WO2015190936A1 - Absorbent system and method for capturing co2 from gas stream - Google Patents
Absorbent system and method for capturing co2 from gas stream Download PDFInfo
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- WO2015190936A1 WO2015190936A1 PCT/NO2015/050106 NO2015050106W WO2015190936A1 WO 2015190936 A1 WO2015190936 A1 WO 2015190936A1 NO 2015050106 W NO2015050106 W NO 2015050106W WO 2015190936 A1 WO2015190936 A1 WO 2015190936A1
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
- C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
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- 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
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- 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
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- 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
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- 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
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- 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
- B01D2252/20489—Alkanolamines with two or more hydroxyl groups
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- 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
- B01D2252/20494—Amino acids, their salts or derivatives
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- 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
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- 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
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- 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
- This invention relates to a liquid absorbent and a system for capturing acidic gases, such as carbon dioxide from an exhaust gas.
- the invention also relates to a method of capturing acid gases from an exhaust gas in a process plant.
- the exhaust gas may come from fossil fuel fired power stations, from natural gas streams, from blast furnace oven off-gases in iron/steel plants, from cement and fertilizer plant exhaust gas and from reformer gases containing CO2 in mixtures
- the method to remove acid gases from a gas stream using solvent is a well-known art.
- Typical absorbent solutions such as amine, carbonate, ammonia or amino acid salt solutions are used to remove the acid gas.
- a simplified conventional layout of such an absorption plant includes the use of an absorber and a desorber where the solution is circulated in a continuous cycle where the absorbent liquid is contacted countercurrent with the upward flowing gas.
- a main issue with these processes, especially in cases of removal of CO2 from low partial pressure flue gases, is the energy required for regenerating the absorbent in the desorber.
- Several technologies using the amine-based process have been developed including the conventional technology like the Fluor Econamine process which has been further improved to the Fluor Econamine FC Plus SM process.
- amine base processes include MHI/KEPCO's KS-1 , 2, and 3 (sterically hindered amines); Cansolv® Absorbent DC101TM (tertiary amines with a
- U.S. Pat. No. 1 ,990,217 teaches the use of a salt of an organic acid and an inorganic base for gas purification, while US. Pat. No. 2, 176,441 teaches the use of a salt of amino acids and inorganic or organic bases whereby the amino acid should be derived from a primary, secondary or tertiary amine having at least two nitrogen atoms.
- US 2007/0264180 A1 discloses use of an absorbent solution comprising compounds capable of forming two separable phases by addition of an acid that is stronger than the acid compounds of the gaseous effluent to be treated: a first phase rich in acid compounds and a second phase poor in acid compounds wherein amine, amino acids or amino-acid alkaline salts are used as activators to favour absorption of compounds to be eliminated.
- the process includes acid neutralization of multiamines to form two phase liquid and a process for separation of the two phase liquid.
- AU-B-67247/81 describes the use of an aqueous scrubbing solution comprising a mixture of a basic salt, potassium carbonate, and an activator for the said basic salt comprising at least one, sterically hindered amine and a sterically hindered amino acid as a cosolvent for the sterically hindered amine.
- the amino acid here serves to prevent two phase separation of the aqueous solution at high temperatures.
- BE 767, 105 discloses a process for removing acid gases from gaseous streams by contacting the gaseous streams with a solution comprising potassium carbonate and an amino acid.
- WO 2012/030630 A1 teaches the use of a system comprising an amine and/or amino acid salt capable of absorbing the CO2 and/or SO2 to produce a CO2- and/or SO2-containing solution; an amine regenerator to regenerate the amine and/or amino acid salt; and, when the system captures CO2, an alkali metal carbonate regenerator comprising an ammonium catalyst capable of catalyzing the aqueous alkali metal bicarbonate into the alkali metal carbonate and CO2 gas.
- This disclosure does not allow precipitation in the absorber. Precipitation is only allowed outside the absorber in the amine regenerator unit where a concentrated alkali carbonate is used to regenerate the amine/amino acid salts while producing alkali bicarbonate precipitate.
- WO 03/095071 A1 discloses a concept for the use of slurries from precipitating amino acid salt for CO2 capture.
- U.S. 2010/0092359 A1 discloses a method for capturing CO2 from exhaust gas in an absorber, wherein the CO2 containing gas is passed through an aqueous absorbent slurry.
- the aqueous absorbent slurry comprises an inorganic alkali carbonate, bicarbonate and at least one of an absorption promoter and a catalyst.
- CO2 is converted to solids by precipitation in the absorber.
- Said slurry having the precipitated solids is conveyed to a separating device, in which the solids are separated off, essentially all of at least one of the absorption promoter and catalyst is recycled together with the remaining aqueous phase to the absorber.
- WO 2013/053853 A1 discloses a method for regeneration of bicarbonate slurry formed in a carbonate process.
- the object of the present invention is to provide an absorbent system and method that improves carbon dioxide removal efficiency when compared with conventional amine, absorbent from organic acid neutralized with inorganic base carbonate based and ammonia absorbent systems.
- the present invention provides an absorbent for capturing CO2 from an exhaust gas comprising an aqueous absorbing mixture of at least an amine and a fast reacting amino acid salt, wherein the amine is selected from high bicarbonate forming amines, the mixture forms precipitates during CO2 absorption in the absorber.
- the high bicarbonate forming amines are sterically hindered and/or are tertiary amines.
- preferred amines are: 2-amino-2- methylpropanol (AMP), 2-amino-2-methyl-1 ,3-propanediol (AMPD), 2- (diethylamino)-ethanol(DEEA), ⁇ , ⁇ -dimethylethanolamine (DMMEA) and methyl diethanolamine (MDEA), triethanolamine (TEA), 1 -(diethylamino)-2-propanol, 3- (diethylamino)-l -propanol, tripropylamine, 2-pyrrolidinoethanol, 3-(diethylamino)- 1 ,2-propanediol , N-piperidineethanol, 1 -methylpiperidine-2-ethanol, 1 - piperidinepropanol.
- AMP 2-amino-2- methylpropanol
- AMPD 2-amino-2-methyl
- Amino acid salts are products of neutralization between an amino acid and an inorganic base or an organic base.
- the amino acid preferably has a pKa > 9.
- Suitable amino acids are glycine, taurine, sarcosine, proline, alanine, lysine, serine, pipecolinic acid, arginine, threonine and cysteine.
- suitable inorganic bases are potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH).
- organic bases are amines selected from amines with pKa > 9, said amines include methylaminopropylamine (MAPA), piperazine (PZ), N-2- hydroxyethylpiperazine, N-(hydroxypropyl)piperazine, diethanol triamine (DETA), 2-((2-aminoethyl)amino)ethanol (AEEA), piperidine, pyrrolidine, dibutylamine, trimethyleneimine, 1 ,2-diaminopropane and 1 ,3-diaminopropane, N-2- hydroxyethylpiperazine, N-(hydroxypropyl)piperazine, monoethanolamone (MEA), diethanolamine (DEA), diisopropanolamine (DIPA), 3-aminopropanol (AP), 2,2- dimethyl-1 ,3-propanediamine (DMPDA), 3-amino-1 -cyclohexylaminopropane (ACHP), diglycolamine (D
- the aqueous absorbent mixture comprises from 0.5 to 8.0 mol/kg of the fast reacting amino acid salt, and preferably from 1 to 4 mol/kg.
- the aqueous absorbent mixture comprises from 0.5 to 10.0 mol/kg of the amine, preferably from of 1 .0 - 6.0 mol/kg.
- the aqueous absorbent mixture comprises from 10 to 85% water.
- Another aspect of the invention is a system for capturing CO2 from an exhaust gas comprising:
- Precipitation occurs in two steps, the first precipitation of amine bicarbonate complex occurs at an earlier stage in CO2 absorption and the first precipitate is withdrawn at the end of the first absorber section and conveyed through a cross heat exchanger to a flash regenerator where the precipitate dissolves with CO2 release.
- a low grade heat can be used in the flash regenerator.
- a second precipitation of metal bicarbonate complex occurs at the end of the second absorber section or a CO2 rich absorbent system at the end of the second section is conveyed through a second cross heat exchanger to the absorbent regeneration unit /desorber.
- the heat of regeneration is supplied through a reboiler and the hot lean absorbent is used as pre-heater for the CO2 rich slurries withdrawn from the first and second sections of the absorber.
- the lean absorbents from the flash regenerator and the desorber are remixed and returned to the top of the absorber to continue the cycle wherein the CO2 released from the flash regenerator and the desorber is collected and sent to compression.
- a slurry of amine bicarbonate complexes from the first absorber is passed through a solid-liquid separator from which the more concentrated slurry is conveyed to the flash generator where the precipitate dissolves with CO2 release.
- the liquid phase is returned to the top of the second absorber in a countercurrent manner with the upcoming gas stream to continue CO2 absorption.
- the system contains two absorbers, it further comprises a solid-liquid separator from which the more concentrated slurry is conveyed to the flash regenerator and from which the liquid phase is returned to the top of the second absorber section in a countercurrent manner with the upcoming gas stream to continue CO2 absorption.
- the inventive absorbent system improves carbon dioxide removal efficiency due to its higher CO2 removal ability per cycle when compared with conventional amine, absorbent from organic acid neutralized with inorganic base and carbonate based absorbent system. It exhibits less solvent vaporisation loss because part of the absorbent is in salt form.
- the present invention also provides a method of capturing CO2 from an exhaust gas in a process plant comprising:
- obtaining a rich CO2 liquid absorbent in a second section of the absorber conveying the rich CO2 liquid absorbent from the second section to a desorber, wherein the rich CO2 liquid absorbent is heated resulting in release of CO2 and a hot lean absorbent to be recycled to the absorber.
- the slurry withdrawn from the first absorption section is heated to dissolve the precipitate with CO2 release in the amine flash regeneration tank.
- the first precipitate may be heated by heat transfer with the hot lean absorbent coming from the desorber.
- the first precipitate may be regenerated in the flash regenerator by an available low grade heat in the process plant.
- a second precipitate of metal bicarbonates may occur in the second section of the absorber and form a second rich CO2 absorbent slurry.
- the slurry or the rich CO2 liquid absorbent from the second section is withdrawn from the bottom of the absorber and sent to the regenerator for desorption with CO2 release.
- the slurry or the rich CO2 liquid absorbent from the second section may be passed through a second heat exchanger to be heated by heat transfer with the hot lean absorbent from the desorber.
- the lean amine and amino acid salt mixture from the flash regenerator and desorber are preferably mixed and returned to the top of the absorber.
- slurry of the first precipitate from the first absorber section is passed through a solid-liquid separator from which the more concentrated slurry is conveyed to the flash regenerator.
- the first precipitate dissolves with CO2 release in the flash regenerator, and the liquid phase will be returned to the top of the second absorber section in countercurrent manner with the upcoming gas stream to continue CO2 absorption.
- Figure 1 is a simplified sketch of the slurry-slurry process for CO2 capture.
- Figure 2 is a simplified sketch of the slurry-slurry process for CO2 capture with two separate absorber sections.
- Figure 3 shows XRD analysis result.
- FIG. 4 shows an example vapour liquid solid equilibrium (VLSE) at 40°C and 120 ° C.
- the present invention came out of the desire of the inventors to shorten the time required for the formation of solid precipitate in certain amino acid salt systems and increase the absorption rate of such system. Precipitation of CO2 as solid in a process will increase the CO2 driving force into the liquid and result in increased loading capacity.
- Certain amino acid salt systems such as potassium sarcosinate have very good absorption kinetics, (Aronu UE, Ciftja AF, Kim I, Hartono A ; Understanding precipitation in amino acid salt systems at process conditions, Energy procedia 37 (2013) 233-240), but formation of solid potassium bicarbonate (KHCO3) occurs very late at the point when the absorption kinetic is very slow making it unfavorable precipitating system candidate since the benefit of precipitation at process condition cannot be fully exploited.
- KHCO3 solid potassium bicarbonate
- the inventors therefore searched for a method to enhance early precipitation for such a system. It is known that certain amines, such as 2-amino-2-methylpropanol (AMP), at high CO2 loading or high concentration can precipitate in a process.
- AMP 2-amino-2-methylpropanol
- Step 1 Formation of solid precipitate of amine bicarbonate
- R and R' represent hydrogen, C1-4 alkyl, C1-4 alkanol, or a straight chain, cyclic or aromatic amine groups, wherein at least one of R and R' is an C1-4 alkyl, C1-4 alkanol or a straight chain, cyclic or aromatic amine group, wherein the straight chain contains up to 7 carbon atoms, and the cyclic or aromatic amine groups contain from 3 to 6 carbon atoms.
- M can be selected from K, Li or Na
- the amino acid salt used in the present invention is the product of neutralization between an amino acid and an inorganic base or organic base.
- the amino acids that can be used include but are not limited to glycine, taurine, sarcosine, proline, alanine, lysine, serine, pipecolinic acid, arginine, threonine and cysteine.
- the inorganic bases that can be used for amino acid neutralization in the present invention include but are not limited to potassium hydroxide, sodium hydroxide and lithium hydroxide.
- the organic bases that can be used for amino acid neutralization include amines; such amines include but are not limited to: methylaminopropylamine (MAPA), piperazine (PZ), N-2-hydroxyethylpiperazine, N-(hydroxypropyl)- piperazine, diethanol triamine (DETA), 2-((2-aminoethyl)amino)ethanol (AEEA), piperidine, pyrrolidine, dibutylamine, trimethyleneimine, 1 ,2-diaminopropane, 1 ,3- diaminopropane, 2-amino-2-methylpropanol (AMP), 2-(diethylamino)- ethanol(DEEA), 3-amino-1 -cyclohexylaminopropane (ACHP), 3-aminopropanol (AP), 2,2-dimethyl-1 ,3-propanediamine (DMPDA), 1 -amino-2-propanol (MIPA), 2- methyl-methanol
- the pKa of the amine is at least greater than the pKa of amino acid used.
- the amine blended with the amino acid salt is preferably a strong or high bicarbonate forming amine like a sterically hindered and/or a tertiary amine.
- Such amines include but are not limited to 2-amino-2-methylpropanol (AMP), 2-amino-2- methyl-1 ,3-propanediol (AMPD), 2-(diethylamino)-ethanol(DEEA), N,N-dimethyl- ethanolamine (DMMEA), methyl diethanolamine (MDEA), triethanolamine (TEA), 1 -(diethylamino)-2-propanol, 3-(diethylamino)-1 -propanol, tripropylamine,
- 2-pyrrolidino-"ethanol 3-(diethylamino)-1 ,2-propanediol , N-piperidineethanol, 1 - methylpiperidine-2-ethanol andl -piperidinepropanol.
- FIG 1 a simplified process diagram of the method used to capture CO2 using the absorbent according to the invention is disclosed.
- the C02-containing gas stream 1 enters the absorber A1 in the bottom and flows upwards. It meets a liquid absorbent stream 12 in two stages.
- stream 12 is a stream containing a slurry of water, a mixture of the metal bicarbonate of amine ( Li, Na, or K); carbamates of amine, amino acid; amino acid salt and amine.
- stream 12 is stream containing a slurry of water, a mixture of the bicarbonate of amine; carbamate of amine, amino acid; amino acid salt and amine.
- a slurry of water a mixture of the bicarbonate of amine; carbamate of amine, amino acid; amino acid salt and amine.
- the aqueous phase is partially or fully saturated with the bicarbonates such that the flow contains both solids and liquid.
- the aqueous solution contains a precipitation promoting amine and an absorption rate promoting amino acid salt or a precipitation promoting amino acid salt and an absorption rate promoting amine.
- C02-containing gas stream 1 b from absorber section 2 enters the bottom of absorber section 1 and flows upwards in contact with the downward flowing stream 12.
- the withdrawn slurry, stream 3 is passed through a solid-liquid separator where more concentrated slurry, stream 4 is sent to the flash
- the operating temperature of the absorber will depend on the inlet flue gas temperature and will typically be from 30° C to 80° C, preferably from 40° C to 60° C. Further cooling or pre-treatment of the flue gas may be required to remove/reduce fly ash in cases with high temperature and water content, some cooling and water removal might be necessary. Some cooling may be required in the bottom region of section 1 before withdrawal of stream 3 to further enhance solid precipitation in this region.
- the stream 3 region in the absorber is preferably maintained at 30°C to 50°C.
- the CO2 is absorbed into the aqueous slurry and the exhaust, stream 2 with reduced CO2 content leaves the absorber, after a water wash section. This water wash is only needed to retain the amine, depending on its volatility.
- the absorption tower is preferably a plate tower that can handle slurries.
- a spray tower, packed tower or any other suitable tower able to handle slurries can also be used.
- the additional reactions described in Eq. 2 and 3 take place in section 1 before the withdrawal of stream 3 while the additional reactions described in Eq. 4 and 5 takes place in section 2 before the withdrawal of stream 7 at the bottom of the absorber.
- the entering stream 12 will typically be high in amino acid salt and amine content.
- the fast reacting amino acid salt enhances the transport of gaseous CO2 into the liquid absorbent.
- the CO2 in the liquid phase is further stored away into the amine as bicarbonate.
- amine bicarbonate formed grows until the solubility limit is exceeded resulting in precipitation as solid amine bicarbonate slurry in the bottom of section 1 , where the bicarbonate slurry is withdrawn as stream 3 at a temperature from 30 ° C to 60 ° C.
- Withdrawal of stream 3 has a significant benefit; complete withdrawal of CO2 saturated slurry from the absorber will shift equilibrium further to the right enhancing more CO2 containing liquid phase products.
- the slurry withdrawal will also significantly reduce the viscosity of the absorbent system at this stage. This combined effect will accelerate mass transport of CO2 into the liquid phase even at the middle of the absorption resulting in enhanced absorption capacity. Further, a withdrawal of the first precipitate from the solution as stream 3 will result in a less volume of solution for regeneration in the desorber.
- the amino acid salt containing CO2 in low proportion and amine saturated with CO2 as carbamate and/bicarbonate will remain in solution and continue contacting CO2 in the absorber section 2.
- Ability of the amino acid salt for fast reaction with CO2 and increased gas to liquid in this section allows further uptake of CO2 along the absorber in section 2 forming more amino acid carbamate, which undergoes hydrolysis to produce KHCO3 as in Eq. 5.
- KHCO3 will precipitate and form a slurry containing amine bicarbonate/carbamate as well as amino acid carbamate/amino acid.
- This second stage precipitation in absorber section 2 will also result in another absorption rate and capacity enhancement since CO2 bound as precipitate will not participate in the equilibrium backpressure over the solution.
- the slurry leaves the bottom of the absorber as stream 7 at a temperature from 40 to 70 ° C.
- the slurry in stream 7 is passed through the cross exchanger HX1 and is heated up like in a conventional amine process by heat transfer with the lean absorbent stream 9 from the desorber.
- the filtration and/or crystallization often proposed for a precipitating process is not required.
- the slurry is sufficiently saturated with solids and a smaller liquid volume will be treated in the desorber because part of the total liquid has been withdrawn as stream 3 as precipitate slurry.
- the heated slurry stream 8 is delivered into the desorber D1 from the top where the solid precipitate is completely dissolved with CO2 released in stream 13. CO2 desorption is enhanced on further contact with upcoming stripping vapour from a reboiler R1 .
- the precipitate in the slurry may be completely dissolved before in enters the reboiler through stream 15 depending on the desorber operating conditions. Hot vapour from the desorber is returned into the bottom of the desorber column by stream 16.
- the typical temperature range in the desorber is 100 ° C to 200 ° C.
- the KHCO3 decomposes with CO2 release likewise the bicarbonate/carbamate of the amine and amino acid resulting in the regeneration of the amino acid salt and amine in the absorbent.
- the desorber can be a packed tower, a plate tower, a spray tower, a flash tank or any other suitable tower.
- Stream 9 emerges the cross changer as stream 10 with lower temperature 60 ° C -1 10 ° C but with sufficient heat to transfer at the cross exchanger HX2 to stream 3.
- Stream 3 emerges from HX2 as stream 4 at higher temperature 60 - 1 10 ° C, sufficient to completely dissolve the precipitate and further strip off CO2 from the liquid phase.
- the stream 4 is fed into the flash regenerator F1 where CO2 is released in stream 6 and combined with stream 13 to form stream 14 containing CO2 for storage.
- CO2 pressure for compression will vary significantly based on the mode of operation of the desorber.
- the produced CO2 pressure can be in the range 3 - 50 bar.
- Stream 10 emerges from HX2 as stream 1 1 at lower temperature and is combined with stream 5, lean absorbent from the flash regenerator, F1 to form stream 12; the lean absorbent is returned to the top of the absorber A1 .
- Stream 5 can also be combined with stream 8 delivered into the desorber D1 .
- the process can also be configured such that the lean stream 9 is first used to heat up stream 3 in HX2 before using it to heat up stream 7 in HX1 .
- the gas phase leaving the reactor is cooled and CO2 content is analysed online by IR.
- the absorption test gives fast relative comparison of absorption rate, it also allows the possibility to study the precipitate behaviour, crystal formation and dissolution during the experiment.
- the absorption process terminates when the concentration of CO2 in the effluent reaches 9.5 vol% representing about 9.5 kPa partial pressure of CO2 or when the absorption rate becomes too low.
- a liquid sample containing both the rich liquid and precipitated crystal is collected for analysis at the end of absorption.
- a similar sample is collected, filtered and dried for precipitate analysis by XRD.
- Precipitate dissolution was monitored by heating up the solvent in the range 40°C to 90°C while bubbling pure N2 gas at 2.25 NL/min through the solution in the reactor bottle. It was observed that the CO2 content of the effluent gas increases as N2 bubbles through the solution while the precipitate dissolution is monitored and logged. Gas phase analysis was used to determine the liquid phase CO2 concentration during the experiment.
- Example 1 except that a 7 mol/kg solution containing 3mol/kg potassium glycine (KGLY) and 4 mol/kg 2-amino-2-methylpropanol (AMP) as an absorbent was used as an absorbing solution in Example 2. This absorbent was found to form two liquid phase before CO2 absorption, but forms one phase as the loading progresses before precipitation start. In example 3, a 7 mol/kg solution containing 3 mol/kg sodium glycine (NaGLY) and 4 mol/kg 2-amino-2-methylpropanol (AMP) was the absorbent used. The results obtained are shown in Table 1.
- Example 2 An absorption experiment was carried out in the same manner as in Example 1 , except that an aqueous solution containing 5 mol/kg potassium sarcosine (KSAR) as an absorbent in comparative example 1 while in comparative example 2-3 aqueous solution containing 4mol/kg 2-amino-2-methylpropanol (AMP) and 4.9mol/kg of monoethanolamine (MEA) was used, respectively.
- KSAR potassium sarcosine
- AMP 2-amino-2-methylpropanol
- MEA monoethanolamine
- the slurry formed after absorption experiment was filtered and the filtrate dried at room temperature.
- X-ray diffraction (XRD) analysis was conducted on the filtered solid cake.
- the XRD analysis results are shown in FIG 3.
- the filtrate from the comparative example 1 was identified as KHCO3 by XRD analysis, while the filtrate from comparative example 2 is identified as the bicarbonate of AMP. From the figure, it can be observed that the solid phase spectra of Example 1 and 2 contain spectra of comparative example 1 and 2 at variable degrees. This shows that two precipitate types are found in the solution and these two precipitates are a mixture containing the precipitate of comparative example 1 and 2.
- Example 1 shows that the first precipitate in Example 1 and 2 is needle-like as was observed in comparative example 2.
- the spectra confirm that formation of first precipitate of AMP bicarbonate and as loading further increases a second precipitate, KHCO3 is formed.
- the absorption solid phase of Example 3 appears somewhat different from the rest of the spectra. Although two precipitation stages occurred, precipitates with different morphology are formed.
- Example 3 is the only solution containing sodium salt; the other precipitates contain potassium salt.
- VLSE vapour liquid solid equilibrium
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Abstract
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Priority Applications (5)
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EP15806638.1A EP3166710B1 (en) | 2014-06-13 | 2015-06-12 | Absorbent system and method for capturing co2 from gas streams |
AU2015272142A AU2015272142A1 (en) | 2014-06-13 | 2015-06-12 | Absorbent system and method for capturing CO2 from gas stream |
PL15806638T PL3166710T3 (en) | 2014-06-13 | 2015-06-12 | Absorbent system and method for capturing co2 from gas streams |
US15/318,228 US10413860B2 (en) | 2014-06-13 | 2015-06-12 | Absorbent system and method for capturing CO2 from a gas stream |
CA2951411A CA2951411C (en) | 2014-06-13 | 2015-06-12 | Absorbent system and method for capturing co2 from a gas stream |
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US201462011790P | 2014-06-13 | 2014-06-13 | |
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EP (1) | EP3166710B1 (en) |
AU (1) | AU2015272142A1 (en) |
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CN116212591A (en) * | 2023-04-11 | 2023-06-06 | 华北电力大学(保定) | Low-corrosiveness phase change absorbent and application thereof in carbon dioxide capturing |
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- 2015-06-12 CA CA2951411A patent/CA2951411C/en active Active
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- 2015-06-12 EP EP15806638.1A patent/EP3166710B1/en active Active
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CN105749718A (en) * | 2016-03-24 | 2016-07-13 | 大唐环境产业集团股份有限公司 | Efficient dust removing and flow equilibrating device of square-box type desulfurizing tower |
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RU2751200C2 (en) * | 2018-12-05 | 2021-07-12 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" | Method for obtaining carbon dioxide for soda production by the ammonia method |
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CA2951411A1 (en) | 2015-12-17 |
EP3166710B1 (en) | 2019-12-11 |
CA2951411C (en) | 2022-09-13 |
EP3166710A4 (en) | 2018-01-31 |
US20170106331A1 (en) | 2017-04-20 |
EP3166710A1 (en) | 2017-05-17 |
PL3166710T3 (en) | 2020-06-01 |
US10413860B2 (en) | 2019-09-17 |
AU2015272142A1 (en) | 2016-12-15 |
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