference characters denote a same apparatus or stream.
- permeate stream 57 is compressed and partially condensed by compressor 5 and exchanger 10 to produce stream 60 .
- stream 60 is received in a first phase separator 12 of two in-series phase separators 12 a , 12 b .
- the gaseous overhead from phase separator 12 a exits as stream 62 a , is partially expanded across a Joule-Thomson valve, further cooled at exchanger 10 , and partially condensed in phase separator 12 b .
- the resulting vent gas stream 62 b from phase separator 12 b is optionally further expanded in expander 13 b.
- the bottom CO 2 -rich liquid exits phase separators 12 a , 12 b as streams 68 a , 68 b .
- Streams 68 a , 68 b are optionally expanded at Joule-Thomson valves 18 a , 18 b and fed to distillation column 16 .
- CO 2 -deficient vapor exits from a top of column 16 as vapor stream 18 and high purity liquid CO 2 exits a bottom of column 16 as high purity liquid CO 2 stream 68 .
- Vapor stream 18 is combined with vent gas stream 62 b to form CO 2 -depleted vent gas 62 .
- the pressure stream 68 is boosted at cryo-pump 14 and then vaporized at exchanger to form gaseous CO 2 product stream 59 .
- Suitable materials for use in the gas separation membranes include polymeric materials having a CO 2 permeance is >100 GPU and a CO 2 /N 2 selectivity >20 at the selected operational temperature and pressure.
- suitable polymeric materials exhibit a CO 2 solubility at 35° C. and 10 bar pressure of >0.03 [(cm 3 of CO 2 at STP)/(cm 3 of polymeric material)(cmHg)] and a glass transition temperature of >210° C.
- Particular polymeric materials meeting these requirements are disclosed in U.S. Pat. No. 8,617,292, the contents of which are incorporated herein by reference.
- “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing i.e. anything else may be additionally included and remain within the scope of “comprising.” “Comprising” is defined herein as necessarily encompassing the more limited transitional terms “consisting essentially of” and “consisting of”; “comprising” may therefore be replaced by “consisting essentially of” or “consisting of” and remain within the expressly defined scope of “comprising”.
- Providing in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.
- Optional or optionally means that the subsequently described event or circumstances may or may not occur.
- the description includes instances where the event or circumstance occurs and instances where it does not occur.
- Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
- None.
- 1. Field of the Invention
- The present invention relates to a process and apparatus for the separation of gaseous mixture containing carbon dioxide as main component. It relates in particular to processes and apparatus for purifying carbon dioxide, for example coming from combustion of a carbon containing fuel, such as takes place in an air-fired or oxycombustion fossil fuel or biomass power plant.
- 2. Related Art
- Various techniques based on solvent, sorbents, and membranes have been proposed for CO2 capture from power plants or industrial sources. Some techniques utilize a medium (e.g., amines) for capturing CO2 through chemical affinity. However, the energy needed for regenerating the medium (having chemical affinity for CO2) is significantly high. Other solvents and adsorbents capture CO2 through physical affinity. While the energy necessary for regenerating such solvents and adsorbents is relatively lower than that the media having chemical affinity for CO2, they typically have a relatively lower capacity for CO2 resulting in higher equipment capital costs On the other hand, membranes use a combination of physical affinity and diffusivity. The driving force for transport through membranes is the difference between CO2 partial pressure across the membrane (i.e., the feed partial pressure minus the permeate partial pressure).
- Regardless of the technique employed to recover CO2, high CO2 recoveries from feed gases is desirable for a variety of reasons. For example, the U.S. Department of Energy (DOE) has set a target recovery for recovering CO2 from power plants. As another example, high CO2 recoveries allow more CO2 product gas to be sold or used in order to recover the costs associated with the pre-treatment of the flue gas necessary for recovery. However, in the case of CO2 recovery utilizing membrane separation, as more and more CO2 is sought to be recovered, the driving force across the membrane decreases and approaches a pinch point beyond which additional recovery comes at the expense of high compression energy costs or high membrane surface areas. Thus, for some levels of CO2 recovery, this problem has the potential to increase capital and operating expenses to unsatisfactory levels.
- Each of U.S. Pat. No. 8,617,292, U.S. Pat. No. 8,663,364, and U.S. Pat. No. 8,734,569 discloses that operation of membranes at relatively cold temperatures is highly effective for CO2 capture. Cold temperature operation leads to high membrane selectivity with negligible membrane permeance loss or even possibly an enhancement in membrane permeance. While operation of cold membranes is quite efficient, higher and higher CO2 recoveries may be desired without concomitant unsatisfactorily high increases in capital and operating expenses.
- Membranes are known to be efficient for bulk separation of gases when the driving force is high. They have been used in combination with other, subsequent, gas separation techniques in order to achieve an overall CO2 recovery. Such hybrid systems are known where a membrane performs a bulk CO2 separation from natural gas followed by amine treatment of the lower concentration membrane residue stream. Hybrid combinations of solvent (e.g. piperazine) and membrane have also been studied for CO2 capture from flue gas.
- One particular two unit separation process is disclosed by U.S. Pat. No. 8,728,201 including a membrane utilizing a vacuum on a permeate side that is followed with an absorption (solvent) to remove CO2 from the membrane residue. There is little integration between the two unit operations.
- One particular U.S. Department of Energy funded project uses a costly and cumbersome plate and frame membrane system to operate with an air sweep at low pressures. In this approach, the membrane is placed in series—after the solvent unit or in parallel with the solvent unit (Freeman, et al. “Bench-Scale Development of a Hybrid Membrane-Absorption CO2 Capture Process (DE-FE0013118)”, Dec. 20, 2013 Kickoff Meeting).
- Hybrid processes combining adsorption and membranes are also known. For example, U.S. Pat. No. 8,591,769 and U.S. Pat. No. 6,183,628 discuss membrane treatment of PSA vent gas to recover H2. However, if this technique was applied to flue gas, such a scheme would require use of a less optimum adsorbent that is exposed to many impurities Co-adsorption of moisture and other acid gas components in flue gas prevents optimum adsorption of CO2.
- WO14009449 A1 proposes to combine membrane and adsorption processes for moisture removal.
- Membranes can be swept with a sweep gas in order to overcome the above-described membrane driving force pinch problem. U.S. Pat. No. 8,734,569 discloses that this can be done by diverting a small fraction of gas (that is derived from the low CO2 concentration residue) to sweep the permeate side of a membrane module. For a low sweep rate, the permeate CO2 concentration decreases marginally but the membrane area can be decreased significantly. However for high sweep rates, permeate CO2 concentrations can decrease significantly.
- Another sweep concept, particularly applicable to CO2 capture from flue gas, utilizes a two step membrane process (Merkel, et al., “Power plant post-combustion carbon dioxide capture: An opportunity for membranes”, Journal of Membrane Science 359 (2010) 126-139). The 1st permeate at relatively high CO2 purity is sent for further CO2 purification. The 2nd membrane is swept with an air stream to achieve high CO2 recovery. The air stream is then sent to the boiler island where the recovered CO2 dilutes the overall stream, imposing a small energy penalty for combustion.
- There is a need for membrane-based CO2 recovery processes that do not require unsatisfactorily high capital and operating expenses.
- There is also a need for increased integration of hybrid membrane gas separation schemes for recovery of CO2, especially from flue gas.
- There is a yet another need for a hybrid membrane gas separation scheme for recovery of CO2, especially from flue gas, that does not require the use of less than optimal adsorbents and/or adsorbents which must be contacted with too many impurities.
- There is yet another need for a sweep gas-based membrane separation scheme for recovery of CO2, especially from flue gas, that that does not result in an unsatisfactory decrease in the permeate CO2 concentration.
- There is disclosed a method for recovering CO2 from flue gas that comprises the following steps. Impurities are removed from a flue gas stream to provide a purified flue gas stream. The purified flue gas stream is compressed at a first compressor and fed to a gas separation membrane unit comprising one or more gas separation membranes to produce a permeate stream and a non-permeate stream deficient in CO2 compared to the permeate stream. The permeate stream is compressed at a second compressor. The permeate stream is cooled to produce a partially condensed permeate stream. The partially condensed permeate stream is separated into a CO2-deficient vent gas stream deficient in CO2 compared to partially condensed permeate stream and high purity liquid CO2 product. The CO2-deficient vent gas stream is recycled to the gas separation membrane unit. The non-permeate stream is fed to a PSA unit comprising one or more adsorbent beds to produce a further CO2-depleted vent gas stream depleted in CO2 compared to the non-permeate stream, a CO2 blow-down stream enriched in CO2 compared to the non-permeate stream, and a regeneration product stream. The CO2 blow-down stream is compressed at the second compressor along with the permeate stream. The regeneration product stream is combusted at a combustor that produces the flue gas. The regeneration product stream is produced by feeding a stream of air to the PSA unit to regenerate one of said one or more adsorbent beds and desorb CO2 therefrom. The regeneration product stream is air enriched with the desorbed CO2.
- There is disclosed a system for recovering CO2 from flue gas, comprising: a combustor adapted and configured to combust fuel, oxidant, and supplemental oxidant to produce a flue gas stream; a purification unit in fluid communication with the combustor that is adapted and configured to purify the flue gas stream and produce a purified flue gas stream; a first compressor in fluid communication with the purification unit that is adapted and configured to compress the purified flue gas stream; a gas separation membrane unit in fluid communication with the first compressor that comprising one or more gas separation membranes adapted and configured to receive a feed gas stream from the first compressor and separate the feed gas stream into a permeate gas stream and a non-permeate gas stream that is deficient in CO2 compared to the permeate gas stream; a second compressor in fluid communication with the gas separation membrane unit that is adapted and configured to receive and compress the permeate gas stream to produce a compressed permeate gas stream; at least one heat exchanger, at least one of the at least one heat exchanger being in heat transfer relation with the compressed permeate gas stream and being adapted and configured to partially condense the compressed permeate gas stream to produce a partially condensed permeate stream, at least one of the at least one heat exchanger being in heat transfer relation with the feed gas stream; a PSA unit comprising one or more adsorbent beds in fluid communication with the gas separation membrane unit that is adapted and configured to receive the non-permeate gas stream and an air stream and produce a CO2 blow-down gas stream is enriched in CO2 compared to the non-permeate gas stream, a further CO2-depleted vent gas stream, and a regeneration product stream, the one or more adsorbent beds being adapted and configured to adsorb CO2 from the non-permeate stream, the regeneration product stream comprising air and CO2 desorbed from the one or more adsorbent beds by the air stream, the second compressor being further adapted and configured to compress the CO2 blow-down stream from the PSA unit along with the permeate stream, the combustor being further adapted and configured to receive the regeneration product stream from the PSA unit; and a phase separation unit in fluid communication with the second compressor that is adapted and configured to receive the partially condensed permeate stream from the heat exchanger and separate the partially condensed permeate stream into a CO2-deficient vent gas stream deficient in CO2 compared to partially condensed permeate stream and a high purity liquid CO2 stream, wherein the first compressor is further adapted and configured to compress the CO2-deficient vent gas stream along with the compressed purified flue gas.
- The method and/or system may include one or more of the following aspects:
- the compressed purified flue gas stream is cooled at a heat exchanger to a temperature ranging from 20° C. to −60° C.
- the further CO2-depleted vent gas stream is expanded to lower a temperature thereof, wherein the compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the expanded further CO2-depleted vent gas stream.
- the compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the CO2-deficient vent gas stream prior to feeding the CO2-deficient gas stream to the gas separation membrane unit.
- the CO2-deficient vent gas stream is heat exchanged two times with the compressed purified flue gas stream and the CO2-deficient vent gas stream is expanded to lower a temperature thereof in between the two times.
- the high purity liquid CO2 product is vaporized at the heat exchanger to produce a high purity CO2 product gas, wherein the compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the high purity liquid CO2 product.
- the non-permeate stream is expanded to lower a temperature thereof prior to being fed to the PSA unit, wherein compressed purified flue gas stream is cooled through heat exchange at the heat exchanger with the expanded non-permeate stream.
- the non-permeate stream is heat exchanged two times with the compressed purified flue gas stream and the non-permeate stream is expanded in between the two times.
- said step of separating is performed by separating the partially condensed permeate stream in a phase separator.
- step of separating is performed by: separating the partially condensed permeate stream in a first phase separator into a first CO2-deficient vent gas stream deficient in CO2 compared to partially condensed permeate stream and a first high purity liquid CO2 stream; expanding the first CO2-deficient vent gas stream for partial condensation thereof; separating the partially condensed first CO2-deficient vent gas stream into a second CO2-deficient vent gas stream deficient in CO2 compared to partially condensed permeate stream and a second high purity liquid CO2 stream; and combining the first and second high purity liquid CO2 streams to produce the high purity liquid CO2 product.
- said step of separating is performed by: separating the partially condensed permeate stream in a first phase separator into a first CO2-deficient vent gas stream deficient in CO2 compared to partially condensed permeate stream and a first high purity liquid CO2 stream; expanding the first CO2-deficient vent gas stream for partial condensation thereof; separating the partially condensed first CO2-deficient vent gas stream into a second CO2-deficient vent gas stream deficient in CO2 compared to partially condensed permeate stream and a second high purity liquid CO2 stream; expanding each of the first and second high purity liquid CO2 streams at first and second Joule-Thomson expanders; feeding the expanded high purity liquid CO2 streams to a distillation column; withdrawing the high purity liquid CO2 product from a bottom of the distillation column; and withdrawing a CO2-deficient vapor stream from a top of the distillation column, wherein the CO2-deficient vent gas stream is comprised of the second CO2-deficient vent gas stream and the CO2-deficient vapor stream.
- an expander is adapted and configured to expand the further CO2-depleted vent gas stream to lower a temperature of the further CO2-depleted vent gas stream, wherein at least one of the at least one heat exchanger is in heat transfer relation between, on one hand, the further CO2-depleted vent gas stream, and on the other hand, either the feed gas stream or the compressed permeate stream.
- at least one of the at least one heat exchanger is in heat transfer relation between the feed gas stream and the CO2-deficient vent gas stream.
- at least one of the at least one heat exchanger is in heat transfer relation between the high purity liquid CO2 product and the feed gas stream and is further adapted and configured to vaporize the high purity liquid CO2 product to produce a high purity CO2 gas product.
- an expander is adapted and configured to expand the non-permeate stream to lower a temperature thereof, wherein at least one of the at least one heat exchanger is in heat transfer relation between the expanded non-permeate stream and the feed gas stream.
- the phase separation unit comprises one phase separator vessel.
- the phase separation unit comprises first and second phase separator vessels and a Joule-Thomson expander; the first phase separator vessel is in fluid communication with the second compressor and is adapted and configured to receive the partially condensed permeate stream for phase separation into a first CO2-deficient vent gas stream and a first liquid CO2 stream; the Joule-Thomson expander is in fluid communication between the first and second phase separator vessels and is adapted and configured to expand the first CO2-deficient vent gas stream for partial condensation thereof; the second phase separator vessel is in fluid communication with the Joule-Thomson valve and is adapted and configured to receive the partially condensed first CO2-deficient vent gas stream for separation into a second CO2-deficient vent gas stream and a second liquid CO2 stream; the high purity liquid CO2 product is comprised of the first and second high purity liquid CO2 streams; and the first compressor is in fluid communication with the second phase separator vessel to receive the second CO2-deficient vent gas stream as the CO2-deficient vent gas stream.
- the phase separation unit comprises first and second phase separator vessels, first, second, and third Joule-Thomson valves, and a distillation column; the first phase separator vessel is in fluid communication with the second compressor and is adapted and configured to receive the partially condensed permeate stream for phase separation into a first CO2-deficient vent gas stream and a first liquid CO2 stream; the first Joule-Thomson expander is in fluid communication between the first and second phase separator vessels and is adapted and configured to expand the first CO2-deficient vent gas stream for partial condensation thereof; the second phase separator vessel is in fluid communication with the first Joule-Thomson valve and is adapted and configured to receive the partially condensed first CO2-deficient vent gas stream for separation into a second CO2-deficient vent gas stream and a second liquid CO2 stream; the second and third Joule-Thomson valves are in fluid communication between the first and second phase separator vessel, respectively, and the distillation column; the second and third Joule-Thomas valves are adapted and configured to expand the first and second liquid CO2 streams; the distillation column is adapted and configured to receive the expanded first and second liquid CO2 streams and produce a high purity liquid CO2 stream and a CO2-deficient vapor stream; the high purity liquid CO2 product is comprised of the high purity liquid CO2 stream; and first compressor is in fluid communication with the second phase separator vessel to receive the second CO2-deficient vent gas stream and the distillation column to receive the CO2-deficient vapor stream.
- the flue gas contains 3-90% vol CO2.
- a non-CO2 balance of the flue gas is predominantly N2.
- the flue gas is obtained from an air-fired coal combustion plant and contains 8-16% vol CO2.
- the flue gas is obtained from an air-fired natural gas combustion plant and contains 3-10% vol CO2.
- the flue gas is obtained from an oxycoal combustion plant combusting coal with pure oxygen or synthetic air and contains 60-90% vol CO2.
- the flue gas is obtained from a steam methane reformer and contains 15-90% vol CO2.
- the flue gas is obtained from a blast furnace and contains 20-90% CO2.
- the flue gas comprises 4-30% vol CO2.
-
FIG. 1 is a schematic of the inventive method and system. -
FIG. 2 is a schematic of an embodiment of the inventive method and system. -
FIG. 3 is a schematic of another embodiment of the inventive method and system. -
FIG. 4 is a schematic of a two-phase separator alternative to the single phase separator ofFIG. 2 orFIG. 3 . -
FIG. 5 is a schematic of a two-phase separator plus distillation column alternative to the single phase separator ofFIG. 2 orFIG. 3 . - Disclosed is a method and system of recovering CO2 from flue gas to provide purified CO2. The method combines the benefits of the gas separation techniques of membranes and adsorption, but integrates the two to maximize efficiencies. For example, a recovery of greater than approximately 90% of the CO2 from the flue gas of an existing air-fired coal power plant may be possible with a less than approximately 35% increase in the plant's cost of electricity.
- The flue gas may be obtained or derived from suitable combustion processes such as steam methane reforming (SMR), blast furnaces, and air-fired or oxygen-enhanced combustion of fossil fuels (such as in power plants). In the case of oxygen-enhanced fossil fuel combustion processes, the combustion may be full oxycombustion or partial oxycombustion. In full oxycombustion, the primary and secondary oxidants (and tertiary and quaternary oxidants, if present) may be pure oxygen or synthetic air comprising oxygen and recycled flue gas. In partial oxycombustion, one or more of the oxidants may be air and one or more of the remaining oxidants may be oxygen or synthetic air (a mixture of oxygen and recycled flue gas), or alternatively, one or more of the oxidants may be oxygen-enriched air. Pure oxygen means that the oxidant has a concentration typically found in conventional industrial oxygen production processes such as in cryogenic air separation units. The oxygen concentration of synthetic air may range from a concentration at, or above that, of oxygen in air to a concentration less than pure oxygen.
- The flue gas contains 3-90% vol CO2. Other components that may be contained within the flue gas include but are not limited to other combustion byproducts, such as water, methane, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen. Typically, the non-CO2 balance of the flue gas is predominantly N2. Flue gas obtained from an air-fired coal combustion plant typically contains 8-16% vol CO2, while flue gas obtained from an air-fired natural gas combustion plant typically contains 3-10% vol CO2. Flue gas obtained from an oxycoal combustion plant (i.e., coal combusted with pure oxygen or synthetic air) typically contains 60-90% vol CO2 with a balance of water, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen. Flue gas obtained from a steam methane reformer typically contains 15-90% vol CO2 with a balance of water, methane, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen. Flue gas obtained from a blast furnace typically contains 20-90% CO2 with a balance of water, hydrogen, nitrogen, oxygen, argon, carbon monoxide, oxides of sulfur, and oxides of nitrogen. Typically, the flue gas comprises 4-30% vol CO2.
- As best illustrated in
FIG. 1 , afuel stream 51, one or more oxidant streams 52 and asupplemental oxidant stream 66 are combusted at acombustor 1, thereby producing a rawflue gas stream 53. While the type of fuel infuel stream 51 and the type ofcombustor 1 are not limited, typically the fuel is natural gas or coal and thecombustor 1 is a boiler. One or more streams of the one or more oxidant streams 52 may be air, oxygen-enriched air, and/or industrially pure oxygen. Thesupplemental oxidant stream 66 is described below. It or they may be fed as primary air with or without secondary air, tertiary air, and quaternary air. One of ordinary skill in the field of combustion will recognize that the terms “primary air”, “secondary air”, “tertiary air”, and “quaternary air” are not meant as being limited to air, but rather encompass oxygen-enriched air and industrially pure oxygen as well. -
Raw stream 53 is fed to apurification unit 2 for removal of impurities. Suitable treatment methods include but are not limited to those disclosed in WO 2009010690, WO 2009095581, and U.S. Published Patent Application Nos. US 2009013717, US2009013868, and US2009013871, the treatment methods of which are incorporated herein by reference in their entireties. The moisture content of theraw stream 53 should be reduced to a low level for a variety of reasons. First, it is desirable to avoid competition for the adsorbent (in the downstream PSA unit 7) by moisture and CO2. In the case of sub-ambient membrane operation in gasseparation membrane unit 4, it is desirable to avoid the freezing of moisture on cold surfaces in any heat exchanger present. Known drying materials and adsorbent-based processes include alumina, silica, or molecular sieves. Condensation of moisture through cooling may also be used to lower the moisture content ofraw gas stream 53. In addition to moisture, thepurification unit 2 typically removes particulates with filters and acid gases, such as NOx and Sox, with scrubbers. - The purified
flue gas stream 54 is then compressed at acompression unit 3 to boost its pressure to about 4-20 bar. Thecompression unit 3 includes one or more compressors. In between multiple compression stages (in the case of a multi-stage compressor),stream 54 may be cooled with water, other non-water coolant, or a coolant gas whereby additional water may be removed fromstream 54 through condensation (i.e., knocked out). In the case of a boiler forcombustor 1,stream 54 may be cooled with boiler feed water. In this manner, the boiler feed water may be pre-heated prior to introduction in theboiler combustor 1 and the efficiency of theboiler combustor 1 andcompression unit 3 are both increased. For example, whenstream 54 is compressed to 16 bar, sufficient heat is generated to pre-heat boiler feed water to approximately 147° C. In a coal power plant, such pre-heating allows more steam turbine energy to be used for electricity generation. Suitable types of compressors include centrifugal, screw, reciprocating, and axial compressors. - With continued reference to
FIG. 1 , compressed, purifiedflue gas stream 55 is fed to an inlet of a gasseparation membrane unit 4. The membranes of the gasseparation membrane unit 4 allow selective permeation to form a low pressure CO2 enrichedpermeate stream 57 and a CO2 depleted streamnon-permeate stream 58. The gas separation membranes ofunit 4 may be operated at ambient or sub-ambient temperature. - When the gas separation membranes of
unit 4 are operated at ambient temperature, the upstream water cooling is sufficient to bringstream 55 to ambient temperature. - When the membrane is operated at a sub-ambient temperature, such as 5° C. to −60° C., the required cold temperature is achieved through heat exchange between
stream 56 and non-permeate stream 58 (after expansion of stream 58) and/or betweenstream 56 and PSA vent gas 64 (after expansion of stream 64). This heat exchange may be accomplished with a conventional heat exchanger, such as a plate fin, shell-in-tube, spiral wound, or brazed aluminum plate heat exchanger, or it may be a falling film evaporator as disclosed in EP 1008826, a heat exchanger derived from an automobile radiator as disclosed in US 2009/211733, or plate heat exchangers manufactured as disclosed in FR 2,930,464, FR 2,930,465, and FR 2,930,466. The heat exchangers in the cited patent publications are all incorporated herein by reference in their entireties. Typically, the heat exchanger is a brazed aluminum plate exchanger having multiple parallel cores allowing it to cool/heat a number of streams. The temperature ofstream 54 should be maintained above its water freezing point. It should be noted that, with regard to all heating or cooling steps performed at heat exchangers, the skilled artisan will recognize that selection of which stream or streams are used to cool another stream or streams at a particular heat exchanger is well within the knowledge of a chemical engineer in the field of industrial gases. - The
permeate stream 57 is fed to a suction inlet of acompression unit 5 where the combined stream is compressed to about 16-30 bar. Thecompression unit 5 contains one or more compressors selected from centrifugal, screw, reciprocating, and axial compressors. Thecompression unit 5 also typically uses boiler feed water for cooling ofstream 57 so that further water may be knocked out (or optionally, to avoid flooding of a water removal adsorbent) and the boiler feed water may be preheated. - With continued reference to
FIG. 1 , the compressedstream 60, typically containing >60% vol CO2) is then fed to aliquefaction unit 6 to produce high purity (<95% vol) liquid CO2 and avent gas stream 62. The high purity liquid CO2 is re-gasified to produce gaseous CO2 product 59. The cold temperature required for liquefaction of the CO2 is substantially generated through heat exchange with stream 58 (after expansion) and/or stream 64 (after expansion). The cold temperature required for liquefaction may optionally also be generated through heat exchange with a portion of the high purity liquid CO2 so as to cool compressedstream 60 and vaporize the high purity liquid CO2. Theliquefaction unit 6 may also include a pump to boost the pressure of high purity liquid CO2 prior to re-gasification to produce the CO2 product 61. - The CO2-depleted vent gas 62, containing about 20-40% vol CO2, is also fed to the gas
separation membrane unit 4. Depending upon the pressure of the CO2-depleted vent gas 62, it can first be expanded to the pressure ofstream 55 as necessary. - The
non-permeate stream 58, containing about 4-15% vol CO2, is fed to pressure swing adsorption (PSA)unit 7. ThePSA unit 7 contains a plurality of adsorbent columns. AtPSA unit 7, CO2 fromstream 58 is selectively adsorbed so that a further CO2 depletedvent gas 64 is produced that contains anywhere from 10 ppm vol to 4% vol of CO2. The CO2 depletedvent gas 64 is expanded at a turbo-expander 8 to recover useful energy and vented to atmosphere asstream 65. - The adsorbed CO2 is partially recovered as a CO2 blow-
down stream 69. The CO2 concentration of the CO2 blow-down stream 69 is equal to or higher than that ofstream 58 and is fed to the suction inlet ofcompressor 5. In the event that the CO2 concentration for the CO2 blow-down stream 69 is lower than that ofstream 58, as shown by the dotted line, it may instead be fed to the suction inlet ofcompressor 3. - With continued reference to
FIG. 1 , the adsorbent inPSA unit 7 is regenerated by anair stream 63, thereby producing avent stream 66 that contains air and substantially the remaining desorbed CO2. The air and desorbed CO2-containing stream 66 is fed tocombustor 1 as the entirety of, or as a portion of, the primary, secondary, tertiary (if present), and/or quaternary (if present) oxidant that is fed to the combustor.Stream 66 may be mixed with a portion of oxidant from one or more ofstreams 52 or may be fed tocombustor 1 separately fromstreams 52. A wide variety of oxidant injection schemes are known in the field of combustion (especially combustion performed with recycled flue gas) and their details need not be recited herein. Some degree of moisture may remain adsorbed on adsorbent inPSA unit 7 after CO2 desorption. In order to more effectively desorb that moisture, a portion of the air ofstream 63 may either be dried (e.g. with zeolite 3A) or pre-heated upstream ofPSA unit 7. - As shown in
FIG. 2 , one embodiment includes sub-ambient membrane separation and expansion of a non-permeate stream downstream of PSA separation. -
Fuel 51 with one or more oxidant streams 52 andsupplemental oxidant stream 66 are combusted incombustor 1 which is a boiler. The resultingflue gas stream 53 is purified inpurification unit 2 for removal of impurities as described above. Thepurification unit 2 may optionally include a blower in order to provide adequate suction pressure forcompressor 3. - As described above, the purified
flue gas stream 54 is fed to the suction inlet of acompressor 3. As described above,compressor 3 may include one or more compressors which also typically includes water cooling of the compressed CO2 enriched stream that may be used to preheat boiler feed water and for further water knock-out. - The compressed, purified
flue gas stream 55 after water cooling is dried with an adsorbent-based moisture removal unit 9 that contains one or more adsorbent beds containing adsorbents known in the art for removal of moisture from gases. - The dried, compressed, purified
flue gas stream 67 is then cooled at aheat exchanger 10.Exchanger 10 may be a multi-stream type heat exchanger adapted and configured to exchange heat between a plurality of streams. Typically, the multi-stream heat exchanger is a brazed aluminum plate exchanger having multiple parallel cores allowing it to cool/heat the plurality of streams. Alternatively,exchanger 10 could be a combination of several smaller heat exchangers not necessarily exchanging heat between each of the streams illustrated. A combination of several smaller heat exchangers is useful for segregation of higher pressure streams from low pressure streams. - If several smaller heat exchangers are utilized instead of a multi-stream heat exchanger (such as illustrated in
FIGS. 2-3 ), each particular heat exchanger will exchange heat between less than all of the streams illustrated. In this case, it should be noted that, with regard to all heating or cooling steps described and/or illustrated, the skilled artisan will recognize that selection of which stream or streams are used to cool another stream or streams at a particular heat exchanger is well within the knowledge of a chemical engineer in the field of industrial gases. - With continued reference to
FIG. 2 , the cold, dried, compressed, purifiedflue gas stream 68 is fed to a gasseparation membrane unit 4. As described above, the membranes of the gasseparation membrane unit 4 allow selective permeation to form a low pressure CO2 enrichedpermeate stream 57 and a CO2 depleted streamnon-permeate stream 58. The gas separation membranes ofunit 4 may be operated at ambient or sub-ambient temperature as described above. - The CO2 enriched
permeate gas 57 is re-compressed to about 6-30 bar incompressor 5.Compressor 5 also typically includes water cooling ofstream 57 where the thus-heated water may be used as preheated boiler feed water. The water cooling ofstream 57 also allows further water knock-out, but additional adsorbent-based drying may be included, if needed. The dried and compressed CO2 enrichedstream 60, having a concentration of >60% vol CO2, is cooled inexchanger 10 to partially condense the CO2. - The gaseous and liquid CO2 phases are separated in
phase separator 12. As shown inFIG. 2 ,phase separator 12 is a one pot phase separation unit producing a high purity, liquid CO2 stream 68 and acold vent stream 62. The pressure of the high purity, liquid CO2 stream 68 is boosted to about 60-150 bar by a cryo-pump 14 and then warmed/vaporized atexchanger 10 to form high purity (>95% vol CO2)product gas stream 59. - The
cold vent stream 62 is passed throughexchanger 10 and is optionally partially expanded inexpander 15 to match the pressure ofstream 67. After heat exchange and optional partial expansion,stream 62 is combined withstream 67. - The
membrane residue stream 58 is warmed atexchanger 10 and fed to a PSA unit.FIG. 2 illustrates a PSA unit with fouradsorbent bed columns FIG. 2 theadsorbent bed columns -
- a) CO2 adsorption mode 71,
- b) let down of pressure in CO2 blow down
mode 72, - c) regeneration of adsorbent by desorption with
air 73, and - d) using warmed
stream 58,repressurization 74.
- With continued reference to
FIG. 2 , CO2 is selectively adsorbed from warmedstream 58 by the adsorbent incolumn 71. A further CO2 depleted (10 ppm-4%) vent gas is expanded atexpander 75 to provide a cold, expanded, CO2-depleted stream 64. The cold, expanded, CO2-depleted stream 64 is passed throughexchanger 10 to provide the necessary cold energy (i.e., for removal of enthalpy) tocool stream 67 for sub-ambient membrane operation and also to partially condensestream 60. Depending on the available pressure and flow rate ofstream 64 downstream ofexchanger 10, it may be heated atheat exchanger 76 and then further expanded at turbo-expander 8 for energy recovery and vented asinert vent gas 65. - The pressure in
column 72 is let down through venting to produce CO2 blow-down stream 69. CO2 blow-down stream 69 has a CO2 concentration equal to or higher than that ofstream 58 and is fed to the suction inlet ofcompressor 5. In the event that CO2 blow-down stream 69 has a CO2 concentration lower than that ofstream 58, as shown by the dotted line, it may instead be fed to the suction inlet ofcompressor 3. -
Air stream 63 at close to ambient pressure flows throughcolumn 73 to desorb CO2. Some degree of moisture may remain adsorbed on adsorbent incolumn 73 after CO2 desorption. In order to more effectively desorb that moisture, a final portion of the air ofstream 63 may either be dried (e.g., with zeolite 3A) or pre-heated upstream of the PSA unit. The CO2-enriched air stream 66 is fed tocombustor 1 as described above. -
Column 74 is pressurized with warmedstream 58. At the end of this step, the adsorbent is in position to begin the adsorption cycle again. Thus, in the next adsorption cycle, thecolumns -
- e) CO2 adsorption mode in
column 74, - f) let down of pressure in CO2 blow down mode in
column 71, - g) regeneration of adsorbent by desorption with air in
column 72, and - h) using
stream 58, repressurization incolumn 73.
- e) CO2 adsorption mode in
- The
columns -
- a) CO2 adsorption mode in
column 73, - b) let down of pressure in CO2 blow down mode in
column 74, - c) regeneration of adsorbent by desorption with air in
column 71, and - d) using
stream 58, repressurization incolumn 72.
- a) CO2 adsorption mode in
- The
columns -
- a) CO2 adsorption mode in
column 72, - b) let down of pressure in CO2 blow down mode in
column 73, - c) regeneration of adsorbent by desorption with air in
column 74, and - d) using
stream 58, repressurization incolumn 71.
- a) CO2 adsorption mode in
- Subsequently, operation of the
columns -
- a) CO2 adsorption mode in
column 71, - b) let down of pressure in CO2 blow down mode in
column 72, - c) regeneration of adsorbent by desorption with air in
column 73, and - d) using
stream 58, repressurization incolumn 74.
- a) CO2 adsorption mode in
- As shown in
FIG. 3 , another embodiment also includes sub-ambient membrane separation and expansion of a non-permeate stream downstream of PSA separation. The embodiment ofFIG. 3 is the same asFIG. 2 except for the following differences. - The further CO2-depleted vent gas 74 from
column 71 is not expanded for purposes of providing the necessary cold energy for cooling the combination ofstreams stream 60. Rather, stream 74 is heated atheat exchanger 76 and then further expanded at turbo-expander 8 for energy recovery and vented asinert vent gas 65. - Also, after passing through
exchanger 10 immediately downstream of the gasseparation membrane unit 4, thenon-permeate stream 58 is expanded atexpander 76. The now-cold, expandednon-permeate stream 58 is passed throughexchanger 10 in order to provide the necessary cold energy for coolingstream 67 and for partial condensation ofstream 60,prior stream 58 being fed tocolumn 71. In the embodiment ofFIG. 3 , the adsorption of CO2 fromstream 58 incolumn 71 takes place at a lower pressure and temperature than in the embodiment ofFIG. 2 . - While the embodiments of
FIGS. 2 and 3 show onephase separator 12 for effecting separation of the partially liquefiedstream 60 intovent gas stream 62 and CO2 product 59, other schemes and apparatuses may be used for this separation. For example, instead of a single phase separator 12 (as inFIGS. 2 and 3 ),FIG. 4 includes twophase separators FIG. 4 can be thought of as a variation of the embodiment ofFIG. 2 or a variation of the embodiment ofFIG. 3 where all like-numbered reference characters denote a same apparatus or stream. - As described above,
permeate stream 57 is compressed and partially condensed bycompressor 5 andexchanger 10 to producestream 60. Instead of being received in phase separator 12 (as inFIGS. 2 and 3 ),stream 60 is received in afirst phase separator 12 of two in-series phase separators phase separator 12 a exits asstream 62 a, is partially expanded across a Joule-Thomson valve, further cooled atexchanger 10, and partially condensed inphase separator 12 b. The resultingvent gas stream 62 b fromphase separator 12 b is optionally further expanded inexpander 13 b to providevent gas stream 62. - The bottom CO2-rich liquids exiting
phase separators stream 68 is boosted at cryo-pump 14 and then vaporized at exchanger to form gaseous CO2 product stream 59. - As another example of a different scheme or apparatus for achieving separation of the partially condensed
stream 60,FIG. 5 includes twophase separators FIG. 5 can be thought of as a variation of the embodiment ofFIG. 2 or a variation of the embodiment ofFIG. 3 where all like-numbered reference characters denote a same apparatus or stream. - As explained above,
permeate stream 57 is compressed and partially condensed bycompressor 5 andexchanger 10 to producestream 60. Instead of being received in phase separator 12 (as inFIGS. 2 and 3 ),stream 60 is received in afirst phase separator 12 of two in-series phase separators phase separator 12 a exits asstream 62 a, is partially expanded across a Joule-Thomson valve, further cooled atexchanger 10, and partially condensed inphase separator 12 b. The resultingvent gas stream 62 b fromphase separator 12 b is optionally further expanded inexpander 13 b. - The bottom CO2-rich liquid exits
phase separators Thomson valves distillation column 16. CO2-deficient vapor exits from a top ofcolumn 16 asvapor stream 18 and high purity liquid CO2 exits a bottom ofcolumn 16 as high purity liquid CO2 stream 68.Vapor stream 18 is combined withvent gas stream 62 b to form CO2-depleted vent gas 62. Thepressure stream 68 is boosted at cryo-pump 14 and then vaporized at exchanger to form gaseous CO2 product stream 59. - Suitable materials for use in the gas separation membranes include polymeric materials having a CO2 permeance is >100 GPU and a CO2/N2 selectivity >20 at the selected operational temperature and pressure. A variety of materials satisfying these criteria are well-known to those skilled in the art of gas separation membranes. For sub-ambient operation of the membranes, suitable polymeric materials exhibit a CO2 solubility at 35° C. and 10 bar pressure of >0.03 [(cm3 of CO2 at STP)/(cm3 of polymeric material)(cmHg)] and a glass transition temperature of >210° C. Particular polymeric materials meeting these requirements are disclosed in U.S. Pat. No. 8,617,292, the contents of which are incorporated herein by reference.
- The skilled artisan in the field of gas separation will recognize that there is a wide variety of adsorbents known as effective for separating CO2 from CO2-containing gas mixtures through adsorption and the details of such adsorbents need not be replicated herein. The skilled artisan will similarly recognize that there is a wide variety of PSA techniques known as effective for separating gases from gas mixtures and the details of such adsorbents need not be replicated herein. Thus, the invention should be considered to be limited to the particular PSA technique described above with regard to
FIGS. 2 and 3 - While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims. The present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed. Furthermore, if there is language referring to order, such as first and second, it should be understood in an exemplary sense and not in a limiting sense. For example, it can be recognized by those skilled in the art that certain steps can be combined into a single step.
- The singular forms “a”, “an” and “the” include plural referents, unless the context clearly dictates otherwise.
- “Comprising” in a claim is an open transitional term which means the subsequently identified claim elements are a nonexclusive listing i.e. anything else may be additionally included and remain within the scope of “comprising.” “Comprising” is defined herein as necessarily encompassing the more limited transitional terms “consisting essentially of” and “consisting of”; “comprising” may therefore be replaced by “consisting essentially of” or “consisting of” and remain within the expressly defined scope of “comprising”.
- “Providing” in a claim is defined to mean furnishing, supplying, making available, or preparing something. The step may be performed by any actor in the absence of express language in the claim to the contrary.
- Optional or optionally means that the subsequently described event or circumstances may or may not occur. The description includes instances where the event or circumstance occurs and instances where it does not occur.
- Ranges may be expressed herein as from about one particular value, and/or to about another particular value. When such a range is expressed, it is to be understood that another embodiment is from the one particular value and/or to the other particular value, along with all combinations within said range.
- All references identified herein are each hereby incorporated by reference into this application in their entireties, as well as for the specific information for which each is cited.
Claims (19)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/638,631 US9452385B1 (en) | 2015-03-04 | 2015-03-04 | Hybrid membrane and adsorption-based system and process for recovering CO2 from flue gas and using combustion air for adsorbent regeneration |
CA2922891A CA2922891C (en) | 2015-03-04 | 2016-03-03 | Hybrid membrane and adsorption-based system and process for recovering co2 from flue gas and using combustion air for adsorbent regeneration |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/638,631 US9452385B1 (en) | 2015-03-04 | 2015-03-04 | Hybrid membrane and adsorption-based system and process for recovering CO2 from flue gas and using combustion air for adsorbent regeneration |
Publications (2)
Publication Number | Publication Date |
---|---|
US20160256819A1 true US20160256819A1 (en) | 2016-09-08 |
US9452385B1 US9452385B1 (en) | 2016-09-27 |
Family
ID=56850319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/638,631 Active US9452385B1 (en) | 2015-03-04 | 2015-03-04 | Hybrid membrane and adsorption-based system and process for recovering CO2 from flue gas and using combustion air for adsorbent regeneration |
Country Status (2)
Country | Link |
---|---|
US (1) | US9452385B1 (en) |
CA (1) | CA2922891C (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160003532A1 (en) * | 2014-07-03 | 2016-01-07 | Pioneer Energy Inc | Systems and methods for recovering carbon dioxide from industrially relevant waste streams, especially ethanol fermentation processes, for application in food and beverage production |
US9546785B1 (en) * | 2016-06-13 | 2017-01-17 | Membrane Technology And Research, Inc. | Sweep-based membrane separation process for removing carbon dioxide from exhaust gases generated by multiple combustion sources |
CN106587061A (en) * | 2017-01-10 | 2017-04-26 | 宁夏坤辉气化有限公司 | System for purifying carbon dioxide by utilizing air discharged in decarbonization |
US9782718B1 (en) | 2016-11-16 | 2017-10-10 | Membrane Technology And Research, Inc. | Integrated gas separation-turbine CO2 capture processes |
US9856769B2 (en) | 2010-09-13 | 2018-01-02 | Membrane Technology And Research, Inc. | Gas separation process using membranes with permeate sweep to remove CO2 from combustion exhaust |
WO2018228716A1 (en) * | 2017-06-14 | 2018-12-20 | Linde Aktiengesellschaft | Method and system for producing a gas product containing carbon monoxide |
CN110156016A (en) * | 2019-06-14 | 2019-08-23 | 林千果 | The combined recovery device and method of carbon dioxide in flue gas, nitrogen and oxygen |
IT201900013281A1 (en) * | 2019-07-30 | 2021-01-30 | Leonardo Spa | Process for obtaining carbon dioxide from the combustion fumes of the boilers |
EP4186583A1 (en) * | 2021-11-24 | 2023-05-31 | Linde GmbH | Method and arrangement for separating carbon dioxide from a feed stream containing carbon dioxide |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11148097B2 (en) | 2019-09-03 | 2021-10-19 | Korea Institute Of Energy Research | Low-temperature membrane separation device and method for capturing carbon dioxide at high concentration |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2786858B1 (en) | 1998-12-07 | 2001-01-19 | Air Liquide | HEAT EXCHANGER |
US6183628B1 (en) | 1999-03-19 | 2001-02-06 | Membrane Technology And Research, Inc. | Process, including PSA and membrane separation, for separating hydrogen from hydrocarbons |
DK1608445T3 (en) * | 2003-04-03 | 2013-09-30 | Fluor Corp | Carbon Capture Configurations and Methods |
FR2891901B1 (en) | 2005-10-06 | 2014-03-14 | Air Liquide | METHOD FOR VAPORIZATION AND / OR CONDENSATION IN A HEAT EXCHANGER |
US20090013868A1 (en) | 2007-07-11 | 2009-01-15 | Arthur Darde | Process and apparatus for the separation of a gaseous mixture |
US7708804B2 (en) | 2007-07-11 | 2010-05-04 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the separation of a gaseous mixture |
FR2918578B1 (en) | 2007-07-13 | 2010-01-01 | Air Liquide | PROCESS FOR PURIFYING GAS CONTAINING CO2 |
WO2009013717A2 (en) | 2007-07-23 | 2009-01-29 | Element Six Limited | Encapsulated material |
FR2926876B1 (en) | 2008-01-28 | 2010-03-05 | Air Liquide | METHOD FOR COMBUSTING CARBON FUELS WITH FILTRATION OF COMBUSTION FUME BEFORE COMPRESSION. |
FR2930464A1 (en) | 2008-04-28 | 2009-10-30 | Air Liquide | Plate heat exchanger fabricating method, involves arranging block between plates, injecting fluid in inner space of block, brazing exchanger, forming depression in hollow space of block to liberate space between plates, and removing block |
FR2930466B1 (en) | 2008-04-28 | 2010-09-17 | Air Liquide | CALE FOR MAINTAINING PASSAGES OF EXCHANGERS WITH PLATES AND BRASSE FINS |
FR2930465B1 (en) | 2008-04-28 | 2010-09-24 | Air Liquide | METHOD FOR MANUFACTURING A PLATE HEAT EXCHANGER USING A PLATE ASSEMBLY |
US8535417B2 (en) * | 2008-07-29 | 2013-09-17 | Praxair Technology, Inc. | Recovery of carbon dioxide from flue gas |
DE102008062497A1 (en) * | 2008-12-16 | 2010-06-17 | Linde-Kca-Dresden Gmbh | Process and apparatus for treating a carbon dioxide-containing gas stream from a large combustion plant |
DE102009016015A1 (en) | 2009-04-02 | 2010-10-07 | Forschungszentrum Jülich GmbH | Apparatus and method for removing carbon dioxide (CO2) from the flue gas of a combustion plant after the energy conversion |
US8617292B2 (en) | 2009-12-15 | 2013-12-31 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture |
US8663364B2 (en) | 2009-12-15 | 2014-03-04 | L'Air Liquide, Société Anonyme pour l'Étude et l'Éxploitation des Procédés Georges Claude | Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture |
US8734569B2 (en) | 2009-12-15 | 2014-05-27 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture |
EP2590898B1 (en) * | 2010-07-09 | 2020-12-09 | Arnold Keller | Carbon dioxide capture and liquefaction |
US20130205828A1 (en) * | 2011-10-06 | 2013-08-15 | Rustam H. Sethna | Integration of a liquefied natural gas liquefier with the production of liquefied natural gas |
US8591769B2 (en) | 2011-12-15 | 2013-11-26 | Air Liquide Large Industries U.S. Lp | Hydrogen production with reduced carbon dioxide generation and complete capture |
EP2685190A1 (en) | 2012-07-13 | 2014-01-15 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Process and apparatus for the separation of a stream containing carbon dioxide, water and at least one light impurity including a separation step at subambient temperature |
-
2015
- 2015-03-04 US US14/638,631 patent/US9452385B1/en active Active
-
2016
- 2016-03-03 CA CA2922891A patent/CA2922891C/en active Active
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9856769B2 (en) | 2010-09-13 | 2018-01-02 | Membrane Technology And Research, Inc. | Gas separation process using membranes with permeate sweep to remove CO2 from combustion exhaust |
US20160003532A1 (en) * | 2014-07-03 | 2016-01-07 | Pioneer Energy Inc | Systems and methods for recovering carbon dioxide from industrially relevant waste streams, especially ethanol fermentation processes, for application in food and beverage production |
US9546785B1 (en) * | 2016-06-13 | 2017-01-17 | Membrane Technology And Research, Inc. | Sweep-based membrane separation process for removing carbon dioxide from exhaust gases generated by multiple combustion sources |
CN110022963A (en) * | 2016-11-16 | 2019-07-16 | 膜技术与研究公司 | The CO integrated in gas separation-turbine2Catching method |
US9782718B1 (en) | 2016-11-16 | 2017-10-10 | Membrane Technology And Research, Inc. | Integrated gas separation-turbine CO2 capture processes |
US10464014B2 (en) | 2016-11-16 | 2019-11-05 | Membrane Technology And Research, Inc. | Integrated gas separation-turbine CO2 capture processes |
CN106587061A (en) * | 2017-01-10 | 2017-04-26 | 宁夏坤辉气化有限公司 | System for purifying carbon dioxide by utilizing air discharged in decarbonization |
WO2018228716A1 (en) * | 2017-06-14 | 2018-12-20 | Linde Aktiengesellschaft | Method and system for producing a gas product containing carbon monoxide |
US20200131647A1 (en) * | 2017-06-14 | 2020-04-30 | Linde Aktiengesellschaft | Method and system for producing a gas product containing carbon monoxide |
CN110156016A (en) * | 2019-06-14 | 2019-08-23 | 林千果 | The combined recovery device and method of carbon dioxide in flue gas, nitrogen and oxygen |
IT201900013281A1 (en) * | 2019-07-30 | 2021-01-30 | Leonardo Spa | Process for obtaining carbon dioxide from the combustion fumes of the boilers |
EP3771485A1 (en) * | 2019-07-30 | 2021-02-03 | Leonardo S.p.A. | Process for obtaining carbon dioxide from furnace combustion fumes |
US11406938B2 (en) | 2019-07-30 | 2022-08-09 | Leonardo S.P.A. | Process for obtaining carbon dioxide from furnace combustion fumes |
EP4186583A1 (en) * | 2021-11-24 | 2023-05-31 | Linde GmbH | Method and arrangement for separating carbon dioxide from a feed stream containing carbon dioxide |
Also Published As
Publication number | Publication date |
---|---|
CA2922891C (en) | 2022-01-18 |
CA2922891A1 (en) | 2016-09-04 |
US9452385B1 (en) | 2016-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2922891C (en) | Hybrid membrane and adsorption-based system and process for recovering co2 from flue gas and using combustion air for adsorbent regeneration | |
CA2922887C (en) | Hybrid membrane and adsorption-based system and process for recovering co2 from flue gas and using combustion air for adsorbent regeneration | |
US7927573B2 (en) | Multi-stage process for purifying carbon dioxide and producing acid | |
US9895653B2 (en) | Process and apparatus for the separation of a stream containing carbon dioxide, water and at least one light impurity including a separation step at subambient temperature | |
US9856769B2 (en) | Gas separation process using membranes with permeate sweep to remove CO2 from combustion exhaust | |
EP2512622B1 (en) | Method of obtaining carbon dioxide from a carbon dioxide-containing gas mixture by means of a membrane with a sweep stream | |
US8012446B1 (en) | Recycle TSA regen gas to boiler for oxyfuel operations | |
CA2732129C (en) | Recovery of carbon dioxide from flue gas | |
US8025715B2 (en) | Process for separating carbon dioxide from flue gas using parallel carbon dioxide capture and sweep-based membrane separation steps | |
AU2019226284B2 (en) | Helium extraction from natural gas | |
US9005335B2 (en) | Hybrid parallel / serial process for carbon dioxide capture from combustion exhaust gas using a sweep-based membrane separation step | |
US8663364B2 (en) | Method of obtaining carbon dioxide from carbon dioxide-containing gas mixture | |
EP3395428A2 (en) | Method of obtaining carbon dioxide from a carbon dioxide-containing gas mixture | |
US20080245101A1 (en) | Integrated Method and Installation for Cryogenic Adsorption and Separation for Producing Co2 | |
JP2019537511A (en) | Integrated CO2 capture process in gas separation turbine | |
US20240001283A1 (en) | Carbon Dioxide Capture |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: L'AIR LIQUIDE, SOCIETE ANONYME POUR L'ETUDE ET L'E Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AMERICAN AIR LIQUIDE, INC.;REEL/FRAME:035584/0462 Effective date: 20150505 Owner name: AMERICAN AIR LIQUIDE, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:KULKARNI, SUDHIR S.;REEL/FRAME:035584/0384 Effective date: 20150505 |
|
FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 4 |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Year of fee payment: 8 |