WO2013067648A1 - Capture de co2 avec une anhydrase carbonique et une filtration sur membrane - Google Patents

Capture de co2 avec une anhydrase carbonique et une filtration sur membrane 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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WO
WIPO (PCT)
Prior art keywords
absorption
membrane
carbonic anhydrase
stage
desorption
Prior art date
Application number
PCT/CA2012/050802
Other languages
English (en)
Inventor
Geert Frederik Versteeg
Original Assignee
Co2 Solutions Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Co2 Solutions Inc. filed Critical Co2 Solutions Inc.
Priority to EP12846957.4A priority Critical patent/EP2776143A4/fr
Publication of WO2013067648A1 publication Critical patent/WO2013067648A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1425—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)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne un procédé de capture de CO2 comprenant la mise en œuvre d'un système de capture de CO2 avec un grand changement de température entre l'étape d'absorption et l'étape de désorption ; l'utilisation d'un solvant hybride comprenant de l'eau, de l'anhydrase carbonique et un composé d'absorption dans l'étape d'absorption ; une élimination par filtration sur membrane de l'anhydrase carbonique du solvant hybride entre l'étape d'absorption et l'étape de désorption et avant le grand changement de température ; et un recyclage de l'anhydrase carbonique filtrée vers l'étape d'absorption pour maintenir une concentration élevée en enzyme dans l'étape d'absorption.
PCT/CA2012/050802 2011-11-11 2012-11-13 Capture de co2 avec une anhydrase carbonique et une filtration sur membrane WO2013067648A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12846957.4A EP2776143A4 (fr) 2011-11-11 2012-11-13 Capture de co2 avec une anhydrase carbonique et une filtration sur membrane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA201108315 2011-11-11
ZA201108315 2011-11-11

Publications (1)

Publication Number Publication Date
WO2013067648A1 true WO2013067648A1 (fr) 2013-05-16

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PCT/CA2012/050802 WO2013067648A1 (fr) 2011-11-11 2012-11-13 Capture de co2 avec une anhydrase carbonique et une filtration sur membrane

Country Status (2)

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EP (1) EP2776143A4 (fr)
WO (1) WO2013067648A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722068A (zh) * 2017-04-18 2018-11-02 北京化工大学 一种可降解的过滤除菌膜及制备方法
WO2022115923A1 (fr) * 2020-12-02 2022-06-09 Petróleo Brasileiro S.A. - Petrobras Procédé de séparation de dioxyde de carbone d'un courant gazeux et utilisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2714304A1 (fr) * 2001-07-13 2003-01-13 Co2 Solution Inc. Bioreacteur a anhydrase carbonique et procede pour le traitement d'effluents gazeux contenant du co2
WO2008095057A2 (fr) * 2007-01-31 2008-08-07 Novozymes A/S Anhydrases carboniques stables à la chaleur et leur utilisation
WO2012036843A1 (fr) * 2010-09-15 2012-03-22 Alstom Technology Ltd Solvant et procédé de capture de co2 à partir d'un gaz d'évacuation

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
US20070246406A1 (en) * 2006-03-31 2007-10-25 Dibel Kevin R Tangential flow filtration apparatuses, systems, and processes for the separation of compounds
CA2672641C (fr) * 2006-12-15 2014-07-08 Sinvent As Procede de capture du co<sb>2</sb> a partir d'un gaz d'echappement
EP2461893A4 (fr) * 2009-08-04 2013-01-09 Co2 Solution Inc Formulation et procédé de capture de co2 utilisant des acides aminés et des
CN103429318A (zh) * 2011-02-03 2013-12-04 二氧化碳处理公司 使用根据反应性液膜厚度定尺寸的酶粒子用于增强催化作用的co2处理

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2714304A1 (fr) * 2001-07-13 2003-01-13 Co2 Solution Inc. Bioreacteur a anhydrase carbonique et procede pour le traitement d'effluents gazeux contenant du co2
WO2008095057A2 (fr) * 2007-01-31 2008-08-07 Novozymes A/S Anhydrases carboniques stables à la chaleur et leur utilisation
WO2012036843A1 (fr) * 2010-09-15 2012-03-22 Alstom Technology Ltd Solvant et procédé de capture de co2 à partir d'un gaz d'évacuation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2776143A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108722068A (zh) * 2017-04-18 2018-11-02 北京化工大学 一种可降解的过滤除菌膜及制备方法
WO2022115923A1 (fr) * 2020-12-02 2022-06-09 Petróleo Brasileiro S.A. - Petrobras Procédé de séparation de dioxyde de carbone d'un courant gazeux et utilisation
GB2615941A (en) * 2020-12-02 2023-08-23 Petroleo Brasileiro Sa Petrobras Process for separating carbon dioxide from a gas stream and use

Also Published As

Publication number Publication date
EP2776143A4 (fr) 2016-01-27
EP2776143A1 (fr) 2014-09-17

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