WO2013067648A1 - Co2 capture with carbonic anhydrase and membrane filtration - Google Patents

Co2 capture with carbonic anhydrase and membrane filtration Download PDF

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Publication number
WO2013067648A1
WO2013067648A1 PCT/CA2012/050802 CA2012050802W WO2013067648A1 WO 2013067648 A1 WO2013067648 A1 WO 2013067648A1 CA 2012050802 W CA2012050802 W CA 2012050802W WO 2013067648 A1 WO2013067648 A1 WO 2013067648A1
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Prior art keywords
absorption
membrane
carbonic anhydrase
stage
desorption
Prior art date
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PCT/CA2012/050802
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French (fr)
Inventor
Geert Frederik Versteeg
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Co2 Solutions Inc.
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Publication date
Application filed by Co2 Solutions Inc. filed Critical Co2 Solutions Inc.
Priority to EP12846957.4A priority Critical patent/EP2776143A4/en
Publication of WO2013067648A1 publication Critical patent/WO2013067648A1/en

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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
    • 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
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • 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
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
    • 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 C02 capture and more particularly to the field of enzymatically enhanced C02 capture.
  • Carbonic anhydrase has been used for enhancing absorption of C02 from C02 containing gases by catalyzing the hydration reaction of C02 into bicarbonate and hydrogen ions.
  • Carbonic anhydrase may be provided according to various delivery methods, such as immobilized on packing material, dissolved in solution, or immobilized on particles flowing with liquid through the system.
  • Absorption compounds have also been used for C02 capture.
  • Absorption compounds such as amines, can be used in combination with water to provide aqueous solvents for absorbing C02 from C02 containing gases.
  • aqueous solvents may be used in a two stage absorption-desorption system for capturing C02.
  • hybrid solvents including carbonic anhydrase, an absorption compound and water can also be used for absorption of C02 from C02 containing gases.
  • there is a process for treating a C02 containing gas comprising: contacting the C02 containing gas with a hybrid solvent comprising carbonic anhydrase, water and an absorption compound, at a low absorption temperature, to produce a C02 depleted gas and an ion loaded solution; subjecting the ion loaded solution to membrane filtering to produce an enzyme deplete ion loaded solution and an enzyme component; heat treating the enzyme deplete ion loaded solution to produce a heated ion loaded solution; subjecting the heated ion loaded solution to desorption, at a high desorption temperature, to produce a C02 stream and a regenerated solution; cooling the regenerated solution to produce a cooled regenerated solution; and recycling the cooled regenerated solution and at least some of the enzyme component back for absorption.
  • the carbonic anhydrase are heat degradable above 40C.
  • the low absorption temperature is 35-45C.
  • the high desorption temperature is 105-120.
  • the difference between the low absorption temperature and the high desorption temperature is between 60-85C.
  • the absorption compound comprises an amine.
  • the membrane filtration comprises nano-filtration.
  • the membrane filtration uses pores or pore layers below 15 nm in diameter.
  • the membrane filtration uses pores with an average pore diameter of 1 -5 nm.
  • the absorption compound is selected and provided to enable an aggressive hybrid solvent.
  • the membrane filtration uses membranes that are resistant to aggressive and/or heated solvents.
  • the membrane comprises polyethersulfone (PES). In some implementations, the membrane comprises polyethersulfone (PES) with a separating layer of sulfonated polyethersulfone (SPES).
  • PES polyethersulfone
  • SPES sulfonated polyethersulfone
  • the membrane comprises a mixture of PES and SPES.
  • the membrane comprise hollow fibers utilizing inside/out filtration.
  • the process comprises operating the membrane filtration by periodically changing flow direction relative to the membrane to enable opposite filtration direction.
  • the carbonic anhydrase have a molecular mass of 5-50 kiloDaltons.
  • the membrane and the carbonic anhydrase are provided such that the pore size to molecular mass ratio is 0.02 nm/kilodalton - 3 nm/kilodalton.
  • the process includes providing an enzyme carbonic anhydrase concentration for absorption so as to enhance efficiency of the process.
  • the cooled regenerated solution and at least some of the enzyme component are combined prior to recycling to absorption as at least part of the hybrid solvent.
  • the process includes operating the desorption such that enzymatic acceleration of the dehydration reaction would have a negligible effect on process efficiency.
  • there is a method for C02 capture comprising: operating a C02 capture system comprising an absorption stage and a desorption stage operated with a large temperature swing in between the absorption stage and the desorption stage; utilizing a hybrid solvent comprising water, carbonic anhydrase and an absorption compound in the absorption stage for absorbing C02 out of a C02 containing gas; membrane filtering the carbonic anhydrase out of the hybrid solvent in between the absorption stage and the desorption stage and prior to the large temperature swing; and recycling the filtered carbonic anhydrase back into the absorption stage to maintain high enzyme concentration in the absorption stage.
  • the above method may also include one or more features as mentioned above or herein.
  • Fig 1 is a system diagram. DETAILED DESCRIPTION
  • the C02 capture system 10 may include an absorber 12 and a regenerator also referred to as a desorber 14.
  • the C02 containing gas 16 and the hybrid solvent 18 enter the absorber 12 to produce C02 depleted gas 20 and an ion loaded solution 22.
  • the ion loaded solution also includes carbonic anhydrase and is supplied to a membrane filtration device 24, which produces an enzyme depleted stream 26 and an enzyme fraction 28.
  • the enzyme fraction is recycled at least in part to the absorber 12, and the enzyme depleted stream undergoes a temperature swing, optionally by heating the stream in a heater 30 and then supplying the heated stream into the desorber 14.
  • the desorber 14 produces a C02 stream 32 and a regenerated solution 34 that may be cooled, operationally by the same heat exchanger 30.
  • Carbonic anhydrase that accelerate the absorption of C02 in water may be found naturally in living organisms. Some carbonic anhydrase may not be resistant to high temperatures used in various C02 absorption-desorption systems and are thus susceptible to heat degradataion, for example at temperatures above 40C. While some work has been conducted into developing heat stable enzymes, operation of such enzymes at high temperatures such as 105-120C has proven quite difficult.
  • the absorption stage may be operated at 35-45C and the regeneration stage may be operated at 105-120C so as to promote the function of the absorption compound, for example one or more various amines.
  • the process includes a membrane filtration step to filter out the carbonica anhydrase before the ion loaded solution is supplied to the regeneration stage. The filtered enzyme may then be recycled back into the absorption stage.
  • there is a method of capturing carbon dioxide includes the steps:
  • an enzyme based hybrid C0 2 capturing process for capturing carbon dioxide may include includes:
  • nano-filtration membrane means for filtering the accelerating enzymes from the reactive components of the hybrid C02 capturing process before thermal swing desorption
  • thermo swing desorption means for desorption of the absorbed carbon dioxide.
  • the reactive solutions may be classic mildly reactive solutions.
  • the method may increase process efficiency.
  • the method may reduce degradation of the enzymes.
  • the step of filtering of the enzymes may occur with a typical molecular mass of 5-50 kilo Dalton.
  • the method may include the step of recycling of the filtered enzymes to the reactive solutions to increase the concentrations of enzymes in the hybrid absorber to enhance C0 2 absorption.
  • the filtration membranes may preferably have pore sizes below 15 nanometer.
  • the filtration membranes may typically have average pore sizes between 1 -5 nanometer.
  • Nano-filtration membranes made of Polyethersulfone (PES) combined with a separating layer of Sulfonated polyethersulfone (SPES) and/or membranes based on mixtures of PES and SPES may be included. Hollow fiber nano-filtration membranes optimized to filter inside/out may be included.
  • an enzyme based hybrid C0 2 capturing process for capturing carbon dioxide in accordance with the invention may include:
  • nano-filtration membrane means for filtering the accelerating enzymes from the reactive components of the hybrid C02 capturing process before thermal swing desorption
  • thermo swing desorption means for desorption of the absorbed carbon dioxide.
  • the method(s) of capturing carbon dioxide for enzyme based hybrid C0 2 capturing processes in accordance with the invention include the introduction of filtration membranes (typically nano-filtration) to filter out the enzymes before the solvent is entering the regeneration phase of the C0 2 capturing process and to recycle the concentrated enzyme containing filtrate to the absorption part of the C02 capturing process. In this way the enzymes are protected against thermal shock and enzyme degradation will be limited significantly or even totally prevented.
  • filtration membranes typically nano-filtration
  • membrane filtration is advantageous for this type of hybrid reactive and enzyme based solvent processes.
  • the use of nano-filtration membranes is foreseen as these membranes will give typically the best overall performance in filtration versus filtration backpressure required to filter the solvent.
  • Membranes with separating pores or pore layers of diameter ⁇ 15 nanometer (nm) are useful, specifically nano-filtration membranes with average separating pore diameter of between 1 and 5 nanometer are preferred.
  • the solvent is typically aggressive for standard nano-filtration membranes used in water based filtration processes. At the same time, significant membrane filtration area is required to allow for efficient solvent filtration. Preferred nano-membranes need to be cost effective and resistant to aggressive heated solvents. It was found that nano-filtration membranes based Polyethersulfone (PES) combined with a separating layer of Sulfonated polyethersulfone (SPES) or membranes based on mixtures of PES and SPES provide good enzyme filtration properties and good chemical resistance against hybrid reactive C02 absorption solvents. Furthermore, it has been found that hollow fiber membranes optimized for filtration inside/out show benefits over membranes produced for opposite filtration direction.
  • PES Polyethersulfone
  • SPES Sulfonated polyethersulfone
  • there is a process including: contacting the C02 containing gas with a hybrid solvent comprising carbonic anhydrase, water and an absorption compound, at a low absorption temperature, to produce a C02 depleted gas and an ion loaded solution; subjecting the ion loaded solution to membrane filtering to produce an enzyme deplete ion loaded solution and an enzyme component; heat treating the enzyme deplete ion loaded solution to produce a heated ion loaded solution; subjecting the heated ion loaded solution to desorption, at a high desorption temperature, to produce a C02 stream and a regenerated solution; cooling the regenerated solution to produce a cooled regenerated solution; and recycling the cooled regenerated solution and at least some of the enzyme component back for absorption.
  • there is a process including: operating a C02 capture system comprising an absorption stage and a desorption stage operated with a large temperature swing in between the absorption stage and the desorption stage; utilizing a hybrid solvent comprising water, carbonic anhydrase and an absorption compound in the absorption stage for absorbing C02 out of a C02 containing gas; membrane filtering the carbonic anhydrase out of the hybrid solvent in between the absorption stage and the desorption stage and prior to the large temperature swing; and recycling the filtered carbonic anhydrase back into the absorption stage to maintain high enzyme concentration in the absorption stage.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)

Abstract

The method for CO2 capture includes operating a CO2 capture system with a large temperature swing in between the absorption stage and the desorption stage; utilizing a hybrid solvent comprising water, carbonic anhydrase and an absorption compound in the absorption stage; membrane filtering the carbonic anhydrase out of the hybrid solvent in between the absorption stage and the desorption stage and prior to the large temperature swing; and recycling the filtered carbonic anhydrase back into the absorption stage to maintain high enzyme concentration in the absorption stage.

Description

C02 CAPTURE WITH CARBONIC ANHYDRASE AND MEMBRANE FILTRATION
TECHNICAL FIELD
The present invention generally relates to the field of C02 capture and more particularly to the field of enzymatically enhanced C02 capture.
BACKGROUND
Carbonic anhydrase has been used for enhancing absorption of C02 from C02 containing gases by catalyzing the hydration reaction of C02 into bicarbonate and hydrogen ions. Carbonic anhydrase may be provided according to various delivery methods, such as immobilized on packing material, dissolved in solution, or immobilized on particles flowing with liquid through the system.
Absorption compounds have also been used for C02 capture. Absorption compounds, such as amines, can be used in combination with water to provide aqueous solvents for absorbing C02 from C02 containing gases. Such aqueous solvents may be used in a two stage absorption-desorption system for capturing C02.
In addition, hybrid solvents including carbonic anhydrase, an absorption compound and water can also be used for absorption of C02 from C02 containing gases.
There are various challenges related to the employment of hybrid solvents for C02 capture operations.
SUMMARY OF INVENTION
In some implementations, there is a process for treating a C02 containing gas comprising: contacting the C02 containing gas with a hybrid solvent comprising carbonic anhydrase, water and an absorption compound, at a low absorption temperature, to produce a C02 depleted gas and an ion loaded solution; subjecting the ion loaded solution to membrane filtering to produce an enzyme deplete ion loaded solution and an enzyme component; heat treating the enzyme deplete ion loaded solution to produce a heated ion loaded solution; subjecting the heated ion loaded solution to desorption, at a high desorption temperature, to produce a C02 stream and a regenerated solution; cooling the regenerated solution to produce a cooled regenerated solution; and recycling the cooled regenerated solution and at least some of the enzyme component back for absorption.
In some implementations, the carbonic anhydrase are heat degradable above 40C.
In some implementations, the low absorption temperature is 35-45C.
In some implementations, the high desorption temperature is 105-120.
In some implementations, the difference between the low absorption temperature and the high desorption temperature is between 60-85C.
In some implementations, the absorption compound comprises an amine.
In some implementations, the membrane filtration comprises nano-filtration.
In some implementations, the membrane filtration uses pores or pore layers below 15 nm in diameter.
In some implementations, the membrane filtration uses pores with an average pore diameter of 1 -5 nm.
In some implementations, the absorption compound is selected and provided to enable an aggressive hybrid solvent.
In some implementations, the membrane filtration uses membranes that are resistant to aggressive and/or heated solvents.
In some implementations, the membrane comprises polyethersulfone (PES). In some implementations, the membrane comprises polyethersulfone (PES) with a separating layer of sulfonated polyethersulfone (SPES).
In some implementations, the membrane comprises a mixture of PES and SPES.
In some implementations, the membrane comprise hollow fibers utilizing inside/out filtration.
In some implementations, the process comprises operating the membrane filtration by periodically changing flow direction relative to the membrane to enable opposite filtration direction.
In some implementations, the carbonic anhydrase have a molecular mass of 5-50 kiloDaltons.
In some implementations, the membrane and the carbonic anhydrase are provided such that the pore size to molecular mass ratio is 0.02 nm/kilodalton - 3 nm/kilodalton.
In some implementations, the process includes providing an enzyme carbonic anhydrase concentration for absorption so as to enhance efficiency of the process.
In some implementations, the cooled regenerated solution and at least some of the enzyme component are combined prior to recycling to absorption as at least part of the hybrid solvent.
In some implementations, the process includes operating the desorption such that enzymatic acceleration of the dehydration reaction would have a negligible effect on process efficiency.
In some implementations, there is a method for C02 capture, comprising: operating a C02 capture system comprising an absorption stage and a desorption stage operated with a large temperature swing in between the absorption stage and the desorption stage; utilizing a hybrid solvent comprising water, carbonic anhydrase and an absorption compound in the absorption stage for absorbing C02 out of a C02 containing gas; membrane filtering the carbonic anhydrase out of the hybrid solvent in between the absorption stage and the desorption stage and prior to the large temperature swing; and recycling the filtered carbonic anhydrase back into the absorption stage to maintain high enzyme concentration in the absorption stage.
The above method may also include one or more features as mentioned above or herein.
BRIEF DESCRIPTION OF DRAWINGS
Fig 1 is a system diagram. DETAILED DESCRIPTION
Referring to Fig 1 , the C02 capture system 10 may include an absorber 12 and a regenerator also referred to as a desorber 14. The C02 containing gas 16 and the hybrid solvent 18 enter the absorber 12 to produce C02 depleted gas 20 and an ion loaded solution 22. The ion loaded solution also includes carbonic anhydrase and is supplied to a membrane filtration device 24, which produces an enzyme depleted stream 26 and an enzyme fraction 28. The enzyme fraction is recycled at least in part to the absorber 12, and the enzyme depleted stream undergoes a temperature swing, optionally by heating the stream in a heater 30 and then supplying the heated stream into the desorber 14. The desorber 14 produces a C02 stream 32 and a regenerated solution 34 that may be cooled, operationally by the same heat exchanger 30.
Carbonic anhydrase that accelerate the absorption of C02 in water may be found naturally in living organisms. Some carbonic anhydrase may not be resistant to high temperatures used in various C02 absorption-desorption systems and are thus susceptible to heat degradataion, for example at temperatures above 40C. While some work has been conducted into developing heat stable enzymes, operation of such enzymes at high temperatures such as 105-120C has proven quite difficult.
In some embodiments, the absorption stage may be operated at 35-45C and the regeneration stage may be operated at 105-120C so as to promote the function of the absorption compound, for example one or more various amines. In some embodiments, the process includes a membrane filtration step to filter out the carbonica anhydrase before the ion loaded solution is supplied to the regeneration stage. The filtered enzyme may then be recycled back into the absorption stage.
In some implementations, there is a method of capturing carbon dioxide includes the steps:
(a) of absorbing carbon dioxide in an enzyme based hybrid C02 capturing process by means of reactive solutions and accelerating enzymes;
(b) of filtering the accelerating enzymes from the reactive components of the hybrid C02 capturing process by means of nano-filtration membranes before thermal swing desorption; and
(c) of thermal swing desorption of the absorbed carbon dioxide operated with a high accelerating enzyme concentration.
In some implementations, an enzyme based hybrid C02 capturing process for capturing carbon dioxide may include includes:
(a) absorption means for absorbing carbon dioxide by means of reactive solutions and accelerating enzymes;
(b) nano-filtration membrane means for filtering the accelerating enzymes from the reactive components of the hybrid C02 capturing process before thermal swing desorption; and
(c) thermal swing desorption means for desorption of the absorbed carbon dioxide.
The reactive solutions may be classic mildly reactive solutions. The method may increase process efficiency. The method may reduce degradation of the enzymes. The step of filtering of the enzymes may occur with a typical molecular mass of 5-50 kilo Dalton. The method may include the step of recycling of the filtered enzymes to the reactive solutions to increase the concentrations of enzymes in the hybrid absorber to enhance C02 absorption. The filtration membranes may preferably have pore sizes below 15 nanometer. The filtration membranes may typically have average pore sizes between 1 -5 nanometer. Nano-filtration membranes made of Polyethersulfone (PES) combined with a separating layer of Sulfonated polyethersulfone (SPES) and/or membranes based on mixtures of PES and SPES may be included. Hollow fiber nano-filtration membranes optimized to filter inside/out may be included.
In some implementations, an enzyme based hybrid C02 capturing process for capturing carbon dioxide in accordance with the invention may include:
(a) absorption means for absorbing carbon dioxide by means of reactive solutions and accelerating enzymes;
(b) nano-filtration membrane means for filtering the accelerating enzymes from the reactive components of the hybrid C02 capturing process before thermal swing desorption; and
(c) thermal swing desorption means for desorption of the absorbed carbon dioxide.
In some implementations, the method(s) of capturing carbon dioxide for enzyme based hybrid C02 capturing processes in accordance with the invention, include the introduction of filtration membranes (typically nano-filtration) to filter out the enzymes before the solvent is entering the regeneration phase of the C02 capturing process and to recycle the concentrated enzyme containing filtrate to the absorption part of the C02 capturing process. In this way the enzymes are protected against thermal shock and enzyme degradation will be limited significantly or even totally prevented.
Although, enzymes are also showing benefit in desorbing C02 from water, this property may be of minor significance in hybrid reactive solvents in the case that the bond of C02 in the solvent is too strong to be easily broken or released by the enzyme and mass transfer is not limiting the process for the release of C02. It is therefore found that removing enzymes from the hybrid reactive solvent before solvent regeneration may be done without negative effect on the performance of C02 desorption.
Recycling filtered enzymes to the hybrid reactive solvent to concentration up to several grams per liter of hybrid solvent enhances C02 absorption significantly as absorption often is often mass transfer limited.
The methods including membrane filtration is advantageous for this type of hybrid reactive and enzyme based solvent processes. Especially, the use of nano-filtration membranes is foreseen as these membranes will give typically the best overall performance in filtration versus filtration backpressure required to filter the solvent. Membranes with separating pores or pore layers of diameter < 15 nanometer (nm) are useful, specifically nano-filtration membranes with average separating pore diameter of between 1 and 5 nanometer are preferred.
As the used solvent is a hybrid of reactive components and enzymes, the solvent is typically aggressive for standard nano-filtration membranes used in water based filtration processes. At the same time, significant membrane filtration area is required to allow for efficient solvent filtration. Preferred nano-membranes need to be cost effective and resistant to aggressive heated solvents. It was found that nano-filtration membranes based Polyethersulfone (PES) combined with a separating layer of Sulfonated polyethersulfone (SPES) or membranes based on mixtures of PES and SPES provide good enzyme filtration properties and good chemical resistance against hybrid reactive C02 absorption solvents. Furthermore, it has been found that hollow fiber membranes optimized for filtration inside/out show benefits over membranes produced for opposite filtration direction.
In some implementations, there is a method of capturing carbon dioxide which includes the steps:
(a) of absorbing carbon dioxide in an enzyme based hybrid C02 capturing process by means of reactive solutions and accelerating enzymes; (b) of filtering the accelerating enzymes from the reactive components of the hybrid C02 capturing process by means of nano-filtration membranes before thermal swing desorption; and
(c) of thermal swing desorption of the absorbed carbon dioxide operated with a high accelerating enzyme concentration.
In some implementations, there is a process including: contacting the C02 containing gas with a hybrid solvent comprising carbonic anhydrase, water and an absorption compound, at a low absorption temperature, to produce a C02 depleted gas and an ion loaded solution; subjecting the ion loaded solution to membrane filtering to produce an enzyme deplete ion loaded solution and an enzyme component; heat treating the enzyme deplete ion loaded solution to produce a heated ion loaded solution; subjecting the heated ion loaded solution to desorption, at a high desorption temperature, to produce a C02 stream and a regenerated solution; cooling the regenerated solution to produce a cooled regenerated solution; and recycling the cooled regenerated solution and at least some of the enzyme component back for absorption.
In some implementations, there is a process including: operating a C02 capture system comprising an absorption stage and a desorption stage operated with a large temperature swing in between the absorption stage and the desorption stage; utilizing a hybrid solvent comprising water, carbonic anhydrase and an absorption compound in the absorption stage for absorbing C02 out of a C02 containing gas; membrane filtering the carbonic anhydrase out of the hybrid solvent in between the absorption stage and the desorption stage and prior to the large temperature swing; and recycling the filtered carbonic anhydrase back into the absorption stage to maintain high enzyme concentration in the absorption stage.

Claims

1 . A process for treating a C02 containing gas comprising: contacting the C02 containing gas with a hybrid solvent comprising carbonic anhydrase, water and an absorption compound, at a low absorption temperature, to produce a C02 depleted gas and an ion loaded solution; subjecting the ion loaded solution to membrane filtering to produce an enzyme deplete ion loaded solution and an enzyme component; heat treating the enzyme deplete ion loaded solution to produce a heated ion loaded solution; subjecting the heated ion loaded solution to desorption, at a high desorption temperature, to produce a C02 stream and a regenerated solution; cooling the regenerated solution to produce a cooled regenerated solution; and recycling the cooled regenerated solution and at least some of the enzyme component back for absorption.
2. The process of claim, wherein the carbonic anhydrase are heat degradable above 40C.
3. The process of claim, wherein the low absorption temperature is 35-45C.
4. The process of claim, wherein the high desorption temperature is 105-120.
5. The process of claim, wherein the difference between the low absorption temperature and the high desorption temperature is between 60-85C.
6. The process of claim, wherein the absorption compound comprises an amine.
7. The process of claim, wherein the membrane filtration comprises nano-filtration.
8. The process of claim, wherein the membrane filtration uses pores or pore layers below 15 nm in diameter.
9. The process of claim, wherein the membrane filtration uses pores with an average pore diameter of 1 -5 nm.
10. The process of claim, wherein the absorption compound is selected and provided to enable an aggressive hybrid solvent.
1 1 . The process of claim, wherein the membrane filtration uses membranes that are resistant to aggressive and/or heated solvents.
12. The process of claim, wherein the membrane comprises polyethersulfone (PES).
13. The process of claim, wherein the membrane comprises polyethersulfone (PES) with a separating layer of sulfonated polyethersulfone (SPES).
14. The process of claim, wherein the membrane comprises a mixture of PES and SPES.
15. The process of claim, wherein the membrane comprise hollow fibers utilizing inside/out filtration.
16. The process of claim, further comprising operating the membrane filtration by periodically changing flow direction relative to the membrane to enable opposite filtration direction.
17. The process of claim, wherein the carbonic anhydrase have a molecular mass of 5- 50 kiloDaltons.
18. The process of claim, wherein the membrane and the carbonic anhydrase are provided such that the pore size to molecular mass ratio is 0.02 nm/kilodalton - 3 nm/kilodalton.
19. The process of claim, comprising providing an enzyme carbonic anhydrase concentration for absorption so as to enhance efficiency of the process.
20. The process of claim, wherein the cooled regenerated solution and at least some of the enzyme component are combined prior to recycling to absorption as at least part of the hybrid solvent.
21 . The process of claim, comprising operating the desorption such that enzymatic acceleration of the dehydration reaction would have a negligible effect on process efficiency.
22. A method for C02 capture, comprising: operating a C02 capture system comprising an absorption stage and a desorption stage operated with a large temperature swing in between the absorption stage and the desorption stage; utilizing a hybrid solvent comprising water, carbonic anhydrase and an absorption compound in the absorption stage for absorbing C02 out of a C02 containing gas; membrane filtering the carbonic anhydrase out of the hybrid solvent in between the absorption stage and the desorption stage and prior to the large temperature swing; and recycling the filtered carbonic anhydrase back into the absorption stage to maintain high enzyme concentration in the absorption stage.
23. The method of claim, comprising one or more features of any one of claims 1 to 21 .
PCT/CA2012/050802 2011-11-11 2012-11-13 Co2 capture with carbonic anhydrase and membrane filtration WO2013067648A1 (en)

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