WO2013159228A1 - Capture de co2 à l'aide d'une anhydrase carbonique et de solvants amino tertiaires pour un rapport de flux amélioré - Google Patents

Capture de co2 à l'aide d'une anhydrase carbonique et de solvants amino tertiaires pour un rapport de flux amélioré Download PDF

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Publication number
WO2013159228A1
WO2013159228A1 PCT/CA2013/050314 CA2013050314W WO2013159228A1 WO 2013159228 A1 WO2013159228 A1 WO 2013159228A1 CA 2013050314 W CA2013050314 W CA 2013050314W WO 2013159228 A1 WO2013159228 A1 WO 2013159228A1
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WIPO (PCT)
Prior art keywords
absorption
solution
carbonic anhydrase
compound
tertiary amino
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PCT/CA2013/050314
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English (en)
Inventor
Geert F. Versteeg
Nathalie J.M.C. Penders
Sylvie Fradette
Julie Gingras
Jonathan A. CARLEY
Glenn R. Kelly
Normand Voyer
Peter W. J. DERKS
Olivera Ceperkovic
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Co2 Solutions Inc.
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Application filed by Co2 Solutions Inc. filed Critical Co2 Solutions Inc.
Priority to EP13780585.9A priority Critical patent/EP2849872A4/fr
Priority to CN201380033637.4A priority patent/CN104602789A/zh
Publication of WO2013159228A1 publication Critical patent/WO2013159228A1/fr

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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
    • 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
    • B01D2252/60—Additives
    • B01D2252/602—Activators, promoting agents, catalytic agents or enzymes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/804—Enzymatic
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention generally relates to the field of C0 2 capture and more particularly relates to C0 2 capture using carbonic anhydrase and an absorption compound.
  • One technique involves using an absorption compound in combination with carbonic anhydrase enzyme.
  • a process for treating a C0 2 containing gas comprising contacting the gas with an aqueous absorption solution comprising carbonic anhydrase and an amount of tertiary amino absorption compound sufficient to increase the enzymatically enhanced flux of C0 2 absorbed into the aqueous absorption solution by at least 6 times.
  • the tertiary amino absorption compound comprises a tertiary alkanolamine and/or a tertiary amine.
  • the tertiary alkanolamine comprises MDEA, TEA, DEMEA, DMMEA or TIPA or a combination thereof.
  • the tertiary amino absorption compound has a structure NR ⁇ Rs, wherein R is hydroxyethyl, isopropyl, methyl or ethyl, R 2 is methyl, ethyl, isopropyl or hydroxyethyl, and R 3 is methyl, ethyl, isopropyl or hydroxyethyl.
  • the tertiary amino absorption compound has a concentration of at least 0.4 M, at least 1 M, at least 2 M, at least 3 M or at least 4 M.
  • the tertiary amino absorption compound has a concentration between 0.4 M and 4 M, between 0.5 M and 3 M, between 0.75 M and 1.75 M or between 1 M and 2 M.
  • the flux ratio between the enzymatically enhanced flux of C0 2 over the non-enzymatic flux of C0 2 is above 8 or above 10.
  • the flux ratio between the enzymatically enhanced flux of C0 2 over the non-enzymatic flux of C0 2 is between 6 and 12.
  • the carbonic anhydrase is provided free in the aqueous absorption solution as dissolved enzymes or as enzyme aggregates.
  • the carbonic anhydrase is provided on or in particles that flow with the aqueous absorption solution, being entrapped in pores of the particles, covalently bonded to the particles, or otherwise immobilized with respect to the particles.
  • the carbonic anhydrase is provided on or in packing material.
  • the tertiary amino absorption compound and the carbonic anhydrase are provided in relative quantities between about 0.5 M per 0.2 g/L to about 2 M per 0.2 g/L, between about 1 M per 0.2 g/L to about 1.5 M per 0.2 g/L, in a range that may be determined from one or more of Figs 3 to 9.
  • a process for treating a C0 2 containing gas comprising contacting the gas with an aqueous absorption solution comprising carbonic anhydrase and an amount of a slow absorption compound sufficient to increase the enzymatically enhanced flux of C0 2 absorbed into the aqueous absorption solution by at least 6 times.
  • a process for treating a C0 2 containing gas comprising contacting the gas with an aqueous absorption solution comprising carbonic anhydrase and a tertiary amino absorption compound having the structure NR ⁇ F ⁇ , wherein Ri is hydroxyethyl, isopropyl, methyl or ethyl, R 2 is methyl, ethyl, isopropyl or hydroxyethyl, and R 3 is methyl, ethyl, isopropyl or hydroxyethyl.
  • the tertiary amino absorption compound is an alkanolamine.
  • a process for treating a C0 2 containing gas comprising contacting the gas with an aqueous absorption solution comprising carbonic anhydrase and a tertiary amino absorption compound, wherein the concentrations of the carbonic anhydrase and tertiary amino absorption compound are selected to enhance the enzymatic catalysis and inhibit viscosifying of the absorption solution or enzyme denaturing that would lower the overall C0 2 absorption rate.
  • the ion lean solution has a lean C0 2 loading and comprises water and a tertiary amino compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly); contacting the C0 2 containing gas with the absorption solution in the presence of carbonic anhydrase or an analogue thereof, thereby producing a C0 2 depleted gas and an ion loaded solution that are released from the absorption unit, wherein the ion loaded solution has a rich C0 2 loading; supplying ion loaded solution to a desorption unit for producing a C0 2 stream and a regenerated solution; and recycling at least part of the regenerated solution as at least part of the ion lean solution supplied to the absorption unit.
  • DEMEA diethylmonoethanolamine
  • DMEA dimethylmonoethanolamine
  • DMgly dimethylglycine
  • the rich C0 2 loading of the ion loaded solution is between about 0.05 and about 1. In some scenarios, the lean CO 2 loading of the ion lean solution is between about 0 and about 0.2
  • absorption is conducted at a temperature between about 0oC and about 80oC.
  • absorption is conducted at a temperature between about 40oC and about 70oC.
  • absorption is conducted at a temperature between about 15oC and 35oC.
  • absorption is conducted at a temperature about 25oC.
  • the tertiary amino compound has a concentration of at least 1 M in the absorption solution.
  • the tertiary amino compound has a concentration of at least 2 M in the absorption solution.
  • the tertiary amino compound has a concentration of at least 3 M. in the absorption solution.
  • the tertiary amino compound has a concentration of at least 4 M in the absorption solution.
  • the carbonic anhydrase or analogue thereof is provided as part of the absorption solution at a concentration of at least 100 mg/L.
  • the carbonic anhydrase or analogue thereof is provided as part of the absorption solution at a concentration of at least 200 mg/L.
  • the carbonic anhydrase or analogue thereof is provided as part of the absorption solution at a concentration of at least 400 mg/L.
  • the carbonic anhydrase or analogue thereof is provided as part of the absorption solution at a concentration of at least 800 mg/L.
  • the tertiary amino and the carbonic anhydrase or analogue thereof are provided in concentrations sufficient to increase an overall forward reaction rate constant (k 0 v) by at least about 250 s -1 compared to a corresponding solution comprising N-methyl-diethanolamine (MDEA).
  • the tertiary amino and the carbonic anhydrase or analogue thereof are provided in concentrations sufficient to increase an overall forward reaction rate constant (k 0 v) by at least about 1250 s "1 compared to a corresponding solution comprising N-methyl-diethanolamine (MDEA).
  • MDEA N-methyl-diethanolamine
  • the tertiary amino and the carbonic anhydrase or analogue thereof are provided in concentrations sufficient to increase an overall forward reaction rate constant (k 0 v) by at least about 2500 s "1 compared to a corresponding solution comprising N-methyl-diethanolamine (MDEA).
  • MDEA N-methyl-diethanolamine
  • the process also comprising selecting the tertiary amino compound in accordance with the pKa thereof.
  • a process for absorbing C0 2 from a C0 2 containing gas comprising contacting the C0 2 containing gas with an absorption solution in the presence of carbonic anhydrase or an analogue thereof, the absorption solution comprising water and a tertiary amino compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly).
  • DEMEA diethylmonoethanolamine
  • DMEA dimethylmonoethanolamine
  • DMgly dimethylglycine
  • a method of enhancing enzymatic impact on C0 2 absorption comprising conducting enzymatically catalysed C0 2 absorption into a solution comprising a tertiary amine compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly)
  • DEMEA diethylmonoethanolamine
  • DMEA dimethylmonoethanolamine
  • DMgly dimethylglycine
  • a method of increasing C0 2 loading in a solution comprising providing a tertiary amine compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly) in the solution and contacting the solution with a C0 2 containing gas in the presence of carbonic anhydrase or an analogue thereof.
  • a tertiary amine compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly) for C0 2 absorption in the presence of carbonic anhydrase or an analogue thereof.
  • a formulation for absorbing C0 2 comprising water, carbonic anhydrase or an analogue thereof, and a tertiary amine compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly).
  • DEMEA diethylmonoethanolamine
  • DMEA dimethylmonoethanolamine
  • DMgly dimethylglycine
  • a formulation for absorbing C0 2 comprising water, carbonic anhydrase or an analogue thereof, and a tertiary amine compound having the formula R ⁇ NRa; wherein is selected from the group consisting of methyl, ethyl and propyl; R 2 is selected from the group consisting of methyl, ethyl and propyl; and R 3 is selected from the group consisting of 2-hydroxyethyl and carboxymethyl.
  • Ri and R 2 are the same or different. In some scenarios, Ri and R 2 are selected from the group consisting of methyl and ethyl.
  • the tertiary amine compound is selected form from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA), dimethylglycine (DMgly) and diethylglycine (DEgly).
  • the tertiary amine compound has a pKa of at least 8.8, at least 9, at least 9.2, or at least 9.7.
  • the ion loaded solution comprises water, bicarbonate and hydrogen ions and a tertiary amino compound selected from diethylmonoethanolamine (DEMEA), dimethylmonoethanolamine (DMMEA) and dimethylglycine (DMgly); providing carbonic anhydrase or an analogue thereof in the desorption unit in order to catalyze a dehydration reaction of the bicarbonate and hydrogen ions, thereby producing a C0 2 stream and a regenerated ion lean solution; and releasing the C0 2 stream and the regenerated ion lean solution from the desorption unit.
  • DEMEA diethylmonoethanolamine
  • DMEA dimethylmonoethanolamine
  • DMgly dimethylglycine
  • Fig 1 is a process block flow diagram.
  • Fig 2 is another process block flow diagram.
  • Fig 3 is a graph of C0 2 flux versus concentration for different compounds using enzyme or no enzyme.
  • Fig 4 is a graph of C0 2 flux ratio of enzyme over no enzyme, versus concentration for different compounds.
  • Fig 5 is a graph of overall kinetic rate constant as a function en enzyme concentration in MDEA solutions of 1 , 2, 3 and 4 M at 25 .
  • Fig. 6 is a graph of the overall kinetic rate constant as a function of enzyme concentration in TEA solutions of 1 , 2 and 4 M at 25
  • Fig 7 is a graph of the overall kinetic rate constant as a function of enzyme concentration in DMMEA solutions in 1 and 2 M at 25 ⁇ .
  • Fig 8 is a graph of the overall kinetic reaction rate constant as a function of the enzyme concentration in TIPA solutions at 1 and 2 M at 25°C.
  • Fig 9 is a graph of the overall kinetic rate constant as a function of enzyme concentration in DEMEA solution at 0.5, 1 and 2 M at 25 ⁇ .
  • Fig 10 is a graph of k ov versus enzyme concentration with 1 M of DMMEA.
  • Fig 11 is a graph of k ov versus enzyme concentration with 2 M of DMMEA.
  • Fig 12 is a graph of k ov versus enzyme concentration with different concentrations of DMMEA.
  • Fig 13 is another graph of k ov versus enzyme concentration with different compounds, TEA, MDEA and DMMEA.
  • Fig 14 is a graph of k ov versus pK a with different concentrations of absorption compounds, combined with 100 mg/L of carbonic anhydrase.
  • Fig 15 is a graph of k ov versus pK a with different concentrations of absorption compounds, combined with 200 mg/L of carbonic anhydrase.
  • Fig 16 is a graph of k ov versus pK a with different concentrations of absorption compounds, combined with 400 mg/L of carbonic anhydrase.
  • Fig 17 is a graph of k ov versus pK a with different concentrations of absorption compounds, combined with 800 mg/L of carbonic anhydrase.
  • Fig 18 is a diagram of a stirred cell contactor.
  • Fig 19 is a diagram illustrating phase transfer.
  • Fig 20 is a process flow diagram of an example C0 2 capture system including absorption and desorption stages.
  • Carbonic anhydrase is an enzyme known to catalyse C0 2 hydration through the following reaction:
  • the enzymatic C0 2 hydration rate increases with dissolved C0 2 concentration available in the liquid medium.
  • the reaction limiting step can be related to the H + release from the enzyme to the surrounding liquid medium.
  • One way of accelerating this step is to have present in the liquid medium a compound that will capture this ion such as a base or a buffer solution.
  • the enzymatic impact is higher. At low concentrations, the enzymatic impact may be less pronounced, while at higher concentrations there may be viscosifying or enzyme denaturing effects that can decrease the effectiveness of the enzymatic process. In some scenarios, there is a concentration range enabling enhanced enzymatic impact on the C0 2 capture process.
  • the tertiary alkanolamine and/or tertiary amine may be selected and provided in a concentration that provides an enzymatic enhancement of the C0 2 capture process and does not detrimentally viscosify the absorption solution such that the mass transfer and C0 2 capture rate would be decreased.
  • Tertiary compounds may be selected according to low viscosity characteristics at concentrations that provide enhanced enzymatic catalysis.
  • the present invention provides a carbonic anhydrase catalyzed C0 2 capture process utilizing an absorption solution including a tertiary amine or alkanolamine compound, where the concentration of the tertiary compound is provided in an optimal that enhances the enzymatic impact on absorption.
  • the concentration of the tertiary compound may be above 0.4 M.
  • the concentration of the tertiary compound may be between 0.4 M and 4 M.
  • the concentration may be between 0.75 and 2.5 M, or between 1 M and 2 M.
  • the present invention provides a carbonic anhydrase catalyzed C0 2 capture process utilizing an absorption solution including a tertiary amine or alkanolamine compound, where the concentrations of the carbonic anhydrase and/or the tertiary compound are high enough to enhance the enzymatic catalysis while not too high to cause viscosifying that would lower the overall C0 2 absorption rate.
  • the tertiary concentration may be from about 0.4 M to about 2 M.
  • the enzyme concentration may be sufficiently high to be at or near a maximum absorption rate per quantity of enzyme.
  • the enzyme concentration may be between 250 mg/L and 500 mg/L for an absorption solution including MDEA as a tertiary alkanolamine.
  • the enzyme concentration may be in a concentration range having a high slope of absorption rate versus enzyme concentration relationship.
  • one or more of the appended Figs 3 to 9 may be employed for determining or adjusting the enzyme and/or absorption compound concentration for a C0 2 capture system, in order to provide enhanced enzymatic catalysis of the absorption reaction and/or increase the overall absorption of the system.
  • an example of the overall C0 2 capture system 10 includes a source 12 of C0 2 containing gas 14.
  • the source may be a power plant, an aluminum smelter, refinery or another type of C0 2 producing operation.
  • the C0 2 containing gas 14 is supplied to an absorption unit 16, which is also fed with an aqueous absorption solution 18 for contacting the C0 2 containing gas 14.
  • the aqueous absorption solution 18 comprises carbonic anhydrase and an absorption compound, which may be a tertiary alkanolamine such as TEA and/or MDEA, but may also be other types of compounds which will be discussed further below.
  • the carbonic anhydrase may be free in the aqueous absorption solution 18 as dissolved enzyme or aggregate particles of enzymes.
  • the carbonic anhydrase may be on or in particles that are present in the aqueous absorption solution 18 and flow with it through the absorption unit 16.
  • the carbonic anhydrase may be immobilized with respect to the particles using any method while keeping at least some of its activity. Some immobilization techniques include covalent bonding, entrapment, and so on.
  • the carbonic anhydrase may be immobilized with respect to supports, which may be various structures such as packing material, within the absorption unit 16 so as to remain within the absorption unit 16 as the aqueous absorption solution 18 flows through it.
  • the absorption unit 16 may be various types, such as a packed reactor, a spray reactor or a bubble column type reactor. There may be one or more reactors that may be provided in series or in parallel.
  • the enzyme carbonic anhydrase catalyses the hydration reaction of C0 2 into bicarbonate and hydrogen ions and thus a C0 2 depleted gas 20 and an ion rich solution 22 are produced.
  • the ion rich solution 22 is then supplied to a desorption unit 26 to produce a C0 2 stream 28 and an ion depleted solution 30.
  • the ion rich solution 22 may be supplied to another type of regeneration step such as mineral carbonation.
  • the system 10 may also include a separation unit 32 arranged in between the absorption unit 16 and the desorption unit 26, for removing at least some and possibly all of the carbonic anhydrase in the event the enzyme is flowing with the ion rich solution 22, e.g. when the enzyme is free in solution or provided with respect to particles.
  • the separation unit 32 produces an enzyme depleted stream 34 that may be supplied to the desorption unit 26 and an enzyme rich stream 36 that may be recycled, in whole or in part, to the absorption unit 16.
  • the separation unit may also include one or more separators in series or parallel.
  • the separators may be filters or other types of separators, depending on the removal characteristics for the enzymes and the form of the enzymes or particles.
  • the system may also include various other treatment units for preparing the ion rich solution for the desorption unit and/or for preparing the ion deplete unit for recycling into the absorption unit.
  • treatment units for preparing the ion rich solution for the desorption unit and/or for preparing the ion deplete unit for recycling into the absorption unit.
  • There may be pH adjustment units or various monitoring units.
  • At least some carbonic anhydrase is provided in the desorption unit.
  • the carbonic anhydrase may be provided within the input ion rich solution or added separately.
  • the carbonic anhydrase may be tailored, designed, immobilised or otherwise delivered in order to withstand the conditions in the desorption unit.
  • the system may also include a measurement device for monitoring properties of various streams and adjusting operation of the absorption unit 16 to achieve desired properties. Adjusting could be done by various methods including modifying the liquid and/or gas flow rates, for example.
  • an overall C0 2 capture system and process 10a includes an absorption unit 12a and a desorption unit 14a.
  • the absorption unit 12a may include an absorber reactor 16a which receives a C0 2 -containing gas 18a that can come from a variety of sources.
  • the C0 2 -containing gas 18a is an effluent gas such as power plant flue gas, industrial exhaust gas, aluminum refining flue gas, aluminum smelting off-gas, steel production flue gas, chemical production flue gas, combustion gas from in-situ oil sands production etc.
  • the C0 2 -containing gas 18a includes or is a process gas stream such as raw or semi- processed natural gas, a hydrocarbon cracked gas (such as in ethylene production) or a carbon monoxide catalytic shift gas (such as in ammonia production).
  • the C0 2 -containing gas 18a is a naturally occurring gas such as ambient air.
  • the absorber reactor 16a also receives an absorption solution 20a (which may also be referred to as a "C0 2 -lean solution" herein).
  • the absorber reactor 16a the conversion of C0 2 into bicarbonate and hydrogen ions takes place in the presence of carbonic anhydrase or an analog thereof, thereby producing a C0 2 -depleted gas 22a and an ion-rich solution 24a.
  • the absorber reactor 16a is a direct-contact type reactor, such as a packed tower or spray scrubber or otherwise, allowing the gas and liquid phases to contact and mix together.
  • the ion-rich solution 24a may be pumped by a pump 26a to downstream parts of the process, such as heat exchangers, desorption units, regeneration towers and the like.
  • Part of the ion-rich solution 24a may be recycled back to the absorber reactor 16a via an ion-rich solution return line, which can improve mixing of the bottoms of the absorber reactor to avoid accumulation of precipitates and reactor deadzones, as the case may be.
  • the absorber 16a may also have other recycle or return lines, as desired, depending on operating conditions and reactor design.
  • the ion-rich solution 24a may then be fed to the desorption unit 14a, in which it can be regenerated and a C0 2 gas can be separated for sequestration, storage or various uses.
  • the ion-rich solution 24a is preferably heated, which may be done by one or more heat exchanger 32a, to favor the desorption process.
  • the heat exchanger may use heat contained in one or more downstream process streams in order to heat the ion-rich solution, e.g. ion-depleted solution 42a.
  • the heated ion-rich solution 34a is fed into a desorption reactor 36a.
  • carbonic anhydrase or analogs thereof may be present within the ion- rich solution 34a, allowing the carbonic anhydrase to flow with the ion-rich solution 34a while promoting the conversion of the bicarbonate ions into C0 2 gas 38a and generating an ion-depleted solution 40a.
  • the carbonic anhydrase could also be fixed or immobilized within reactors or particles passing within and/or through the reactors.
  • the enzymes could also be removed from the ion-rich stream prior to feeding it to the desorption reactor 36a.
  • the process also includes releasing the C0 2 gas 38a and the ion-depleted solution 40a from the desorption unit 14a and, preferably, sending a recycled ion-depleted solution 42a to make up at least part of the absorption solution 20a.
  • the ion-depleted solution 42a may be combined with a make-up stream 50a containing water, absorption compound and/or enzyme.
  • the ion-depleted solution 42a is preferably cooled prior to re-injection into the absorption unit, which may be done by the heat exchanger 32a.
  • the desorption reactor 36a may also include various recycle or return streams (not illustrated) as desired.
  • the desorption unit 14a may also include one or more reboilers each of which takes a fraction of the liquid flowing through a corresponding one of the desorption reactors and heats it to generate steam that will create a driving force such that C0 2 will be further released from the solution.
  • absorption is performed around ⁇ - ⁇ , optionally 40'C- 70 , and desorption around 60 -180 , optionally 70 -150 .
  • absorption may be performed between ⁇ 5 and 35 to favor enz ymatic activity in some scenarios, although this may depend on the characteristics and stability of the given CA enzyme that may be used.
  • the absorption unit may be a packed tower, a spray reactor or a bubble column depending on the application and design considerations.
  • the enzyme is provided directly as part of a formulation or solution.
  • the carbonic anhydrase or analogue thereof may be in a free or soluble state in the formulation or immobilised on or in particles or as aggregates, chemically modified or stabilized, within the formulation.
  • enzyme used in a free state may be in a pure form or may be in a mixture including impurities or additives such as other proteins, salts and other molecules coming from the enzyme production process.
  • Immobilized enzyme free flowing in the solutions could be entrapped inside or fixed to a porous coating material that is provided around a support that is porous or non-porous.
  • the enzymes may be immobilised directly onto the surface of a support (porous or non-porous) or may be present as cross linked enzyme aggregates (CLEAs) or cross linked enzyme crystals (CLECs).
  • CLEA include precipitated enzyme molecules forming aggregates that are then cross-linked using chemical agents.
  • the CLEA may or may not have a 'support' or 'core' made of another material which may or may not be magnetic.
  • CLEC include enzyme crystals and cross linking agent and may also be associated with a 'support' or 'core' made of another material.
  • a support it may be made of polymer, ceramic, metal(s), silica, solgel, chitosan, cellulose, alginate, polyacrylamide, magnetic particles and/or other materials known in the art to be suitable for immobilization or enzyme support.
  • the enzymes are immobilised or provided on particles, such as micro-particles, the particles are preferably sized and provided in a particle concentration such that they are pumpable with the solution throughout the process.
  • the micro-particles may be sized in a number of ways.
  • the absorption compound may include a tertiary alkanolamine, such as Triethanolamine (TEA), N-Methyldiethanolamine (MDEA), Diethyl- monoethanolamine (DEMEA) and/or Dimethyl-monoethanolamine (DMMEA).
  • TEA Triethanolamine
  • MDEA N-Methyldiethanolamine
  • DEMEA Diethyl- monoethanolamine
  • DMEA Dimethyl-monoethanolamine
  • Other tertiary amino compounds may also be used (and may or may not be alkanolamines having an alcohol group) such as the tertiary amine Triisopropylamine (TIPA).
  • the tertiary alkanolamine may have the structure NR ⁇ Rs, where Ri is selected from hydroxyethyl, isopropyl, methyl or ethyl, R 2 is selected from methyl, ethyl, isopropyl or hydroxyethyl and R 3 is selected from methyl, ethyl, isopropyl or hydroxyethyl.
  • Ri is selected from hydroxyethyl, isopropyl, methyl or ethyl
  • R 2 is selected from methyl, ethyl, isopropyl or hydroxyethyl
  • R 3 is selected from methyl, ethyl, isopropyl or hydroxyethyl.
  • Tertiary amines and alkanolamines may be seen as examples of slow absorption compounds since they do not react with C0 2 as primary and secondary amines and/or alkanolamines.
  • the absorption solution may include certain tertiary amino compounds, such as diethylmonoethanolamine (also known as diethylethanolamine and abbreviated as “DEMEA” or “DEEA”), dimethylmonoethanolamine (also known as dimethylethanolamine and abbreviated as “DMMEA” or “DMEA”) and/or dimethylglycine (abbreviated as "DMG” or “DMgly”).
  • DEMEA diethylethanolamine
  • DEEA dimethylmonoethanolamine
  • DMG dimethylglycine
  • DMMEA, DEMEA and DMgly also have lower pKa properties than MDEA and TEA.
  • the catalyzing effect of carbonic anhydrase was observed to be generally dependent on the pKa of the alkanolamine in solution, increasing with increasing pKa as observed in the order DMMEA > MDEA > TEA, for example.
  • the tertiary amino compound has the formula R 4 R 5 NR 6 , where R 4 is selected from the group consisting of methyl, ethyl and propyl; R 5 is selected from the group consisting of methyl, ethyl and propyl; and R 6 is selected from the group consisting of 2-hydroxyethyl and carboxym ethyl.
  • R 4 and R 5 may be the same or different and in some examples may be selected from the group consisting of methyl and ethyl.
  • tertiary amino compounds that may be used include diethylglycine (abbreviated as "DEGly”)
  • the absorption solution may also include further chemical additives in addition to the tertiary amino compound.
  • the absorption solution may further include a chemical additive selected from a primary amine, a secondary amine, an additional tertiary amine, a primary alkanolamine, a secondary alkanolamine, an additional tertiary alkanolamine, a primary amino acid, a secondary amino acid, an additional tertiary amino acid, or a carbonate compound, or a combination thereof.
  • the chemical additive may include at least one of the following: piperidine, piperazine, derivatives of piperidine or piperazine which are substituted by at least one alkanol group, monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(2- aminoethylamino)ethanol (AEE), 2-amino-2-hydroxymethyl-1 ,3-propanediol (TRIS), N- methyldiethanolamine (MDEA), triisopropanolamine (TI PA), triethanolamine (TEA), dialkylether of polyalkylene glycols, dialkylether or dimethylether of polyethylene glycol, glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, valine, leucine, isoleucine, alanine, valine, tyrosine, tryp
  • the "theoretical cyclic capacity" and the “real cyclic capacity” are concepts that can be related to C0 2 capture processes.
  • Theoretical cyclic capacity is the difference between the lean and rich C0 2 loadings of the absorption solution when chemical equilibrium is reached.
  • Lean C0 2 loading is the loading of the C0 2 -lean solution 20 entering the absorption unit 12 while the rich C0 2 loading is the loading of the ion-rich solution 24 leaving the absorption unit 12.
  • Real cyclic capacity is the difference between the lean and rich C0 2 loadings of the absorption solution obtained under process conditions. Real cyclic capacity is lower than the theoretical cyclic capacity since chemical equilibrium conditions are not practically reached during process conditions, due to requiring a continued driving force for example.
  • Carbonic anhydrase is an efficient catalyst that enhances the reversible reaction of C0 2 to HC0 3 " .
  • Carbonic anhydrase is not just a single enzyme form, but a broad group of metalloproteins that exists in three genetically unrelated families of isoforms, ⁇ , ⁇ and ⁇ .
  • Carbonic anhydrase (CA) is present in and may be derived from animals, plants, algae, bacteria, etc.
  • the human variant CA II, located in red blood cells, is the most studied and has a high catalytic turnover number.
  • the carbonic anhydrase includes any analogue, fraction and variant thereof and may be alpha, gamma or beta type from human, bacterial, fungal or other organism origins, having thermostable or other stability properties, as long as the carbonic anhydrase can be provided to function in the C0 2 absorption and/or desorption processes to enzymatically catalyse the reaction:
  • carbonic anhydrase added to an absorption solution having slow kinetics results in an increased C0 2 absorption rate and can help a system to reach a real cyclic capacity which is closer to the theoretical cyclic capacity. This is achieved because carbonic anhydrase increases the C0 2 reaction rate in the solution, leading to an increased C0 2 absorption rate into the solution and hence a higher C0 2 concentration in the solution which can also be expressed as C0 2 loading.
  • Using carbonic anhydrase in an absorption unit can enable a higher C0 2 loading of the absorption solution, in the case where equilibrium is not reached without the enzyme under the same operating conditions, and a corresponding increase in the real cyclic capacity.
  • CO 2 loading of an absorption solution means the CO 2 concentration in the solution in the forms of carbonate ions, bicarbonate ions and dissolved CO 2 per mole of absorption compound.
  • reaction rate may be formulated as follows:
  • reaction rate may be formulated as follows:
  • reaction rate may be formulated as follows:
  • reaction rate may be formulated as follows:
  • the overall forward reaction rate constant, k ov is determined by the contributions of each of these four reactions, whose kinetic rate expression is usually given as follows:
  • carbonic anhydrase and analogues thereof may include naturally occurring, modified or evolved carbonic anhydrase enzymes; and analogues thereof may be variants or non-biological small molecules that are naturally occurring or synthesized to achieve or mimic the effect of the enzyme.
  • Tests were performed to compare the effect of carbonic anhydrase on C0 2 flux using with solutions including three different absorption compounds, namely TRIS, TEA and MDEA, at different concentrations.
  • the enzyme concentration was constant at 0.2 g/L for all tests.
  • Fig 3 shows the results of some comparative tests.
  • the tertiary alkanolamines, TEA and MDEA provide higher C0 2 flux compared to TRIS at the higher concentrations of 1 M and 2 M.
  • Fig 4 shows the flux ratio of the three compounds over the concentrations and the tertiary alkanolamines, TEA and MDEA, provide higher enzymatic C0 2 flux ratios compared to TRIS over the concentrations, the trend being particularly pronounced at the higher concentrations of 1 M and 2 M.
  • the enzyme enhanced C0 2 flux for TEA is at least 6 times greater for all concentrations compared to no enzyme.
  • the enzyme enhanced C0 2 flux for MDEA is at least 6 times greater for concentrations estimated above about 0.4 compared to no enzyme; and enzyme enhanced C0 2 flux for MDEA is around 10 or more times greater for concentrations of 1 or 2 M compared to no enzyme.
  • Figs 3 and 4 were obtained from a comparative study including tests that were performed in a 160 mL-stirred cell reactor (Parr).
  • An absorption solution with a specific concentration of a C0 2 absorption compound (MDEA, Tris or TEA), was added into the stirred cell reactor.
  • Carbonic anhydrase was added to reach an enzyme concentration of 0.2 g/L.
  • C0 2 was injected into the stirred cell reactor to reach an initial pressure level of 10 psi.
  • Temperature of the system was 25'C.
  • Stirring conditions were adjusted to maintain a flat liquid-gas interface. The liquid and gas phases were stirred.
  • C0 2 flux across the gas-liquid interface was determined and the data is presented in the Figs.
  • the tertiary alkanolamines have a different response in a carbonic anhydrase enhanced C0 2 capture system at certain conditions, compared to the primary sterically hindered alkanolamine.
  • Tris is a sterically hindered primary alkanolamine.
  • the primary and secondary alkanolamines undergo a fast direct reaction with C0 2 which makes the rate of carbon dioxide absorption rapid.
  • MDEA which is a tertiary alkanolamine, is a compound that does not react directly with C0 2 , since the formation of the above described carbamate moiety is not possible.
  • the molecular structure of MDEA is as follows:
  • MDEA does not compete with C0 2 for reaction and therefore the impact of the enzyme on catalysis is maximized and improved relative to compounds that do compete for reaction with C0 2 such as Tris.
  • the enzymatic enhancement on the C0 2 flux may have an optimal range for tertiary alkanolamines, as evidenced in Fig 4, which shows that the MDEA and TEA curves both have a peak with a maximum at approximately 1.25 M and 1 M respectively, while the TRIS results show a steady decline in the C0 2 flux ratio of enzyme versus no enzyme.
  • tertiary alkanolamines in a concentration range between about 0.4 M to about 2 M for C0 2 absorption, or between about 0.75 M and about 1.75 M, for example.
  • concentration ranges between about 0.4 M to about 2 M for C0 2 absorption, or between about 0.75 M and about 1.75 M, for example.
  • different absorption compound concentration ranges may be used.
  • Tests were performed to evaluate the impact of the concentration of carbonic anhydrase on the C0 2 reaction rate in different tertiary amine solutions. Tests were conducted using a stirred cell. In a typical experiment a tertiary amine solution with desired concentration was prepared by dissolving a known amount of the amine in a known amount water together with a known amount of enzyme solution (human carbonic anhydrase (hCA II) or a thermostable variant of hCA II. Approximately 500 ml of the solution was transferred to the reactor, where inerts were removed by applying vacuum for a short time. Next, the solution was allowed to equilibrate at 298 K before its vapour pressure was recorded.
  • enzyme solution human carbonic anhydrase (hCA II) or a thermostable variant of hCA II.
  • C0 2 gas is introduced in the reactor at a known pressure, liquid agitation in started and C0 2 is absorbed into the solution.
  • the C0 2 pressure is monitored and used to calculate the C0 2 absorption rate.
  • C0 2 absorption data are used to calculate the C0 2 reaction rate in the tertiary amine solution.
  • This reaction rate is the sum of the reaction rate of the reaction between C0 2 and the tertiary amine and the reaction rate of C0 2 hydration reaction catalysed by carbonic anhydrase.
  • Tests were conducted with tertiary amines MDEA, TEA, TIPA, DEMEA, DMMEA at different concentrations ranging from 0.5 to 4M depending on the tertiary amine tested. Enzyme concentrations ranging from 0.05 to 2.2 g/L.
  • the C0 2 reaction in a MDEA solution is a pseudo-first order reaction where the overall reaction rate is governed by the following equation:
  • k ov is the overall pseudo-first order kinetic constant (s "1 ) and C C o2 is the C0 2 concentration in mol/L.
  • the kinetic constant k ov is defined as:
  • C M DEA is the MDEA concentration in mol/m 3 and k 2 is the kinetic constant for the reaction of C0 2 in a MDEA solution.
  • TEA is a more viscosifying compound in aqueous solutions than MDEA.
  • This enhanced enzymatic effect on the reaction rate may be leveraged in various ways. For instance, it may be used to design smaller absorption units; to provide higher flow rates of absorption solution through a given absorption unit to achieve similar C0 2 loadings as a lower flow rate without enzymes; to increase the real cyclic capacity for an existing C0 2 absorption system; and so on.

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Abstract

Les techniques destinées à traiter un gaz contenant du CO2 ci-décrites comprennent la mise en contact du gaz avec une solution d'absorption aqueuse contenant une anhydrase carbonique ainsi qu'un composé d'absorption, qui peut être un composé amino tertiaire pour obtenir un flux de CO2 amélioré par l'enzyme. Le composé d'absorption peut comprendre une MDEA, TEA, DEMEA, DMMEA, TIPA ou DMgly, par exemple. Les techniques selon l'invention peuvent fournir des concentrations pour améliorer la catalyse enzymatique et inhiber la viscosification de la solution d'absorption ou la dénaturation de l'enzyme qui abaisserait le taux d'absorption global du CO2. L'absorption peut être mise en œuvre à une température comprise entre environ 0 et environ 80°C, par exemple. Des procédés, des utilisations et des formulations pour une capture améliorée du CO2 sont également décrits.
PCT/CA2013/050314 2012-04-24 2013-04-23 Capture de co2 à l'aide d'une anhydrase carbonique et de solvants amino tertiaires pour un rapport de flux amélioré WO2013159228A1 (fr)

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CN201380033637.4A CN104602789A (zh) 2012-04-24 2013-04-23 用碳酸酐酶和用于增强通量比的叔氨基溶剂的co2捕获

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EP3620225A1 (fr) 2018-08-29 2020-03-11 INDIAN OIL CORPORATION Ltd. Procédé de capture de co2 à partir de flux gazeux
CN115957820A (zh) * 2022-12-21 2023-04-14 广西大学 一种多重氨基酸修饰zif-8的仿生酶材料的制备方法与应用

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WO2015126925A1 (fr) * 2014-02-18 2015-08-27 Akermin, Inc. Processus et procédés de capture de dioxyde de carbone avec une faible énergie
EP3620225A1 (fr) 2018-08-29 2020-03-11 INDIAN OIL CORPORATION Ltd. Procédé de capture de co2 à partir de flux gazeux
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