CA2509989C - 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 PDF

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CA2509989C
CA2509989C CA2509989A CA2509989A CA2509989C CA 2509989 C CA2509989 C CA 2509989C CA 2509989 A CA2509989 A CA 2509989A CA 2509989 A CA2509989 A CA 2509989A CA 2509989 C CA2509989 C CA 2509989C
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carbonic anhydrase
gas
liquid
reaction
treatment unit
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CA2509989A1 (en
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Sylvie Fradette
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Saipem SpA
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Co2 Solutions Inc
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84Biological processes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Apparatus Associated With Microorganisms And Enzymes (AREA)
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Abstract

A process using a spray absorber bioreactor for the biocatalytic treatment of gases is disclosed. The process comprises the steps of contacting a gas phase, containing a gas to be treated, to a liquid phase containing a reactant capable of chemically reacting with and/or absorbing 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 is characterized in that the gas phase is contacted to spray droplets of liquid phase containing biocatalysts.
The use of droplets of liquid containing the biocatalysts 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.
This process can advantageously be used for cleaning or purifying a gas phase containing a harmful gas. For example, it can be used for extracting CO2 from a gas emission.

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 Al; 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 metabolic 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
3 CO2 by photosynthetic organisms (JP 03-216180) and similar processes bind CO2 through algae (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, C02 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
4 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:
5 PCT/CA2003/001989 - 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.

5 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 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
6 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.
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
7 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.

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
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 C02-containing gas, comprising the steps of:
a) contacting the C02-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 C02-containing gas, comprising:

a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving the C02-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 C02-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 C02-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 002.

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 arbo HCO3+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 C02-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 C02-containing effluent gas into the droplets; the reaction (I) is a forward reaction catalyzing the hydration of dissolved C02 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 C02-containing gas, comprising:

a bioreactor comprising a reaction chamber having a liquid inlet for receiving a liquid, a gas inlet for receiving the C02-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 (I) with carbonic anhydrase, wherein the reaction (I) is as follows:

C02 +H20 erbonic HCO3 +H+ (1) 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 C02-containing gas; the bioreactor comprises a gas inlet for feeding the C02-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 C02 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 C02-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.

The present invention also provides a process for enzymatic treatment of a C02-containing gas, comprising:

8d contacting the C02-containing gas with an aqueous liquid solution comprising a buffer compound in presence of 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.

The present invention also provides a process for enzymatic treatment of a C02-containing gas, comprising:
spraying an aqueous liquid solution into a reaction chamber;

contacting the C02-containing gas with the aqueous liquid solution within the reaction chamber in presence of 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.

The present invention also provides a process for enzymatic treatment of a C02-containing gas, comprising:
spraying an aqueous liquid solution into a reaction chamber; and contacting the C02-containing gas with an aqueous liquid solution in presence of carbonic anhydrase that is entrapped inside a matrix, the carbonic anhydrase catalyzing the hydration reaction of C02 into bicarbonate and hydrogen ions, thereby producing a liquid phase containing the bicarbonate and hydrogen ions and a treated CO2 depleted gas phase.

8e The present invention also provides a process for enzymatic treatment of a C02-containing gas, comprising:
spraying an aqueous liquid solution into a reaction chamber; and contacting the C02-containing gas with an aqueous liquid solution in presence of 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 C02 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.

The present invention also provides a method of reducing the ratio of liquid flow rate to gas flow rate in a carbonic anhydrase C02 absorption bioreactor and decreasing an amount of carbonic anhydrase for achieving a enzymatically catalyzed C02 removal rate, by spraying an aqueous liquid solution comprising carbonic anhydrase into the bioreactor.

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.

8f 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:

C02 +H20 e`b `` a"''yd`I 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+, Cat+, Mgt+, Bat+) 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" + Ca 2+ = 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 (HC03 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 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 5 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 the present application, alkali such as NaOH might be added to the liquid phase to neutralize protons produced during the biological transformation
10 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 expression (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.

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.
11 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 I/min. Carbonic anhydrase was used free within the Tris Solution. The Tris solution is a buffer consisting of 2-amino-2-hydroxymethyl-1,3-propanediol.
The solution was used in a closed loop operation, until the Tris solution was saturated with dissolved C02.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 I/min 0,5 I/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 I/g 0,5 I/g gas flow rate Mass of enzyme within the Less than 100 mg* 275 mg reactor Removal rate of CO2 2,3 x 10 mol of CO2 /min 1,3 x 10 moI of CO2 /min * Five liters of Tris solution contains 100 mg. However, for the absoption of C02, 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 I/g, as for the experiments with the spray absorber of the invention.

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
13 these precise embodiments and that various changes and modifications may be effected therein without departing from the scope or spirit of the invention.

Claims (58)

1. 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.
2. The process of claim 1, comprising removing from the spent liquid phase at least one of the bicarbonate and hydrogen ions, thereby obtaining a recycled liquid phase substantially free of the ions and containing the enzymatic particles;
and recycling the recycled liquid phase to re-contact the CO2-containing gas.
3. The process of claim 2, wherein the removing is performed by a separation process selected from the group consisting of precipitation, membrane filtration, ion exchange and adsorption.
4. The process of any one of claims 1 to 3, comprising removing mist contained in the treated gas phase.
5. The process of any one of claims 1 to 4, wherein the enzymatic particles comprise a support and the carbonic anhydrase are immobilized with respect to the support.
6. The process of any one of claims 1 to 4, wherein the enzymatic particles comprise a solid support and the carbonic anhydrase are immobilized with respect to the solid support.
7. The process of any one of claims 1 to 4, wherein the enzymatic particles comprise a solid support and the carbonic anhydrase are fixed with respect to the solid support.
8. The process of any one of claims 1 to 4, wherein the enzymatic particles comprise a matrix and the carbonic anhydrase are entrapped inside the matrix.
9. The process of any one of claims 1 to 4, wherein the enzymatic particles are formed of intermolecular binding of carbonic anhydrase molecules.
10. The process of any one of claims 1 to 9, wherein the liquid solution is an aqueous liquid phase containing H2O as a reactant.
11. The process of any one of claims 1 to 10, comprising reacting the bicarbonate ions contained in the spent liquid with cations selected from the group consisting of calcium ions, magnesium ions and baryum ions, thereby producing a solution containing carbonate of said cations ; and precipitating the carbonate.
12. The process of claim 11, wherein the cations are calcium ions.
13. The process of claim 12, comprising mixing the spent liquid phase with Ca(OH)2, thereby providing the calcium ions.
14. A process for treatment of a fluid by enzymatic catalysis of reaction (I) with carbonic anhydrase, wherein the reaction (I) is as follows:

CO2+H2O 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.
15. The process of claim 14, 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 to dissolve CO2 from the CO2-containing effluent gas into the droplets; the reaction (I) 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.
16. The process of claim 15, comprising removing from the spent liquid phase at least one of the bicarbonate and hydrogen ions, thereby obtaining a recycled liquid phase substantially free of the ions and containing the enzymatic particles;
and recycling the recycled liquid phase to re-contact the CO2-containing gas.
17. The process of claim 16, wherein the removing is performed by a separation process selected from the group consisting of precipitation, membrane filtration, ion exchange and adsorption.
18. The process of any one of claims 15 to 17, comprising removing mist contained in the treated gas phase.
19. The process of any one of claims 15 to 18, wherein the liquid solution is an aqueous liquid phase containing H2O as a reactant.
20. The process of any one of claims 15 to 19, comprising reacting the bicarbonate ions contained in the spent liquid with cations selected from the group consisting of calcium ions, magnesium ions and baryum ions, thereby producing a solution containing carbonate of said cations ; and precipitating the carbonate.
21. The process of claim 20, wherein the cations are calcium ions.
22. The process of claim 21, comprising mixing the spent liquid phase with Ca(OH)2, thereby providing the calcium ions.
23. The process of any one of claims 14 to 22, wherein the enzymatic particles comprise a support and the carbonic anhydrase are immobilized with respect to the support.
24. The process of any one of claims 14 to 22, wherein the enzymatic particles comprise a solid support and the carbonic anhydrase are immobilized with respect to the solid support.
25. The process of any one of claims 14 to 22, wherein the enzymatic particles comprise a solid support and the carbonic anhydrase are fixed with respect to the solid support.
26. The process of any one of claims 14 to 22, wherein the enzymatic particles comprise a matrix and the carbonic anhydrase are entrapped inside the matrix.
27. The process of any one of claims 14 to 22, wherein the enzymatic particles are formed of intermolecular binding of carbonic anhydrase molecules.
28. 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.
29. The carbonic anhydrase treatment unit of claim 28, wherein the atomizer comprises pressure nozzles.
30. The carbonic anhydrase treatment unit of claim 28 or 29, wherein the atomizer comprises two fluid nozzles.
31. The carbonic anhydrase treatment unit of any one of claims 28 to 30, wherein the atomizer comprises rotary devices.
32. The carbonic anhydrase treatment unit of any one of claims 28 to 31, comprising a separation unit in fluid communication with the liquid outlet for removing reaction products contained in the spent liquid, the separation having a first liquid outlet for discharging a liquid portion substantially free of the reaction products and a second outlet for discharging liquid portion containing the reaction products;
and means for conveying the portion substantially free of the reaction products to the mixing unit.
33. The carbonic anhydrase treatment unit of claim 32, wherein the separation unit is a filtration unit.
34. The carbonic anhydrase treatment unit of claim 32, wherein the separation unit is an ion exchange unit.
35. The carbonic anhydrase treatment unit of claim 32, wherein the separation unit is a precipitation unit.
36. The carbonic anhydrase treatment unit of claim 32, wherein the separation unit is an adsorption unit.
37. The carbonic anhydrase treatment unit of any one of claims 28 to 36, comprising means for removing mist contained in the treated gas.
38. The carbonic anhydrase treatment unit of any one of claims 28 to 37, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a support, the carbonic anhydrase being immobilized with respect to the support.
39. The carbonic anhydrase treatment unit of any one of claims 28 to 37, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a solid support, the carbonic anhydrase being immobilized with respect to the solid support.
40. The carbonic anhydrase treatment unit of any one of claims 28 to 37, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a solid support, the carbonic anhydrase being fixed with respect to the solid support.
41. The carbonic anhydrase treatment unit of any one of claims 28 to 37, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a matrix, the carbonic anhydrase being entrapped inside the matrix.
42. The carbonic anhydrase treatment unit of any one of claims 28 to 37, wherein the atomizer is sized and operated so as to spray the enzymatic particles being formed of intermolecular binding of carbonic anhydrase molecules.
43. A carbonic anhydrase treatment unit for the treatment of a fluid by enzymatic catalysis of reaction (I) with carbonic anhydrase, wherein the reaction (I) is as follows:

CO2+H2O HCO~ + H+ (I) the treatment unit comprising:

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.
44. The carbonic anhydrase treatment unit of claim 43, wherein the fluid is a 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.
45. The carbonic anhydrase treatment unit of claim 44, wherein the atomizer comprises pressure nozzles.
46. The carbonic anhydrase treatment unit of claim 44 or 45, wherein the atomizer comprises two fluid nozzles.
47. The carbonic anhydrase treatment unit of any one of claims 44 to 46, wherein the atomizer comprises rotary devices.
48. The carbonic anhydrase treatment unit of any one of claims 44 to 47, comprising a separation unit in fluid communication with the liquid outlet for removing reaction products contained in the spent liquid, the separation having a first liquid outlet for discharging a liquid portion substantially free of the reaction products and a second outlet for discharging liquid portion containing the reaction products;
and means for conveying the portion substantially free of the reaction products to the mixing unit.
49. The carbonic anhydrase treatment unit of claim 48, wherein the separation unit is a filtration unit.
50. The carbonic anhydrase treatment unit of claim 48, wherein the separation unit is an ion exchange unit.
51. The carbonic anhydrase treatment unit of claim 48, wherein the separation unit is a precipitation unit.
52. The carbonic anhydrase treatment unit of claim 48, wherein the separation unit is an adsorption unit.
53. The carbonic anhydrase treatment unit of any one of claims 44 to 52, comprising means for removing mist contained in the treated gas.
54. The carbonic anhydrase treatment unit of any one of claims 43 to 53, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a support, the carbonic anhydrase being immobilized with respect to the support.
55. The carbonic anhydrase treatment unit of any one of claims 43 to 53, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a solid support, the carbonic anhydrase being immobilized with respect to the solid support.
56. The carbonic anhydrase treatment unit of any one of claims 43 to 53, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a solid support, the carbonic anhydrase being fixed with respect to the solid support.
57. The carbonic anhydrase treatment unit of any one of claims 43 to 53, wherein the atomizer is sized and operated so as to spray the enzymatic particles comprising a matrix, the carbonic anhydrase being entrapped inside the matrix.
58. The carbonic anhydrase treatment unit of any one of claims 43 to 53, wherein the atomizer is sized and operated so as to spray the enzymatic particles being formed of intermolecular binding of carbonic anhydrase molecules.
CA2509989A 2002-12-19 2003-12-18 Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase Expired - Lifetime CA2509989C (en)

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CA002414871A CA2414871A1 (en) 2002-12-19 2002-12-19 Process and apparatus using a spray absorber bioreactor for the biocatalytic treatment of gases
CA2509989A CA2509989C (en) 2002-12-19 2003-12-18 Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase
PCT/CA2003/001989 WO2004056455A1 (en) 2002-12-19 2003-12-18 Process and apparatus using a spray absorber bioreactor for the biocatalytic treatment of gases

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