CA2783190C - Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase - Google Patents
Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase Download PDFInfo
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- CA2783190C CA2783190C CA2783190A CA2783190A CA2783190C CA 2783190 C CA2783190 C CA 2783190C CA 2783190 A CA2783190 A CA 2783190A CA 2783190 A CA2783190 A CA 2783190A CA 2783190 C CA2783190 C CA 2783190C
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- carbonic anhydrase
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- 238000000034 method Methods 0.000 title claims abstract description 82
- 230000008569 process Effects 0.000 title claims abstract description 77
- 102000003846 Carbonic anhydrases Human genes 0.000 title claims abstract description 52
- 108090000209 Carbonic anhydrases Proteins 0.000 title claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 128
- 239000007791 liquid phase Substances 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000007788 liquid Substances 0.000 claims abstract description 65
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000012071 phase Substances 0.000 claims abstract description 32
- 230000002255 enzymatic effect Effects 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 29
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- -1 hydrogen ions Chemical class 0.000 claims abstract description 23
- 238000006703 hydration reaction Methods 0.000 claims abstract description 11
- 239000003595 mist Substances 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 102000004190 Enzymes Human genes 0.000 claims description 47
- 108090000790 Enzymes Proteins 0.000 claims description 47
- 239000011942 biocatalyst Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 22
- 239000006193 liquid solution Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000012528 membrane Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 239000000701 coagulant Substances 0.000 claims description 3
- 238000005188 flotation Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 238000009738 saturating Methods 0.000 claims 2
- 210000001601 blood-air barrier Anatomy 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 239000000872 buffer Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 142
- 229910002092 carbon dioxide Inorganic materials 0.000 description 71
- 239000007921 spray Substances 0.000 description 26
- 239000007795 chemical reaction product Substances 0.000 description 18
- 239000006096 absorbing agent Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 230000002210 biocatalytic effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000010795 gaseous waste Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000000108 ultra-filtration Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008953 bacterial degradation Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 210000003463 organelle Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 241001148471 unidentified anaerobic bacterium Species 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/84—Biological processes
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Gas Separation By Absorption (AREA)
- Treating Waste Gases (AREA)
Abstract
A process for enzymatic treatment of a CO2-containing gas comprising contacting the CO2-containing gas with an aqueous solution, optionally comprising a buffer, in the presence of carbonic anhydrase that catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the ions and a CO2 depleted gas phase. The aqueous solution may be sprayed into a reaction chamber before contact with the CO2-containing gas for producing the CO2 depleted gas phase. The CO2 depleted gas phase may comprise mist of the aqueous solution which is removed from the CO2 depleted gas phase to produce a mist depleted gas. The carbonic anhydrase may be entrapped inside a matrix. The process may comprise releasing the liquid phase from the reaction chamber, precipitating solid particles in the liquid phase, removing the particles from the liquid phase to produce a precipitate removed liquid, and recycling the precipitate removed liquid back into the reaction chamber as the aqueous solution.
Description
USING CARBONIC ANHYDRASE
FIELD OF THE INVENTION
The present invention relates generally to processes for the treatment of gas effluents with a view to cleaning or purifying such effluents. More particularly, it relates to a process and an apparatus using a spray absorber for the biocatalytic treatment of gases.
BACKGROUND OF THE INVENTION
Contemporary industrial activities generate gaseous effluents containing a multitude of chemical compounds and contaminants which interfere with the equilibrium of elements in nature and affect the environment at different levels. Acid rain, the greenhouse effect, smog and the deterioration of the ozone layer are examples that speak volumes about this problem. Reduction of noxious emissions is therefore not surprisingly the subject of more and more legislation and regulation. Industrial activities and applications which must contend with stricter environmental regulatory standards in order to expect any long-term commercial viability will turn more and more to biological and environmentally safe methods. Consequently, there is a real need for new apparatuses and methods aimed at the treatment of gaseous waste or effluents.
There already exists a vast array of technologies aimed at the separation and recovery of individual or mixed gases and a number of different biological methods is known to treat gaseous waste or effluents: bacterial degradation (JP 2000-287679; JP
236870), fermentation by anaerobic bacteria (WO 98/00558), photosynthesis through either plants (CA 2,029,101 A1; JP 04-190782) or microorganisms (JP 03-216180).
Among the more popular are those gained through the harnessing of biological processes such as peat biofilters sprinkled with a flora of microorganisms in an aqueous phase, or biofilter columns comprising immobilized resident microorganisms (Deshusses et al. (1996) Biotechnol. Bioeng. 49, 587-598). Although such biofilters have contributed to technological advances within the field of _________________________________
FIELD OF THE INVENTION
The present invention relates generally to processes for the treatment of gas effluents with a view to cleaning or purifying such effluents. More particularly, it relates to a process and an apparatus using a spray absorber for the biocatalytic treatment of gases.
BACKGROUND OF THE INVENTION
Contemporary industrial activities generate gaseous effluents containing a multitude of chemical compounds and contaminants which interfere with the equilibrium of elements in nature and affect the environment at different levels. Acid rain, the greenhouse effect, smog and the deterioration of the ozone layer are examples that speak volumes about this problem. Reduction of noxious emissions is therefore not surprisingly the subject of more and more legislation and regulation. Industrial activities and applications which must contend with stricter environmental regulatory standards in order to expect any long-term commercial viability will turn more and more to biological and environmentally safe methods. Consequently, there is a real need for new apparatuses and methods aimed at the treatment of gaseous waste or effluents.
There already exists a vast array of technologies aimed at the separation and recovery of individual or mixed gases and a number of different biological methods is known to treat gaseous waste or effluents: bacterial degradation (JP 2000-287679; JP
236870), fermentation by anaerobic bacteria (WO 98/00558), photosynthesis through either plants (CA 2,029,101 A1; JP 04-190782) or microorganisms (JP 03-216180).
Among the more popular are those gained through the harnessing of biological processes such as peat biofilters sprinkled with a flora of microorganisms in an aqueous phase, or biofilter columns comprising immobilized resident microorganisms (Deshusses et al. (1996) Biotechnol. Bioeng. 49, 587-598). Although such biofilters have contributed to technological advances within the field of _________________________________
2 gaseous waste biopurification, the main drawbacks associated with their use are their difficult maintenance and upkeep, lack of versatility, as well as time consuming bacterial acclimation and response to perturbation periods (Deshusses et al.).
A number of biological sanitation/purification methods and products is known to use enzymatic processes, coupled or not to filtration membranes (US 5,250,305;
US 4,033,822; JP 63-129987). However, these are neither intended nor adequate for the cleansing of gaseous waste or effluents. The main reason for this is that, in such systems, contaminants are generally already in solution (US 5,130,237; US
4,033,822;
US 4,758,417; US 5,250,305; WO 97/19196; JP 63-129987). Efficient enzymatic conversion and treatability itself of gaseous waste or effluents in liquids therefore depend on adequate and sufficient dissolution of the gaseous phase in the liquid phase.
However, the adequate dissolution of gaseous waste or effluents into liquids for enzymatic conversion poses a real problem which constitutes the first of a series of important limitations which compound the problem of further technological advances in the field of gas biopurification.
Although triphasic Gas-Liquid-Solid (GLS) reactors are commonly used in a large variety of industrial applications, their utilization remains quite limited in the area of biochemical gas treatment (US 6,245,304; US 4,743,545). Also known in the prior art are the GLS bioprocesses abundantly reported in the literature. A majority of these concerns wastewater treatment (JP 09057289). These GLS processes are characterized in that the gaseous intake serves the sole purpose of satisfying the specific metabdic requirements of the particular organism selected for the wastewater treatment process.
Such GLS treatment processes are therefore not aimed at reducing gaseous emissions.
As previously mentioned, these systems are neither intended nor adequate for the treatment of gaseous waste or effluents. An additional problem associated with the use of these systems is the non retention of the solid phase within the reactor.
Biocatalysts are in fact washed right out of the reactors along with the liquid phase.
Different concepts are, nonetheless, based on this principle for the reduction of gaseous emissions, namely carbon dioxide. Certain bioreactors allow the uptake of CO2 by photosynthetic organisms (JP 03-216180) and similar processes bind CO2 through algae
A number of biological sanitation/purification methods and products is known to use enzymatic processes, coupled or not to filtration membranes (US 5,250,305;
US 4,033,822; JP 63-129987). However, these are neither intended nor adequate for the cleansing of gaseous waste or effluents. The main reason for this is that, in such systems, contaminants are generally already in solution (US 5,130,237; US
4,033,822;
US 4,758,417; US 5,250,305; WO 97/19196; JP 63-129987). Efficient enzymatic conversion and treatability itself of gaseous waste or effluents in liquids therefore depend on adequate and sufficient dissolution of the gaseous phase in the liquid phase.
However, the adequate dissolution of gaseous waste or effluents into liquids for enzymatic conversion poses a real problem which constitutes the first of a series of important limitations which compound the problem of further technological advances in the field of gas biopurification.
Although triphasic Gas-Liquid-Solid (GLS) reactors are commonly used in a large variety of industrial applications, their utilization remains quite limited in the area of biochemical gas treatment (US 6,245,304; US 4,743,545). Also known in the prior art are the GLS bioprocesses abundantly reported in the literature. A majority of these concerns wastewater treatment (JP 09057289). These GLS processes are characterized in that the gaseous intake serves the sole purpose of satisfying the specific metabdic requirements of the particular organism selected for the wastewater treatment process.
Such GLS treatment processes are therefore not aimed at reducing gaseous emissions.
As previously mentioned, these systems are neither intended nor adequate for the treatment of gaseous waste or effluents. An additional problem associated with the use of these systems is the non retention of the solid phase within the reactor.
Biocatalysts are in fact washed right out of the reactors along with the liquid phase.
Different concepts are, nonetheless, based on this principle for the reduction of gaseous emissions, namely carbon dioxide. Certain bioreactors allow the uptake of CO2 by photosynthetic organisms (JP 03-216180) and similar processes bind CO2 through algae
3 (CA 2,232,707; JP 08-116965; JP 04-190782; JP 04-075537). However, the biocatalyst retention problem remains largely unaddressed and constitutes another serious limitation, along with gaseous effluent dissolution, to further technological advancements.
The main argument against the use of ultrafiltration membranes to solve this biocatalyst retention problem is their propensity to clogging. Clogging renders them unattractive and so, their use is rather limited for the retention of catalysts within reactors. However, a photobioreactor for medical applications as an artificial lung (WO 92/00380;
US 5,614,378) and an oxygen recovery system (US 4,602,987; US 4,761,209) are notable exceptions making use of carbonic anhydrase and an ultrafiltration unit.
The patent applications held by the assignee, CO2 Solution Inc., via Les Systemes Envirobio Inc. (EP 0 991 462; WO 98/55210; CA 2,291,785) propose a packed column for the treatment of carbon dioxide using immobilized carbonic anhydrase.
Carbonic anhydrase is a readily available and highly reactive enzyme that is used in other systems for the reduction of carbon dioxide emissions (US 4,602,987; US 4,743,545;
US 5,614,378; US 6,257,335). In the system described by Trachtenberg for the carbonic anhydrase treatment of gaseous effluents (US 6,143,556; CA 2,222,030), biocatalyst retention occurs through a porous wall or through enzyme immobilization.
However, important drawbacks are associated with the use of enzyme immobilization, as will be discussed below.
Other major drawbacks are associated with the use of enzymatic systems. One of these stems from systems where enzymatic activity is specifically and locally concentrated.
This is the case with systems where enzymes are immobilized at a particular site or on a specific part of an apparatus. Examples in point of such systems are those where enzymes are immobilized on a filtration membrane (JP 60014900008A2; US
The main argument against the use of ultrafiltration membranes to solve this biocatalyst retention problem is their propensity to clogging. Clogging renders them unattractive and so, their use is rather limited for the retention of catalysts within reactors. However, a photobioreactor for medical applications as an artificial lung (WO 92/00380;
US 5,614,378) and an oxygen recovery system (US 4,602,987; US 4,761,209) are notable exceptions making use of carbonic anhydrase and an ultrafiltration unit.
The patent applications held by the assignee, CO2 Solution Inc., via Les Systemes Envirobio Inc. (EP 0 991 462; WO 98/55210; CA 2,291,785) propose a packed column for the treatment of carbon dioxide using immobilized carbonic anhydrase.
Carbonic anhydrase is a readily available and highly reactive enzyme that is used in other systems for the reduction of carbon dioxide emissions (US 4,602,987; US 4,743,545;
US 5,614,378; US 6,257,335). In the system described by Trachtenberg for the carbonic anhydrase treatment of gaseous effluents (US 6,143,556; CA 2,222,030), biocatalyst retention occurs through a porous wall or through enzyme immobilization.
However, important drawbacks are associated with the use of enzyme immobilization, as will be discussed below.
Other major drawbacks are associated with the use of enzymatic systems. One of these stems from systems where enzymatic activity is specifically and locally concentrated.
This is the case with systems where enzymes are immobilized at a particular site or on a specific part of an apparatus. Examples in point of such systems are those where enzymes are immobilized on a filtration membrane (JP 60014900008A2; US
4,033,822;
US 5,130,237; US 5,250,305; JP 54-132291; JP 63-129987; JP 02-109986;
DE 3,937,892) or even, at a gas-liquid phase boundary (WO 96/40414; US
6,143,556).
The limited surface contact area obtainable between the dissolved gas substrate, the liquid and the enzyme active site poses an important problem. Hence, these systems generate significantly greater waste of input material, such as expensive purified , enzymes, because the contact surface with the gaseous phase is far from optimal and limits productive reaction rates. Therefore, as mentioned previously, overcoming the contact surface area difficulty should yield further technological advances.
Other examples of prior art apparatuses or methods for the treatment of gas or liquid effluents are given in the following documents: CA 2,160,311; CA 2,238,323;
CA 2,259,492; CA 2,268,641; JP 2000-236870; JP 2000-287679; JP 2000-202239;
US 4,758,417; US 5,593,886; US 5,807,722; US 6,136,577; and US 6,245,304.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an apparatus that is distinct from and overcomes several disadvantages of the prior art bioreactor for the treatment of gas effluent, as will be discussed in detail below.
Another object is to provide a process for the biocatalytic treatment of gases, which is more efficient with respect to the reaction rate of the reactants.
In accordance with the present invention, that object is achieved with a process characterized in that it comprises a step of contacting a gas phase, containing a particular gas to be treated, to spray droplets of liquid phase containing biocatalysts.
More particularly, the present invention proposes a process for the biocatalytic treatment of gases, comprising the steps of:
a) contacting a gas phase, containing a gas to be treated, to a liquid phase containing a reactant capable of absorbing and/or chemically reacting with the gas, thereby producing a spent liquid phase containing at least one reaction product and a treated gas phase substantially free of the gas, such step being performed in the presence of biocatalysts suitable for catalyzing the chemical reaction between the gas and the reactant, the process being characterized in that:
- it comprises, prior to step a) of contacting, the step of mixing the biocatalysts to the liquid phase; and - the step of contacting comprises the step of spraying droplets of the liquid phase containing the biocatalysts.
The liquid phase may be aqueous or non aqueous and the gas to be treated is usually soluble in the liquid. Contact between the gas and liquid phases results in the absorption
US 5,130,237; US 5,250,305; JP 54-132291; JP 63-129987; JP 02-109986;
DE 3,937,892) or even, at a gas-liquid phase boundary (WO 96/40414; US
6,143,556).
The limited surface contact area obtainable between the dissolved gas substrate, the liquid and the enzyme active site poses an important problem. Hence, these systems generate significantly greater waste of input material, such as expensive purified , enzymes, because the contact surface with the gaseous phase is far from optimal and limits productive reaction rates. Therefore, as mentioned previously, overcoming the contact surface area difficulty should yield further technological advances.
Other examples of prior art apparatuses or methods for the treatment of gas or liquid effluents are given in the following documents: CA 2,160,311; CA 2,238,323;
CA 2,259,492; CA 2,268,641; JP 2000-236870; JP 2000-287679; JP 2000-202239;
US 4,758,417; US 5,593,886; US 5,807,722; US 6,136,577; and US 6,245,304.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an apparatus that is distinct from and overcomes several disadvantages of the prior art bioreactor for the treatment of gas effluent, as will be discussed in detail below.
Another object is to provide a process for the biocatalytic treatment of gases, which is more efficient with respect to the reaction rate of the reactants.
In accordance with the present invention, that object is achieved with a process characterized in that it comprises a step of contacting a gas phase, containing a particular gas to be treated, to spray droplets of liquid phase containing biocatalysts.
More particularly, the present invention proposes a process for the biocatalytic treatment of gases, comprising the steps of:
a) contacting a gas phase, containing a gas to be treated, to a liquid phase containing a reactant capable of absorbing and/or chemically reacting with the gas, thereby producing a spent liquid phase containing at least one reaction product and a treated gas phase substantially free of the gas, such step being performed in the presence of biocatalysts suitable for catalyzing the chemical reaction between the gas and the reactant, the process being characterized in that:
- it comprises, prior to step a) of contacting, the step of mixing the biocatalysts to the liquid phase; and - the step of contacting comprises the step of spraying droplets of the liquid phase containing the biocatalysts.
The liquid phase may be aqueous or non aqueous and the gas to be treated is usually soluble in the liquid. Contact between the gas and liquid phases results in the absorption
5 of the gas to be treated and thus to its extraction from the gas phase.
The use of droplets of liquid containing the biocatalysts, sprayed into the reaction chamber, enables to increase the gas-liquid interface, thereby allowing a high mass transfer rate of the gas to be treated from the gas phase to the liquid phase.
These conditions of high mass transfer enable to transform the gas with a maximum reaction rate.
Then, the dissolved gas is transformed in presence of appropriate biocatalysts into one or more products. The role of biocatalysts is to accelerate the transformation reaction of the dissolved gas in the liquid phase environment. In addition to biocatalysts, the liquid phase may contain reactants required for the transformation of the dissolved gas or for a reaction with one or more reaction products of the dissolved gas. Depending on the reactants and biocatalysts present in the liquid phase, products are in a soluble or solid form. Reaction products are preferably further treated to give useful products to be used in other applications or to be disposed of.
Absorption and biocatalytic transformation of the gas take place in the reaction chamber of a spray absorber bioreactor. The gas phase, containing the selected gas to be treated, is fed into the reaction chamber where it is contacted to spray droplets of a liquid phase containing the biocatalysts. Droplets are obtained using atomizers. The gas phase in contact to the liquid phase has one or more components absorbed in the liquid phase.
Then, the dissolved gas is transformed because of biocatalysts activity and presence of reactants, if required. The gas phase is almost free of one or more components and exits the reaction chamber purified. The liquid phase containing the biocatalysts and reaction products (dissolved and/or solid) exits from the reaction chamber. In accordance with a preferred aspect of the invention, the gas is further treated to remove droplets in suspension or to decrease its humidity.
The use of droplets of liquid containing the biocatalysts, sprayed into the reaction chamber, enables to increase the gas-liquid interface, thereby allowing a high mass transfer rate of the gas to be treated from the gas phase to the liquid phase.
These conditions of high mass transfer enable to transform the gas with a maximum reaction rate.
Then, the dissolved gas is transformed in presence of appropriate biocatalysts into one or more products. The role of biocatalysts is to accelerate the transformation reaction of the dissolved gas in the liquid phase environment. In addition to biocatalysts, the liquid phase may contain reactants required for the transformation of the dissolved gas or for a reaction with one or more reaction products of the dissolved gas. Depending on the reactants and biocatalysts present in the liquid phase, products are in a soluble or solid form. Reaction products are preferably further treated to give useful products to be used in other applications or to be disposed of.
Absorption and biocatalytic transformation of the gas take place in the reaction chamber of a spray absorber bioreactor. The gas phase, containing the selected gas to be treated, is fed into the reaction chamber where it is contacted to spray droplets of a liquid phase containing the biocatalysts. Droplets are obtained using atomizers. The gas phase in contact to the liquid phase has one or more components absorbed in the liquid phase.
Then, the dissolved gas is transformed because of biocatalysts activity and presence of reactants, if required. The gas phase is almost free of one or more components and exits the reaction chamber purified. The liquid phase containing the biocatalysts and reaction products (dissolved and/or solid) exits from the reaction chamber. In accordance with a preferred aspect of the invention, the gas is further treated to remove droplets in suspension or to decrease its humidity.
6 Hence, the present invention is also directed to a biocatalytic treatment unit for the biocatalytic treatment of gases, comprising:
- a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving a gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas;
the treatment unit being characterized in that it comprises;
a mixing unit for mixing biocatalysts to the liquid;
means for conveying the liquid from the mixing unit to the liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of liquid containing the biocatalyst.
Biocatalysts are usually very costly. Therefore, it is preferable to recycle the spent liquid phase containing biocatalysts and reactants. However, recycling requires that reaction products be removed from the liquid phase. Therefore, in accordance with a preferred aspect of the invention, the process further comprises the steps of:
b) removing from the spent liquid phase the at least one reaction product, thereby obtaining a recycled liquid phase free of the reaction product and containing the biocatalysts; and c) recycling the recycled liquid phase to step a) of contacting.
In accordance with that aspect of the invention, the treatment unit further comprises a separation unit in fluid communication with the liquid outlet for removing the reaction products contained in the spent liquid. The separation unit has a first liquid outlet for discharging a liquid fraction substantially free of the reaction products and a second outlet for discharging the liquid fraction containing the reaction products.
Conveying means are provided for conveying the fraction substantially free of the reaction products to the mixing unit.
- a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving a gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas;
the treatment unit being characterized in that it comprises;
a mixing unit for mixing biocatalysts to the liquid;
means for conveying the liquid from the mixing unit to the liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of liquid containing the biocatalyst.
Biocatalysts are usually very costly. Therefore, it is preferable to recycle the spent liquid phase containing biocatalysts and reactants. However, recycling requires that reaction products be removed from the liquid phase. Therefore, in accordance with a preferred aspect of the invention, the process further comprises the steps of:
b) removing from the spent liquid phase the at least one reaction product, thereby obtaining a recycled liquid phase free of the reaction product and containing the biocatalysts; and c) recycling the recycled liquid phase to step a) of contacting.
In accordance with that aspect of the invention, the treatment unit further comprises a separation unit in fluid communication with the liquid outlet for removing the reaction products contained in the spent liquid. The separation unit has a first liquid outlet for discharging a liquid fraction substantially free of the reaction products and a second outlet for discharging the liquid fraction containing the reaction products.
Conveying means are provided for conveying the fraction substantially free of the reaction products to the mixing unit.
7 Removal assures that a maximum mass transfer rate of the gas from the gas phase to the liquid phase is achieved at each pass of the liquid phase in the reaction chamber of the spray absorber bioreactor. Removal of dissolved reaction products is preferably obtained using membrane processes such as ultrafiltration, microfiltration processes and/or ion exchange and/or adsorption processes. Removal may also be obtained by first precipitating the reaction products with appropriate reactant (s) and then by removing the particles using separation processes. Solid particles originating from solid reaction products or subsequently precipitated products are preferably removed by using separation processes such as settling, filtration or expression. Moreover, agents facilitating removal of particles, such as coagulants or flocculants or filter aids, may be added to the liquid effluent prior to particle removal units or to the liquid phase entering the spray absorber bioreactor.
A biocatalyst is a biological entity, which can transform a substrate in one or more products. The biocatalysts used in the process are preferably enzymes, cellular organelles (mitochondrion, membranes), animal, vegetal or human cells. The biocatalysts can be used free or immobilized. Immobilization is preferably the result of fixation to a solid support, entrapment inside a solid matrix. Immobilization can also be obtained by using intermolecular binding of biocatalysts molecules or structures. In all these cases, the solid support, the solid matrix and the intermolecular binding must be in the form of micro particles sufficiently small to pass through the atomizer with the liquid phase.
Depending on patterns of spray, droplet size, uniformity of spray, turndown ratio and/or power consumption, available atomizers may fall in three categories: pressure nozzles, two-fluid nozzles or rotary devices. However, any other type of atomizer may be used.
Membrane processes for removal of dissolved products or solid particles may include the use of flat or tubular membranes. Those membranes are preferably involved in ,
A biocatalyst is a biological entity, which can transform a substrate in one or more products. The biocatalysts used in the process are preferably enzymes, cellular organelles (mitochondrion, membranes), animal, vegetal or human cells. The biocatalysts can be used free or immobilized. Immobilization is preferably the result of fixation to a solid support, entrapment inside a solid matrix. Immobilization can also be obtained by using intermolecular binding of biocatalysts molecules or structures. In all these cases, the solid support, the solid matrix and the intermolecular binding must be in the form of micro particles sufficiently small to pass through the atomizer with the liquid phase.
Depending on patterns of spray, droplet size, uniformity of spray, turndown ratio and/or power consumption, available atomizers may fall in three categories: pressure nozzles, two-fluid nozzles or rotary devices. However, any other type of atomizer may be used.
Membrane processes for removal of dissolved products or solid particles may include the use of flat or tubular membranes. Those membranes are preferably involved in ,
8 different modules such as plate-and-frame, spiral-wound, tubular capillary and hollow fiber module. The operation of those modules may be dead-end or cross-flow (co-current, countercurrent, cross-flow with perfect permeate mixing and perfect mixing).
Those filtration units may be used in a single-stage or in a multi-stage process in a single-pass system or a recirculation system.
The present invention also provides a process for the biocatalytic treatment of a CO2-containing gas, comprising the steps of:
a) contacting the CO2-containing gas phase, containing CO2 gas to be treated, to a liquid phase containing carbonic anhydrase capable of catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a spent liquid phase containing the bicarbonate and hydrogen ions and a treated gas phase substantially free of the CO2, the process being characterized in that:
it comprises, prior to step a) of contacting, the step of mixing the carbonic anhydrase to the liquid phase; and the step of contacting comprises the step of spraying droplets of the liquid phase containing the carbonic anhydrase.
The present invention also provides a carbonic anhydrase treatment unit for the treatment of CO2-containing gas, comprising:
a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving the CO2-containing gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas;
the treatment unit being characterized in that it comprises;
a mixing unit for mixing carbonic anhydrase to said liquid;
means for conveying the liquid from the mixing unit to the liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of liquid containing the carbonic anhydrase.
8a The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
mixing enzymatic particles comprising carbonic anhydrase with a liquid solution to form a sprayable mixture;
spraying the sprayable mixture to form droplets thereof comprising the enzymatic particles;
contacting the CO2-containing gas with the droplets such that the carbonic anhydrase catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a spent liquid phase containing the bicarbonate and hydrogen ions and a treated gas phase substantially free of the CO2.
The present invention also provides a process for treatment of a fluid by enzymatic catalysis of reaction (I) with carbonic anhydrase, wherein the reaction (I) is as follows:
CO2 +H20 erbonic anhydral HCO+H+ (I) the process comprising:
feeding the fluid into a reaction zone in the presence of enzymatic particles comprising carbonic anhydrase, the enzymatic particles being sized to be mixed and sprayed with a liquid solution thereby forming droplets comprising the enzymatic particles;
allowing the reaction (I) to occur within the droplets in the reaction zone, to produce a gas stream and a liquid stream; and releasing the gas stream and the liquid stream from the reaction zone. In one embodiment, the process as described above, wherein the fluid is a CO2-containing gas; the process comprises spraying the droplets comprising the enzymatic particles into the reaction zone to contact the CO2-containg gas so as 8b to dissolve CO2 from the CO2-containing effluent gas into the droplets; the reaction (l) is a forward reaction catalyzing the hydration of dissolved CO2 into the bicarbonate and hydrogen ions; and the gas stream is a treated gas phase substantially free of the CO2 and the liquid stream is a spent liquid phase containing the bicarbonate and hydrogen ions.
The present invention further provides a carbonic anhydrase treatment unit for the treatment of CO2-containing gas, comprising:
a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving the CO2-containing gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas;
a mixing unit for mixing enzymatic particles comprising carbonic anhydrase with the liquid to form a sprayable mixture;
means for conveying the sprayable mixture from the mixing unit to the liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of sprayable mixture containing the enzymatic particles into the reaction chamber.
The present invention further provides a carbonic anhydrase treatment unit for the treatment of a fluid by enzymatic catalysis of reaction (l) with carbonic anhydrase, wherein the reaction (l) is as follows:
CO2 +H20 tlrh Inc anhYdral HCO3 +H (l) the treatment unit comprising:
' 8c a bioreactor comprising a reaction chamber for accommodating the reaction (I), a liquid inlet, a liquid outlet for discharging a liquid stream and a gas outlet for releasing a gas stream;
a mixing unit for mixing enzymatic particles comprising carbonic anhydrase with a liquid solution thereby forming a sprayable mixture;
means for conveying the sprayable mixture from the mixing unit to a liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of the sprayable mixture containing the enzymatic particles into the reaction chamber such that the reaction (I) to occur within the droplets. In one embodiment the carbonic anhydrase treatment unit as described above, wherein the fluid is a CO2-containing gas; the bioreactor comprises a gas inlet for feeding the CO2-containing gas into the reaction chamber; the droplets comprising the enzymatic particles; the reaction (I) is a forward reaction catalyzing the hydration of dissolved CO2 into the bicarbonate and hydrogen ions; and the gas is a treated gas phase substantially free of the CO2 and the liquid stream is a spent liquid phase containing the bicarbonate and hydrogen ions.
The present invention also provides a carbonic anhydrase treatment unit comprising a reaction chamber having a liquid inlet for receiving a liquid containing micro-particles comprising carbonic anhydrase, a gas inlet for receiving a CO2-containing gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas, the liquid inlet being sized and configured to feed the liquid and micro-particles into the reaction chamber.
8d The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
a process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethy1-1,3-propanediol; and carbonic anhydrase;
in order to form droplets of the mixture; and contacting the CO2-containing gas with the droplets of the mixture such that the carbonic anhydrase catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase.
The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
a process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethy1-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture within the reaction chamber in presence of the carbonic anhydrase that catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a 8e liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase comprising mist of the aqueous liquid solution; and removing the mist from the CO2 depleted gas phase to produce a mist depleted gas.
The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
a process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethy1-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture in presence of the carbonic anhydrase, the carbonic anhydrase catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a loaded liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase;
releasing the loaded liquid phase from the reaction chamber;
precipitating solid particles in the loaded liquid phase;
removing the precipitated solid particles from the loaded liquid phase to produce a precipitate removed liquid; and recycling the precipitate removed liquid back into the reaction chamber as the aqueous liquid solution.
8f BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic representation of a spray absorber bioreactor according to a preferred embodiment of the present invention.
Figure 2 is a schematic flow chart of a second preferred embodiment of the process according to the present invention.
Figures 3a and 3b are schematic flow charts of a third preferred embodiment of the process according to the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to figure 1, a gas phase containing CO2 is fed to a reaction chamber (1) of a spray absorber bioreactor. The gas phase is preferably fed at the bottom (2) of the reaction chamber (1) of the spray absorber bioreactor. The aqueous liquid phase containing biocatalysts is preferably fed at the top of the reaction chamber (3) through atomizers (4) where the liquid phase forms droplets. Additional atomizers may be found at the side (4) of the reaction chamber. In this preferred embodiment, the gas phase flows upward and contact spray droplets of the liquid phase. During the contact, CO2 is absorbed and then transformed into bicarbonate and hydrogen ions.
This transformation is catalyzed by a biocatalyst accelerating CO2 transformation. The biocatalyst is preferably the enzyme carbonic anhydrase but may be any biological catalyst enabling CO2 transformation. CO2 transformation reaction is the following:
CO2 +1120 karborne anhydra, Hco H+ Equation 1
Those filtration units may be used in a single-stage or in a multi-stage process in a single-pass system or a recirculation system.
The present invention also provides a process for the biocatalytic treatment of a CO2-containing gas, comprising the steps of:
a) contacting the CO2-containing gas phase, containing CO2 gas to be treated, to a liquid phase containing carbonic anhydrase capable of catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a spent liquid phase containing the bicarbonate and hydrogen ions and a treated gas phase substantially free of the CO2, the process being characterized in that:
it comprises, prior to step a) of contacting, the step of mixing the carbonic anhydrase to the liquid phase; and the step of contacting comprises the step of spraying droplets of the liquid phase containing the carbonic anhydrase.
The present invention also provides a carbonic anhydrase treatment unit for the treatment of CO2-containing gas, comprising:
a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving the CO2-containing gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas;
the treatment unit being characterized in that it comprises;
a mixing unit for mixing carbonic anhydrase to said liquid;
means for conveying the liquid from the mixing unit to the liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of liquid containing the carbonic anhydrase.
8a The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
mixing enzymatic particles comprising carbonic anhydrase with a liquid solution to form a sprayable mixture;
spraying the sprayable mixture to form droplets thereof comprising the enzymatic particles;
contacting the CO2-containing gas with the droplets such that the carbonic anhydrase catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a spent liquid phase containing the bicarbonate and hydrogen ions and a treated gas phase substantially free of the CO2.
The present invention also provides a process for treatment of a fluid by enzymatic catalysis of reaction (I) with carbonic anhydrase, wherein the reaction (I) is as follows:
CO2 +H20 erbonic anhydral HCO+H+ (I) the process comprising:
feeding the fluid into a reaction zone in the presence of enzymatic particles comprising carbonic anhydrase, the enzymatic particles being sized to be mixed and sprayed with a liquid solution thereby forming droplets comprising the enzymatic particles;
allowing the reaction (I) to occur within the droplets in the reaction zone, to produce a gas stream and a liquid stream; and releasing the gas stream and the liquid stream from the reaction zone. In one embodiment, the process as described above, wherein the fluid is a CO2-containing gas; the process comprises spraying the droplets comprising the enzymatic particles into the reaction zone to contact the CO2-containg gas so as 8b to dissolve CO2 from the CO2-containing effluent gas into the droplets; the reaction (l) is a forward reaction catalyzing the hydration of dissolved CO2 into the bicarbonate and hydrogen ions; and the gas stream is a treated gas phase substantially free of the CO2 and the liquid stream is a spent liquid phase containing the bicarbonate and hydrogen ions.
The present invention further provides a carbonic anhydrase treatment unit for the treatment of CO2-containing gas, comprising:
a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving the CO2-containing gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas;
a mixing unit for mixing enzymatic particles comprising carbonic anhydrase with the liquid to form a sprayable mixture;
means for conveying the sprayable mixture from the mixing unit to the liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of sprayable mixture containing the enzymatic particles into the reaction chamber.
The present invention further provides a carbonic anhydrase treatment unit for the treatment of a fluid by enzymatic catalysis of reaction (l) with carbonic anhydrase, wherein the reaction (l) is as follows:
CO2 +H20 tlrh Inc anhYdral HCO3 +H (l) the treatment unit comprising:
' 8c a bioreactor comprising a reaction chamber for accommodating the reaction (I), a liquid inlet, a liquid outlet for discharging a liquid stream and a gas outlet for releasing a gas stream;
a mixing unit for mixing enzymatic particles comprising carbonic anhydrase with a liquid solution thereby forming a sprayable mixture;
means for conveying the sprayable mixture from the mixing unit to a liquid inlet of the reaction chamber; and the liquid inlet comprises at least one atomizer mounted within the reaction chamber to spray droplets of the sprayable mixture containing the enzymatic particles into the reaction chamber such that the reaction (I) to occur within the droplets. In one embodiment the carbonic anhydrase treatment unit as described above, wherein the fluid is a CO2-containing gas; the bioreactor comprises a gas inlet for feeding the CO2-containing gas into the reaction chamber; the droplets comprising the enzymatic particles; the reaction (I) is a forward reaction catalyzing the hydration of dissolved CO2 into the bicarbonate and hydrogen ions; and the gas is a treated gas phase substantially free of the CO2 and the liquid stream is a spent liquid phase containing the bicarbonate and hydrogen ions.
The present invention also provides a carbonic anhydrase treatment unit comprising a reaction chamber having a liquid inlet for receiving a liquid containing micro-particles comprising carbonic anhydrase, a gas inlet for receiving a CO2-containing gas to be treated, a liquid outlet for discharging a spent liquid and a gas outlet for releasing a treated gas, the liquid inlet being sized and configured to feed the liquid and micro-particles into the reaction chamber.
8d The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
a process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethy1-1,3-propanediol; and carbonic anhydrase;
in order to form droplets of the mixture; and contacting the CO2-containing gas with the droplets of the mixture such that the carbonic anhydrase catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase.
The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
a process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethy1-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture within the reaction chamber in presence of the carbonic anhydrase that catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a 8e liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase comprising mist of the aqueous liquid solution; and removing the mist from the CO2 depleted gas phase to produce a mist depleted gas.
The present invention also provides a process for enzymatic treatment of a CO2-containing gas, comprising:
a process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethy1-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture in presence of the carbonic anhydrase, the carbonic anhydrase catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a loaded liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase;
releasing the loaded liquid phase from the reaction chamber;
precipitating solid particles in the loaded liquid phase;
removing the precipitated solid particles from the loaded liquid phase to produce a precipitate removed liquid; and recycling the precipitate removed liquid back into the reaction chamber as the aqueous liquid solution.
8f BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic representation of a spray absorber bioreactor according to a preferred embodiment of the present invention.
Figure 2 is a schematic flow chart of a second preferred embodiment of the process according to the present invention.
Figures 3a and 3b are schematic flow charts of a third preferred embodiment of the process according to the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
Referring to figure 1, a gas phase containing CO2 is fed to a reaction chamber (1) of a spray absorber bioreactor. The gas phase is preferably fed at the bottom (2) of the reaction chamber (1) of the spray absorber bioreactor. The aqueous liquid phase containing biocatalysts is preferably fed at the top of the reaction chamber (3) through atomizers (4) where the liquid phase forms droplets. Additional atomizers may be found at the side (4) of the reaction chamber. In this preferred embodiment, the gas phase flows upward and contact spray droplets of the liquid phase. During the contact, CO2 is absorbed and then transformed into bicarbonate and hydrogen ions.
This transformation is catalyzed by a biocatalyst accelerating CO2 transformation. The biocatalyst is preferably the enzyme carbonic anhydrase but may be any biological catalyst enabling CO2 transformation. CO2 transformation reaction is the following:
CO2 +1120 karborne anhydra, Hco H+ Equation 1
9 This reaction is natural. It is at the basis of CO2 transportation and removal phenomenon in the human body and in most living beings. Reaction products are ions in solution in the aqueous liquid phase (6). The treated gas phase (5) exits at the top of the spray absorber bioreactor and is almost free of CO2. However, droplets of the liquid phase may remain in suspension in the purified gas exiting the bioreactor (5). An additional equipment, such as a mist eliminator, is thus preferably added to the spray absorber bioreactor to remove those droplets. Both gas and liquid phases are preferably further treated for proper disposal or reuse.
It is well known that under specific conditions, bicarbonate and/or carbonate ions may react with some cations (Na, Ca2+, Mg2+, Ba2+) to precipitate. For example, if the liquid phase contains calcium ions and the pH is around 9,0, bicarbonate and carbonate ions are present because of natural physicochemical equilibrium reactions. These carbonate ions may react with calcium ions (see Eq. 2 below), for example, by adding Ca(OH)2 to the solution, thus leading to the formation of solid particles of calcium carbonate in the liquid phase. Consequently, bicarbonate ions transform into carbonate ions, because of equilibrium between both species. Those newly formed carbonate ions will then lead to the formation of calcium carbonate. In this case, an agitation device is preferably required to facilitate discharge of solid particles. Moreover, the bottom of the bioreactor preferably has a conical shape.
C032- + Ca2+= CaCO3 Equation 2 Biocatalysts are usually costly material. Therefore, it is interesting to recycle the liquid phase containing the biocatalysts. Figure 2 shows a process implying steps described previously in figure 1. However, for the recycling of the liquid phase, additional considerations have to be made. CO2 removal process is based on absorption, thus removal of the reaction products (HCO3- and H+) is required in order to maintain optimal conditions for CO2 mass transfer. In this case, bicarbonate and hydrogen ions are soluble. Bicarbonate ions are preferably removed in a product removal process (11) such as membrane separation processes (ultrafiltration, nanofiltration), ion exchange or adsorption units separately or in combination.
Referring now to figure 2, the liquid phase containing biocatalysts and rich in reaction products (8) is fed to a product removal process (11). Two effluents (12,10) are 5 generated: one (12) rich in reaction product, bicarbonate ions and one
It is well known that under specific conditions, bicarbonate and/or carbonate ions may react with some cations (Na, Ca2+, Mg2+, Ba2+) to precipitate. For example, if the liquid phase contains calcium ions and the pH is around 9,0, bicarbonate and carbonate ions are present because of natural physicochemical equilibrium reactions. These carbonate ions may react with calcium ions (see Eq. 2 below), for example, by adding Ca(OH)2 to the solution, thus leading to the formation of solid particles of calcium carbonate in the liquid phase. Consequently, bicarbonate ions transform into carbonate ions, because of equilibrium between both species. Those newly formed carbonate ions will then lead to the formation of calcium carbonate. In this case, an agitation device is preferably required to facilitate discharge of solid particles. Moreover, the bottom of the bioreactor preferably has a conical shape.
C032- + Ca2+= CaCO3 Equation 2 Biocatalysts are usually costly material. Therefore, it is interesting to recycle the liquid phase containing the biocatalysts. Figure 2 shows a process implying steps described previously in figure 1. However, for the recycling of the liquid phase, additional considerations have to be made. CO2 removal process is based on absorption, thus removal of the reaction products (HCO3- and H+) is required in order to maintain optimal conditions for CO2 mass transfer. In this case, bicarbonate and hydrogen ions are soluble. Bicarbonate ions are preferably removed in a product removal process (11) such as membrane separation processes (ultrafiltration, nanofiltration), ion exchange or adsorption units separately or in combination.
Referring now to figure 2, the liquid phase containing biocatalysts and rich in reaction products (8) is fed to a product removal process (11). Two effluents (12,10) are 5 generated: one (12) rich in reaction product, bicarbonate ions and one
(10) containing a very low level of bicarbonate ions. This latter liquid phase is preferably enriched in fresh liquid phase (9) or biocatalysts to compensate for possible loss of those two components. Acid or alkali may also be added to the liquid phase in order to control pH
of the liquid phase. pH control may also be done inside the product removal process. In 10 the present application, alkali such as NaOH might be added to the liquid phase to neutralize protons produced during the biological transformation of CO2 (Equation 1).
The resultant liquid phase (7) enters at the top of the bioreactor. The effluent (12) is preferably further treated for proper disposal or use in another process.
Turning now to figures 3a and 3b, when solid particles are present in the liquid phase (14) because of a precipitation reaction (Eq. 2), solid particles have to be removed for recycling of the liquid phase. The particles removal process (15) may consist of one or more separation units, as shown in figure 3a. Separation is preferably performed by settling (by gravity, centrifugal force, heavy media, flotation, magnetic force) and/or filtration (on screens or on filters (by gravity, pressure, vacuum or centrifugal force)) and/or pression (batch presses or continuous presses (screw presses, rolls or belt presses)). Moreover, agents facilitating removal of particles such as coagulants or flocculants or filter aids may be added to the liquid effluent (16) prior to or in the particle removal process or to the liquid phase entering the spray absorber bioreactor (13).The liquid phase (18) exiting the particles removal process is preferably supplemented in fresh liquid phase and/or biocatalysts (9). Moreover, acid or alkali may also be added to liquid phase for pH control. The liquid phase (13) is then fed to the bioreactor. Solid particles (17) obtained may further be treated or be disposed of.
of the liquid phase. pH control may also be done inside the product removal process. In 10 the present application, alkali such as NaOH might be added to the liquid phase to neutralize protons produced during the biological transformation of CO2 (Equation 1).
The resultant liquid phase (7) enters at the top of the bioreactor. The effluent (12) is preferably further treated for proper disposal or use in another process.
Turning now to figures 3a and 3b, when solid particles are present in the liquid phase (14) because of a precipitation reaction (Eq. 2), solid particles have to be removed for recycling of the liquid phase. The particles removal process (15) may consist of one or more separation units, as shown in figure 3a. Separation is preferably performed by settling (by gravity, centrifugal force, heavy media, flotation, magnetic force) and/or filtration (on screens or on filters (by gravity, pressure, vacuum or centrifugal force)) and/or pression (batch presses or continuous presses (screw presses, rolls or belt presses)). Moreover, agents facilitating removal of particles such as coagulants or flocculants or filter aids may be added to the liquid effluent (16) prior to or in the particle removal process or to the liquid phase entering the spray absorber bioreactor (13).The liquid phase (18) exiting the particles removal process is preferably supplemented in fresh liquid phase and/or biocatalysts (9). Moreover, acid or alkali may also be added to liquid phase for pH control. The liquid phase (13) is then fed to the bioreactor. Solid particles (17) obtained may further be treated or be disposed of.
11 The separation unit may, in a particular case, be integrated to the bioreactor. Figure 3b shows a process where separation by gravity is integrated to the bioreactor.
In this particular case, an agitation device is preferably added at the bottom of the bioreactor and the bottom of the bioreactor preferably has a conical shape.
Example An experiment was conducted to validate the concept of a spray absorber for removal of CO2. The process diagram of the spray absorber for the test was similar to the one shown in figure 1. The spray absorber consists of a column having a 7,5 cm diameter and a 70 cm height. A pressure nozzle atomizer was mounted within the reaction chamber. Five litres of a 12 mM Tris solution with 20 mg carbonic anhydrase per litre of solution were pumped into the spray absorber at a flow rate of 1,5 l/min.
Carbonic anhydrase was used free within the Tris Solution. The Tris solution is a buffer consisting of 2-amino-2-hydroxymethy1-1,3-propanediol. The solution was used in a closed loop operation, until the Tris solution was saturated with dissolved CO2.The gas flow rate was 6,0 g/min at a CO2 concentration of 52000 ppm. Gas and solution were at room temperature. The pressure inside the spray absorber was set at 5 psig.
The results obtained showed that the CO2 contained in the gas phase was removed at a rate of 2,3 x 10-3 mol of CO2 /min.
These results were compared with the ones obtained from experiments conducted with a conventional bioreactor using a reaction chamber filled with carbonic anhydrase immobilized on rashig supports. The following table provides a comparison of these results.
,
In this particular case, an agitation device is preferably added at the bottom of the bioreactor and the bottom of the bioreactor preferably has a conical shape.
Example An experiment was conducted to validate the concept of a spray absorber for removal of CO2. The process diagram of the spray absorber for the test was similar to the one shown in figure 1. The spray absorber consists of a column having a 7,5 cm diameter and a 70 cm height. A pressure nozzle atomizer was mounted within the reaction chamber. Five litres of a 12 mM Tris solution with 20 mg carbonic anhydrase per litre of solution were pumped into the spray absorber at a flow rate of 1,5 l/min.
Carbonic anhydrase was used free within the Tris Solution. The Tris solution is a buffer consisting of 2-amino-2-hydroxymethy1-1,3-propanediol. The solution was used in a closed loop operation, until the Tris solution was saturated with dissolved CO2.The gas flow rate was 6,0 g/min at a CO2 concentration of 52000 ppm. Gas and solution were at room temperature. The pressure inside the spray absorber was set at 5 psig.
The results obtained showed that the CO2 contained in the gas phase was removed at a rate of 2,3 x 10-3 mol of CO2 /min.
These results were compared with the ones obtained from experiments conducted with a conventional bioreactor using a reaction chamber filled with carbonic anhydrase immobilized on rashig supports. The following table provides a comparison of these results.
,
12 Parameters Spray absorber Prior art packed according to the bioreactor invention Concentration of CO2 in 52000 pm 50000 ppm the gas phase Liquid flow rate 1,5 l/min 0,5 l/min Biocatalyst Carbonic anhydrase free Carbonic anhydrase in liquid immobilized in the bioreactor Gas flow rate 6,0 g/min 1,5 g/min Ratio of liquid flow rate to 0,25 1/g 0,5 1/g gas flow rate Mass of enzyme within the Less than 100 mg* 275 mg reactor Removal rate of CO2 2,3 x iO3 mol of CO2 /min 1,3 x 10-3 mol of CO2 /min * Five liters of Tris solution contains 100 mg. However, for the absoption of CO2, only a portion of the enzyme ends in the reaction chamber.
These results show that the process according to the invention is surprisingly more efficient than the process known in the prior art, since 1) at all times, the enzyme participating in the removal of CO2 is less, therefore the removal of CO2 requires less enzyme, and 2) even though the ratio of liquid flow rate to gas flow rate is lower with the process according to the invention, the removal rate of CO2 is greater.
Indeed, it is well known for a person skilled in the art that in a process for absorbing a gas, if that ratio decreases, the performance of the process also decreases. In other words, the performance of the packed bioreactor would have been even less if the ratio of liquid flow rate to gas flow rate used had been 0,25 1/g, as for the experiments with the spray absorber of the invention.
These results show that the process according to the invention is surprisingly more efficient than the process known in the prior art, since 1) at all times, the enzyme participating in the removal of CO2 is less, therefore the removal of CO2 requires less enzyme, and 2) even though the ratio of liquid flow rate to gas flow rate is lower with the process according to the invention, the removal rate of CO2 is greater.
Indeed, it is well known for a person skilled in the art that in a process for absorbing a gas, if that ratio decreases, the performance of the process also decreases. In other words, the performance of the packed bioreactor would have been even less if the ratio of liquid flow rate to gas flow rate used had been 0,25 1/g, as for the experiments with the spray absorber of the invention.
13 Although the present invention has been explained hereinabove by way of preferred embodiments thereof, it should be understood that the invention is not limited to these precise embodiments and that various changes and modifications may be effected therein without departing from the scope or spirit of the invention.
Claims (25)
1. A process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethyl-1,3-propanediol; and carbonic anhydrase;
in order to form droplets of the mixture; and contacting the CO2-containing gas with the droplets of the mixture such that the carbonic anhydrase catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase.
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethyl-1,3-propanediol; and carbonic anhydrase;
in order to form droplets of the mixture; and contacting the CO2-containing gas with the droplets of the mixture such that the carbonic anhydrase catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase.
2. The process of claim 1, wherein the carbonic anhydrase is immobilized with respect to supports within the aqueous liquid solution.
3. The process of claim 2, wherein the carbonic anhydrase is immobilized by fixation to a solid support, by entrapment inside a matrix, or by intermolecular binding of biocatalysts molecules or structures.
4. The process of claim 1, wherein the carbonic anhydrase is provided free in the aqueous liquid solution.
5. The process of any one of claims 1 to 4, comprising saturating the aqueous liquid solution with CO2.
6. A process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethyl-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture within the reaction chamber in presence of the carbonic anhydrase that catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase comprising mist of the aqueous liquid solution; and removing the mist from the CO2 depleted gas phase to produce a mist depleted gas.
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethyl-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture within the reaction chamber in presence of the carbonic anhydrase that catalyzes the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase comprising mist of the aqueous liquid solution; and removing the mist from the CO2 depleted gas phase to produce a mist depleted gas.
7. The process of claim 6, wherein the mist depleted gas is sent for disposal or reuse.
8. The process of claim 6 or 7, wherein recovered mist is reused in the process.
9. The process of any one of claims 6 to 8, wherein the carbonic anhydrase is immobilized with respect to supports within the aqueous liquid solution.
10. The process of claim 9, wherein the carbonic anhydrase is immobilized by fixation to a solid support, by entrapment inside a matrix, or by intermolecular binding of biocatalysts molecules or structures.
11. The process of any one of claims 6 to 8, wherein the carbonic anhydrase is provided free in the aqueous liquid solution.
12. The process of any one of claims 6 to 11, comprising saturating the aqueous liquid solution with CO2.
13. A process for enzymatic treatment of a CO2-containing gas, comprising:
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethyl-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture in presence of the carbonic anhydrase, the carbonic anhydrase catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a loaded liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase;
releasing the loaded liquid phase from the reaction chamber;
precipitating solid particles in the loaded liquid phase;
removing the precipitated solid particles from the loaded liquid phase to produce a precipitate removed liquid; and recycling the precipitate removed liquid back into the reaction chamber as the aqueous liquid solution.
spraying a mixture comprising:
an aqueous liquid solution comprising 2-amino-2-hydroxymethyl-1,3-propanediol; and carbonic anhydrase;
into a reaction chamber;
contacting the CO2-containing gas with the mixture in presence of the carbonic anhydrase, the carbonic anhydrase catalyzing the hydration reaction of CO2 into bicarbonate and hydrogen ions, thereby producing a loaded liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase;
releasing the loaded liquid phase from the reaction chamber;
precipitating solid particles in the loaded liquid phase;
removing the precipitated solid particles from the loaded liquid phase to produce a precipitate removed liquid; and recycling the precipitate removed liquid back into the reaction chamber as the aqueous liquid solution.
14. The process of claim 13, wherein the step of removing the precipitated solid particles comprises filtration.
15. The process of claim 14, wherein the filtration utilizes a membrane selected from a flat membrane, a tubular membrane, a plate-and-frame membrane, a spiral-wound membrane, a tubular capillary membrane, a hollow fibre membrane, a dead-end membrane, a cross-flow membrane with co-current, cross-current, cross-flow with perfect permeate mixing and perfect mixing, in single-stage or multi-stage, in a single-pass or a recirculation system.
16. The process of claim 13, wherein the step of removing the precipitated solid particles comprises settling.
17. The process of claim 13, wherein the step of removing the precipitated solid particles comprises one or more separation units selected from gravity settling, centrifugal force, heavy media, flotation, magnetic force, filtration with screens or filters, with gravity, pressure, vacuum or centrifugal force, or batch pressing or continuous presses with a screw press, rolls or belt press.
18. The process of any one of claims 13 to 17, further comprising agitating to facilitate discharge of the precipitated solid particles from the reaction chamber.
19. The process of any one of claims 13 to 18, wherein the reaction chamber has a bottom with a conical shape.
20. The process of claim 13, wherein the step of removing the precipitated solid particles comprises addition of an agent facilitating removal of the precipitated solid particles.
21. The process of claim 20, wherein the agent comprises a coagulant, a flocculant or a filter aid.
22. The process of claim 20 or 21, wherein the agent is added to the loaded liquid phase prior to or in the removal step or to the liquid phase entering the reaction chamber.
23. The process of any one of claims 13 to 22, comprising controlling pH of the aqueous liquid solution.
24. The process of claim 13, wherein the step of removing the precipitated solid particles comprises utilizing a separation unit integrated to the reaction chamber.
25. The method of any one of claims 1 to 24, wherein the CO2-containing gas has a CO2 concentration of at least 52000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2783190A CA2783190C (en) | 2002-12-19 | 2003-12-18 | Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002414871A CA2414871A1 (en) | 2002-12-19 | 2002-12-19 | Process and apparatus using a spray absorber bioreactor for the biocatalytic treatment of gases |
| CA2,414,871 | 2002-12-19 | ||
| CA2509989A CA2509989C (en) | 2002-12-19 | 2003-12-18 | Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase |
| CA2783190A CA2783190C (en) | 2002-12-19 | 2003-12-18 | Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase |
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| CA2509989A Division CA2509989C (en) | 2002-12-19 | 2003-12-18 | Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase |
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| CA2783190A1 CA2783190A1 (en) | 2004-07-08 |
| CA2783190C true CA2783190C (en) | 2015-06-16 |
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| CA2783190A Expired - Lifetime CA2783190C (en) | 2002-12-19 | 2003-12-18 | Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase |
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| WO2006089423A1 (en) * | 2005-02-24 | 2006-08-31 | Co2 Solution Inc. | An improved co2 absorption solution |
| EP2678094A4 (en) * | 2011-02-03 | 2014-12-10 | Co2 Solutions Inc | C02 treatments using enzymatic particles sized according to reactive liquid film thickness for enhanced catalysis |
| CA2886708C (en) * | 2015-03-30 | 2023-09-26 | Co2 Solutions Inc. | Intensification of biocatalytic gas absorption |
| CN115999357B (en) * | 2022-11-30 | 2024-03-15 | 中国船舶集团有限公司第七一一研究所 | Carbon dioxide capturing system and method for ship power |
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| CA2509989C (en) | 2012-12-04 |
| CA2509989A1 (en) | 2004-07-08 |
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