EP2780098A1 - Verfahren und vorrichtung zur abtrennung von sauren gasen aus einer gasmischung - Google Patents
Verfahren und vorrichtung zur abtrennung von sauren gasen aus einer gasmischungInfo
- Publication number
- EP2780098A1 EP2780098A1 EP12773311.1A EP12773311A EP2780098A1 EP 2780098 A1 EP2780098 A1 EP 2780098A1 EP 12773311 A EP12773311 A EP 12773311A EP 2780098 A1 EP2780098 A1 EP 2780098A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- liquid phase
- phase
- absorption medium
- absorber
- 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.)
- Withdrawn
Links
- 239000007789 gas Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 37
- 238000000926 separation method Methods 0.000 title claims abstract description 29
- 238000010521 absorption reaction Methods 0.000 claims abstract description 106
- 239000007791 liquid phase Substances 0.000 claims abstract description 88
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 85
- 238000003795 desorption Methods 0.000 claims abstract description 59
- 239000006096 absorbing agent Substances 0.000 claims abstract description 40
- 150000001412 amines Chemical class 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000005191 phase separation Methods 0.000 claims abstract description 31
- 239000012071 phase Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 4
- 230000005501 phase interface Effects 0.000 claims description 3
- 125000003282 alkyl amino group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 description 10
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 9
- 238000012856 packing Methods 0.000 description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- 235000011089 carbon dioxide Nutrition 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010525 oxidative degradation reaction Methods 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- -1 alkali metal salts Chemical class 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- KYWXRBNOYGGPIZ-UHFFFAOYSA-N 1-morpholin-4-ylethanone Chemical compound CC(=O)N1CCOCC1 KYWXRBNOYGGPIZ-UHFFFAOYSA-N 0.000 description 1
- SAKKGTNWFBSAGP-UHFFFAOYSA-N 2,2,6,6-tetramethyl-n-propylpiperidin-4-amine Chemical compound CCCNC1CC(C)(C)NC(C)(C)C1 SAKKGTNWFBSAGP-UHFFFAOYSA-N 0.000 description 1
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical group CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- QYNFXDVIHNENBG-UHFFFAOYSA-N n',n'-dimethyl-n-(2,2,6,6-tetramethylpiperidin-4-yl)propane-1,3-diamine Chemical compound CN(C)CCCNC1CC(C)(C)NC(C)(C)C1 QYNFXDVIHNENBG-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- LRAJIZNKBMCWJE-UHFFFAOYSA-N n,n,2,2,6,6-hexamethylpiperidin-4-amine Chemical compound CN(C)C1CC(C)(C)NC(C)(C)C1 LRAJIZNKBMCWJE-UHFFFAOYSA-N 0.000 description 1
- FDAKZQLBIFPGSV-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CCCCNC1CC(C)(C)NC(C)(C)C1 FDAKZQLBIFPGSV-UHFFFAOYSA-N 0.000 description 1
- 125000002004 n-butylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JCWMZJIACZLXGL-UHFFFAOYSA-N n-ethyl-n'-(2,2,6,6-tetramethylpiperidin-4-yl)ethane-1,2-diamine Chemical compound CCNCCNC1CC(C)(C)NC(C)(C)C1 JCWMZJIACZLXGL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20415—Tri- or polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20421—Primary amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20426—Secondary amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20431—Tertiary amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20436—Cyclic amines
- B01D2252/20442—Cyclic amines containing a piperidine-ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/20—Organic absorbents
- B01D2252/204—Amines
- B01D2252/20478—Alkanolamines
- B01D2252/20484—Alkanolamines with one hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
- B01D2252/504—Mixtures of two or more absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
-
- 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
-
- 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
- F23J2219/40—Sorption with wet devices, e.g. scrubbers
-
- 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
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Definitions
- the invention relates to a method and a device for separating an acidic gas, in particular CO2, from a gas mixture.
- Alkanolamines used as absorption medium used as absorption medium.
- loaded absorption medium is regenerated by heating, releasing to a lower pressure or stripping, whereby the carbon dioxide is desorbed.
- the absorption medium can be reused.
- These methods are described, for example, in Rolker, J .; Arlt, W .; "Separation of carbon dioxide from flue gases by absorption” in Chemie Ingenieurtechnik 2006, 78, pages 416 to 424 and in Kohl, A.L .; Nielsen, R. B., "Gas Purification", 5th ed., Gulf Publishing,
- An absorption medium comprising water, a hindered amine and an alkali metal carbonate.
- composition of the absorption medium is chosen so that the absorption medium after desorption in the evaporator of the desorption by the
- the invention therefore relates to a process for the separation of acidic gases from a gas mixture which comprises absorbing acid gases by contacting the gas mixture with an absorption medium comprising water and at least one amine in an absorber to obtain a loaded absorption medium and a desorption of acidic gases from the loaded absorption medium by stripping with steam in a desorption column, wherein the absorption medium used in at
- Heating over a demixing temperature in the range of 0 to 130 ° C shows a separation into two liquid phases.
- the desorption is carried out at a temperature at which in the
- the invention also relates to an apparatus for the separation of acidic gases from a gas mixture comprising an absorber (1), a desorption column (2) with a mass transfer zone (3), an evaporator (5) and a
- Phase separation device (6) for the separation of two liquid phases with a feed point (7) and separate
- Phase separation device (6) arranged.
- Phase separation device (6) has removal points (8, 9) for a low-water liquid phase and a water-rich liquid phase.
- the mass transfer zone (3) has a liquid outlet (4), which is connected to the feed point (7) of the phase separation device.
- the device according to the invention also has
- the gas mixture can be any gas mixture.
- Natural gas a methane-containing biogas from a
- Combustion exhaust gas an exhaust gas from a
- Calcination reaction such as the burning of lime or the production of cement
- the gas mixture is a combustion exhaust gas Natural gas or a biogas, more preferably a
- Combustion exhaust gas for example, from a power plant.
- the gas mixture contains at least one acidic gas
- CO2 preferably one or more acidic gases from the series CO2, COS, H 2 S, CH 3 SH and S O 2 , particularly preferably CO 2 .
- Combustion exhaust gas is preferably previously desulfurized, i. S O2 is extracted from the gas mixture with a desulfurization process known from the prior art,
- the gas mixture preferably has a content of CO2 in the atmosphere before being brought into contact with the absorption medium
- Range of 0.1 to 50% by volume more preferably in the range of 1 to 20% by volume, and most preferably in the range of 10 to 20% by volume.
- the gas mixture can still be added to acidic gases
- the gas mixture in an absorber is contacted with an absorption medium comprising water and at least one amine which, when heated above a demixing temperature ranging from 0 to 130 ° C, segregates into two liquid phases ,
- the demixing temperature refers to the unloaded absorption medium without acidic gases.
- Demixing temperature in the range of 0 to 130 ° C.
- amines are used which have a solubility of less than 100 g of amine in 1 l of water at 100 ° C., more preferably less than 60 g of amine in 1 liter of water and most preferably less than 10 g of amine in 1 liter of water.
- the content of alkali metal salts in the absorption medium is preferably below 10 wt .-%, more preferably below 5 wt .-% and in particular below 2 wt .-%.
- Absorption medium at least one amine of the formula (I)
- Carbon atoms are those with amino groups or
- Alkylamino groups may be substituted.
- the absorption medium comprises at least one amine of the formula (I), for which the radicals R 1 and R 2 are independently hydrogen or alkyl radicals having 1 to 6 carbon atoms, more preferably R 1 is hydrogen and R 2 is an alkyl radical 1 to 6 carbon atoms.
- R 1 and R 2 are independently hydrogen or alkyl radicals having 1 to 6 carbon atoms, more preferably R 1 is hydrogen and R 2 is an alkyl radical 1 to 6 carbon atoms.
- R 1 and R 2 are independently hydrogen or alkyl radicals having 1 to 6 carbon atoms, more preferably R 1 is hydrogen and R 2 is an alkyl radical 1 to 6 carbon atoms.
- R 1 is hydrogen
- R 2 is an alkyl radical 1 to 6 carbon atoms.
- Most preferred are the compounds 4- (n-propylamino) -
- R 1 is hydrogen and R 2 is n-propyl or n-butyl.
- R 1 is preferably hydrogen and R 2 is an alkyl radical having 1 to 6 carbon atoms, R 2 particularly preferably n-propyl or n-butyl.
- the weight ratio of the first amine of the formula (I) to the second amine of the formula (I) is preferably in the range from 10: 1 to 1:10, particularly preferably in the range from 3: 1 to 1: 5 and in particular in the range from 1 : 1 to 1: 3.
- the absorption medium preferably comprises from 25 to 85% by weight of water and from 15 to 75% by weight of amines of the formula (I), based in each case on unloaded absorption medium without acidic gases.
- an absorption medium containing amines of formula (I) By using an absorption medium containing amines of formula (I), a high capacity for the absorption of CO 2 can be achieved even at low C0 2 partial pressure. In addition, such absorption media are less corrosive, show good stability against
- the absorption medium may contain, in addition to water and amines of the formula (I), at least one sterically unhindered primary or secondary amine as activator.
- a sterically unhindered primary amine in the sense of the invention is a primary amine in which the amino group is attached to a
- Carbon atom is bound to the at least one
- a sterically unhindered secondary amine in the sense of the invention is a secondary amine in which the amino group is bonded to carbon atoms to which in each case at least two hydrogen atoms are bonded.
- the content of sterically unhindered primary or secondary amines is preferably 0.1 to 10 wt .-%, particularly preferably 0.5 to 8 wt .-%.
- Suitable activators are activators known from the prior art, for example ethanolamine, piperazine and 3- (methylamino) -propylamine. Also suitable is 4-amino-2, 2, 6, 6-tetramethylpiperidine. The addition of an activator leads to an acceleration of the absorption of CO 2 from the gas mixture without loss of absorption capacity.
- the absorption medium may contain, in addition to water and amines, one or more physical solvents
- the proportion of physical solvents can be up to 50 wt .-%. As a physical
- Solvents are sulfolane, aliphatic
- Acid amides such as N-formylmorpholine, N-acetylmorpholine,
- N-alkylpyrrolidones in particular N-methyl-2-pyrrolidone, or N-alkylpiperidones, and also diethylene glycol,
- Alkyl ethers in particular diethylene glycol monobutyl ether.
- the absorption medium does not contain a physical solvent.
- the absorption medium may additionally have additives, such as corrosion inhibitors, wetting-requiring additives and defoamers.
- corrosion inhibitors it is possible in the absorption medium to use all substances which are known to the person skilled in the art for the absorption of CO 2 using alkanolamines as suitable corrosion inhibitors, in particular the corrosion inhibitors described in US Pat. No. 4,714,597.
- the amount of corrosion inhibitors can be significantly lower when using amines of the formula (I) than in a conventional
- Ethanolamine-containing absorption medium since absorption media containing amines of formula (I), compared to metallic materials significantly less are corrosive than the commonly used ethanolamine-containing absorption media.
- the wetting-requiring additive used is preferably the nonionic surfactants known from WO 2010/089257 page 11, line 18 to page 13, line 7, zwitterionic surfactants and cationic surfactants.
- Defoamers which may be used in the absorption medium are all substances which are suitable for the person skilled in the art for the absorption of CO 2 using alkanolamines
- the gas mixture is in a
- Absorption column brought into contact with the absorption medium wherein the absorption column is preferably operated in countercurrent, in order to achieve a low residual content of acidic gases in the gas mixture after absorption.
- the absorption is preferably carried out at a temperature in the range of 0 ° C to 70 ° C, more preferably 20 ° C to 50 ° C, wherein the temperature of the absorption medium when entering the absorber below the
- Demixing temperature is. Within the absorber, the temperature can also be above the segregation temperature
- Absorption column is the temperature of the
- Absorbent medium preferably 30 to 60 ° C when entering the column and 35 to 70 ° C when exiting the column.
- the absorption is preferably carried out at a pressure of
- Separation of CO 2 is the initial partial pressure of CO 2 in the gas mixture preferably 0.01 to 4 bar,
- the absorption at a total pressure of the gas mixture in the range of 0.8 to 1.5 bar, in particular 0.9 to 1.1 bar, performed. This particularly preferred embodiment is advisable in the absorption of CO 2 from the combustion exhaust gas of a power plant without compression of the combustion exhaust gas.
- the laden absorption medium obtained in the absorber is a
- the desorption is carried out at a temperature at which separation takes place in the desorption column into a water-rich liquid phase and a water-poor liquid phase.
- the temperature in the desorption is preferably in the range of 50 ° C to 200 ° C, more preferably in the range of 80 ° C to 150 ° C.
- the desorption is preferably carried out at a pressure in the range from 10 mbar to 10 bar, particularly preferably in the range from 100 mbar to 5 bar.
- the water-rich liquid phase resulting from the desorption and the water-poor liquid phase are separated from each other. Part of the water-rich liquid phase is fed to an evaporator in which water vapor is generated, which is fed into the desorption column and stripped with the in the desorption column of acidic gases.
- the low-water liquid phase and the remaining part of the water-rich liquid phase are called
- the low-water liquid phase and the remaining part of the water-rich liquid phase are preferably mixed together at a temperature below the demixing temperature before being returned to the absorber.
- the proportion of water-rich in the evaporator not evaporated liquid phase can optionally be supplied to the desorption column or the absorber.
- Absorption and desorption can be achieved because in the process, the desorption can be carried out to a low residual content of acidic gases and absorption media can be used with a high proportion by weight of amines with which a high loading is achieved in the absorption.
- the thermal and oxidative degradation of the amines used for absorption is low in the inventive method, since only a small part of the amines enters the evaporator and is exposed there to the high temperatures at the heat exchange surfaces.
- the energy requirement of the method according to the invention is compared to
- Methods using a single-phase absorption medium are significantly lower.
- the process according to the invention requires no auxiliary substances in addition to water and amine and can be carried out in simple and inexpensive apparatuses.
- Figure 1 shows a flow diagram of an embodiment of a device according to the invention, in which the
- Desorption column (2) is arranged.
- Figure 2 shows a flow diagram of a preferred embodiment of a device according to the invention, in which the
- Phase separation device (6) within the desorption column (2) below the mass transfer zone (3) is arranged.
- the device according to the invention for the separation of acidic gases from a gas mixture comprises an absorber (1) in which the gas mixture (20) containing acidic gases is brought into contact with a liquid absorption medium.
- absorber all known from the prior art devices for the absorption of a gas from a Gas mixture are used in a liquid.
- a washing column is preferably used, preferably internals to increase the
- Suitable internals are, for example, packing, e.g. Raschig rings or Pall rings, structured column packs, e.g.
- Sheet metal packings as well as column bottoms, e.g. Sieve trays.
- a membrane contactor a radial flow scrubber, a jet scrubber, a venturi scrubber or a rotary scrubber can be used as the absorber.
- the absorber used is particularly preferably a scrubbing column for countercurrent operation, in which the gas mixture containing acidic gases in a lower region of the
- Absorption medium is supplied in an upper region of the wash column.
- the device according to the invention comprises a
- the desorption column is laden with the acidic gas
- Absorption medium supplied from the absorber is preferably fed to the desorption column above the mass transfer zone.
- a desorption column all known from the prior art columns for the desorption of a gas from a liquid can be used.
- Mass transfer zone (3) is preferably in the form of
- Column trays random packings or structured packings are preferably used as internals.
- column trays for example, bubble trays, sieve trays, tunnel trays, valve trays, slotted trays, sieve slotted trays, sieve bubble trays, nozzle trays or
- the mass transfer zone (3) has a liquid outlet (4), on which liquid is collected, which emerges at the lower end of the mass transfer zone.
- the device according to the invention comprises an evaporator (5) in which steam is produced, which is fed to the desorption column (2) to supply heat for the desorption of acidic gas from the loaded absorption medium and with the vapor stream acidic gases from the liquid
- evaporator all known from the prior art evaporators can be used, for example, natural circulation evaporator,
- the device according to the invention comprises a
- Phase separation device (6) for the separation of two liquid phases with a feed point (7) and separate
- Evaporator (5) and the phase separator (6) are arranged separately.
- the liquid outlet (4) of the mass transfer zone (3) is connected to the feed point (7) of the phase separation device in order to remove from the
- Phase separation device can all from the state of
- settling tanks in which a separation of the Phases are done by gravity.
- separators may be used in which the phases are separated by centrifugal forces.
- phase separation device (6) is arranged within the desorption column (2) below the mass transfer zone (3)
- the device according to the invention comprises a
- Device also comprises a connecting line (11) from the discharge point (9) for low-water liquid phase to the absorber (1), is returned to the low-water liquid phase in the absorber.
- the device according to the invention additionally comprises a
- the phase separation device (6) in this embodiment has a level control (18) for a liquid-liquid phase interface in the phase separation device (6), with which the control valve (17) or the controllable pump is driven.
- the device according to the invention additionally comprises a
- Removal point (8) for water-rich liquid phase mixes As a mixing device, all known in the art devices for mixing two liquids can be used. As a mixing device are, for example, stirred containers, containers with a liquid circulation via an external circuit or static mixer.
- Water-rich liquid phase of the mixing device (19) is supplied, heat exchangers (21, 22) arranged, with which let the two phases to a temperature below the demixing temperature of the absorption medium used in the absorber to cool.
- the heat exchangers (21, 22) are arranged so that they heat exchange between the loaded
- Desorption column (2) is supplied, and the liquid phases, which are supplied to the mixing device (19) cause.
- the mixing device By using the mixing device, a uniform flow can be achieved during operation of the device
- composition of the absorption medium in the absorber ensure that variations in the control of the device do not affect the effectiveness of the absorption.
- the device according to the invention preferably additionally comprises a condenser (23), which is connected to the head of the desorption column (2) and connected to the
- FIG. 1 shows an embodiment of the device according to the invention, in which the phase separation device (6) is arranged separately from the desorption column (2) and is designed as a settling tank with an overflow weir.
- Mass transfer zone (3) used in the connecting line between the liquid outlet (4) and the inlet point (7) of the phase separation device koaleszenzufde internals can be arranged, such as
- Coalescing filter to achieve a more complete phase separation in the phase separation device.
- Figure 2 shows a preferred embodiment
- phase separation device (6) within the desorption column (2) below the mass transfer zone (3) is arranged.
- the phase separation device (6) is characterized by a
- Overflow weir (13) formed in the column sump (12), which separates the column sump in a first zone (14) and a second zone (15), and by a feed point (7) to the first zone (14), wherein the feed point with the
- Liquid outlet (4) of the mass transfer zone (3) is connected.
- the liquid drain (4) is preferably formed as a collection tray for liquid with a liquid drain above the first zone.
- the feed point to the first zone (14) may be above the first zone (14) be arranged as shown in Figure 2, or within the first zone (14) below the upper edge of the overflow weir (13) to be arranged.
- a removal point (8) is arranged, which via a connecting line (10) connected to the evaporator (5) is and arranged in the second zone (15) has a removal point (9), which has a
- the device according to the invention may comprise additional pumps, measuring devices, control valves, shut-off valves and buffer containers which are not shown in FIGS. 1 and 2 and which the person skilled in the art has been aware of
- the device according to the invention has a simple structure and can be carried out with commercially available apparatuses. It enables stable operation without
- the absorption medium was placed in a pressure-resistant glass vessel and saturated at 20 ° C and atmospheric pressure by the addition of dry ice with CO 2 .
- the glass jar was then capped and the CO 2 -loaded absorption medium was slowly heated in an oil bath until separation into two liquid phases, that of turbidity of the previously clear mixture
- Butyl TAD 4- (n-butylamino) -2,2,6,6-tetramethylpiperidine
- DM-TAD 4- (dimethylamino) -2,2,6,6-tetramethylpiperidine
- TAT 4- (3-dimethylamino-propylamino) -
- EAE-TAD 4- (2-ethylamino-ethylamino) -
- Evaporator is supplied, containing only small amounts of amine.
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- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
Description
Claims
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DE102011086252 | 2011-11-14 | ||
PCT/EP2012/070380 WO2013072147A1 (de) | 2011-11-14 | 2012-10-15 | Verfahren und vorrichtung zur abtrennung von sauren gasen aus einer gasmischung |
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US (2) | US9221007B2 (de) |
EP (1) | EP2780098A1 (de) |
AU (1) | AU2012339061B2 (de) |
BR (1) | BR112014008497A2 (de) |
CA (1) | CA2855855A1 (de) |
CO (1) | CO6960534A2 (de) |
EA (1) | EA025928B1 (de) |
MX (1) | MX2014005746A (de) |
TN (1) | TN2014000090A1 (de) |
WO (1) | WO2013072147A1 (de) |
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2012
- 2012-10-15 AU AU2012339061A patent/AU2012339061B2/en not_active Expired - Fee Related
- 2012-10-15 WO PCT/EP2012/070380 patent/WO2013072147A1/de active Application Filing
- 2012-10-15 EP EP12773311.1A patent/EP2780098A1/de not_active Withdrawn
- 2012-10-15 EA EA201400577A patent/EA025928B1/ru not_active IP Right Cessation
- 2012-10-15 CA CA2855855A patent/CA2855855A1/en not_active Abandoned
- 2012-10-15 BR BR112014008497A patent/BR112014008497A2/pt not_active IP Right Cessation
- 2012-10-15 MX MX2014005746A patent/MX2014005746A/es unknown
- 2012-11-13 US US13/675,979 patent/US9221007B2/en not_active Expired - Fee Related
-
2014
- 2014-03-03 TN TNP2014000090A patent/TN2014000090A1/en unknown
- 2014-05-13 CO CO14102761A patent/CO6960534A2/es unknown
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2015
- 2015-10-28 US US14/925,183 patent/US20160045857A1/en not_active Abandoned
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Also Published As
Publication number | Publication date |
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WO2013072147A1 (de) | 2013-05-23 |
US20130118350A1 (en) | 2013-05-16 |
EA025928B1 (ru) | 2017-02-28 |
AU2012339061A1 (en) | 2014-03-13 |
CO6960534A2 (es) | 2014-05-30 |
EA201400577A1 (ru) | 2014-10-30 |
BR112014008497A2 (pt) | 2017-04-11 |
US20160045857A1 (en) | 2016-02-18 |
CA2855855A1 (en) | 2013-05-23 |
US9221007B2 (en) | 2015-12-29 |
TN2014000090A1 (en) | 2015-07-01 |
AU2012339061B2 (en) | 2016-10-13 |
MX2014005746A (es) | 2014-07-09 |
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