US008329458B2
`
`(12) United States Patent
`Parent et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 8,329,458 B2
`*Dec. 11, 2012
`
`(54) CARBONIC ANHYDRASE BIOREACTOR
`AND PROCESS FOR CO2 CONTAINING GAS
`EFFLUENT TREATMENT
`
`(75)
`
`Inventors:
`
`Carmen Parent, Quebec (CA); Fr6d6ric
`Dutil, Qu6bec (CA)
`
`(73) Assignee:
`
`CO2 Solutions Inc., Quebec (CA)
`
`(*) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`
`This patent is subject to a terminal dis-
`claimer.
`
`(21) Appl. No.: 12/802,353
`
`(22) Filed:
`
`Jun. 4,2010
`
`(65)
`
`(60)
`
`Prior Publication Data
`
`US 2010/0248323 A1
`
`Sep. 30, 2010
`
`Related U.S. Application Data
`
`Continuation of application No. 12/462,612, filed on
`Aug. 5, 2009, which is a continuation of application
`No. 11/646,758, filed on Dec. 27, 2006, now Pat. No.
`7,579,185, which is a division of application No.
`10/195,848, filed on Jul. 12, 2002, now Pat. No.
`7,176,017.
`
`(30)
`
`Foreign Application Priority Data
`
`Jul. 13, 2001
`
`(CA) ...................................... 2353307
`
`(51)
`
`Int. CI.
`C12M 1/12
`(2006.01)
`C12M 1/14
`(2006.01)
`C12M 3/04
`(2006.01)
`C12M 1/36
`(2006.01)
`C12M 1/38
`(2006.01)
`C12M 1/00
`(2006.01)
`C12M 3/00
`(2006.01)
`(52) U.S. CI ................ 435/299.1; 435/297.1; 435/286.6;
`435/289.1; 435/296.1
`(58) Field of Classification Search ..... 435/283.1 309.4
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`534,498 A
`
`2/1895 Descamps
`
`(Continued)
`
`AU
`
`FOREIGN PATENT DOCUMENTS
`7753398
`12/1998
`(Continued)
`
`OTHER PUBLICATIONS
`
`John R Allen PhD, "An Enzymic Concept for CO2 Control in Closed
`Environmental Control Systems," Technical Report AFFDL-TR-65-
`48, Aug. 1965, 56 pages, Air Force Flight Dynamics Laboratory,
`Research Technology Division, Air Force Systems Command,
`Wright-Patterson Air Force Base, Ohio, USA (56 pages).
`
`(Continued)
`Primary Examiner Nathan Bowers
`Assistant Examiner Lydia Edwards
`(74) Attorney, Agent, or Firm Ware, Fressola, Van Der
`Sluys & Adolphson LLP
`
`ABSTRACT
`(57)
`A triphasic bioreactor for physico-chemically treating a gas is
`disclosed. The triphasic bioreactor comprises a reaction
`chamber with a liquid and biocatalysts in suspension in the
`liquid, for catalyzing a reaction between the gas and the liquid
`to obtain a treated gas and a solution containing a reaction
`product. A gas bubbling means is provided in the reaction
`chamber for bubbling the gas to be treated into the liquid
`thereby dissolving the gas into the liquid and increasing a
`pressure inside the reaction chamber. The bioreactor further
`comprises a liquid inlet in fluid communication with the
`reaction chamber for receiving the liquid and filling the reac-
`tion chamber, a liquid outlet in fluid communication with the
`reaction chamber for releasing the solution and a gas outlet in
`fluid communication with the reaction chamber to release the
`treated gas. The bioreactor further comprises a retention
`device to retain the biocatalysts in the reaction chamber. The
`invention also concerns a process using the triphasic bioreac-
`tor. The triphasic bioreactor may advantageously be used for
`removing carbonic dioxide from a CO2-containing gas.
`
`43 Claims, 4 Drawing Sheets
`
`Akermin, Inc.
`Exhibit 1001
`Page 1
`
`

`

`US 8,329,458 B2
`Page 2
`
`U.S. PATENT
`
`DOCUMENTS
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`
`FOREIGN PATENT DOCUMENTS
`
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`
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`
`Akermin, Inc.
`Exhibit 1001
`Page 2
`
`

`

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`US 8,329,458 B2
`Page 3
`
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`* cited by examiner
`
`Akermin, Inc.
`Exhibit 1001
`Page 3
`
`

`

`U.S. Patent
`
`Dec. 11, 2012
`
`Sheet 1 of 4
`
`US 8,329,458 B2
`
`Akermin, Inc.
`Exhibit 1001
`Page 4
`
`

`

`U.S. Patent
`
`Dec. 11, 2012
`
`Sheet 2 of 4
`
`US 8,329,458 B2
`
`23J
`
`27~
`
`o
`
`o o
`
`O
`
`O o o O
`O
`
`~16
`--2z, 6
`
`29
`
` nnnnnvnvunnuunnunul
`
`FIG. 2
`
`Akermin, Inc.
`Exhibit 1001
`Page 5
`
`

`

`U.S. Patent
`
`Dec. 11, 2012
`
`Sheet 3 of 4
`
`US 8,329,458 B2
`
`j2
`
`~-3
`
`~15
`
`......_.- 19
`
`6
`
`I
`
`1
`
`FIG.
`
`FIG.
`
`FIG. 5
`
`Akermin, Inc.
`Exhibit 1001
`Page 6
`
`

`

`U.S. Patent
`
`Dec. 11, 2012
`
`Sheet 4 of 4
`
`US 8,329,458 B2
`
`Akermin, Inc.
`Exhibit 1001
`Page 7
`
`

`

`US 8,329,458 B2
`
`1
`CARBONIC ANHYDRASE BIOREACTOR
`AND PROCESS FOR CO2 CONTAINING GAS
`EFFLUENT TREATMENT
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`
`This application is a continuation ofU.S. Ser. No. 12/462,
`612 filedAug. 5, 2009 which is a continuation application of
`U.S. Ser. No. 11/646,758 filed Dec. 27, 2006 now U.S. Pat. 10
`No. 7,579,185 which is a divisional ofU.S. Ser. No. 10,/195,
`848 filed Jul. 12, 2002 now U.S. Pat. No. 7,176,017. This
`application also claims priority from Canadian application
`No. 2,353,307 filed Jul. 13, 2001. The aforementioned appli-
`cations are incorporated herein by reference in their entirety. 15
`
`FIELD OF THE INVENTION
`
`2
`5,250,305; WO97/19196; JP63-129987). Efficient enzymatic
`conversion and treatability itself of gaseous waste or effluents
`in liquids therefore depend on adequate and sufficient disso-
`lution of the gaseous phase in the liquid phase. However, the
`5 adequate dissolution of gaseous waste or effluents into liquids
`for enzymatic conversion poses a real problem which consti-
`tutes the first of a series of important limitations which com-
`pound 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 applica-
`tions, their utilization remains quite limited in the area of
`biochemical gas treatment (U.S. Pat. No. 6,245,304; U.S. Pat.
`No. 4,743,545). Also known in the prior art are the GLS
`bioprocesses abundantly reported in the literature. A maj ority
`of these concerns wastewater treatment (JP09057289). 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
`25 these systems is the non retention ofthe solid phase within the
`is 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 gas-
`eous emissions, namely carbon dioxide. Certain bioreactors
`30 allow the uptake of CO2 by photosynthetic organisms
`(CA229101; JP03-216180) and similar processes bind CO~
`through algae (CA2232707; JP08-116965; JP04-190782;
`JP04-075537). However, the biocatalyst retention problem
`remains largely unaddressed and constitutes another serious
`35 limitation, along with gaseous effluent dissolution, to further
`technological advancements.
`The main argument against the use of ultrafiltration mem-
`branes to solve this biocatalyst retention problem is their
`propensity to clogging. Clogging renders them unattractive
`40 and so their use is rather limited for the retention of catalysts
`within reactors. However, a photobioreactor for medical
`applications as an artificial lung (WO9200380; U.S. Pat. No.
`5,614,378) and an oxygen recovery system (U.S. Pat. No.
`4,602,987; U.S. Pat. No. 4,761,209) are notable exceptions
`45 making use of carbonic anhydxase and an ultrafiltration unit.
`The patent applications held by the assignee, CO2 Solution
`Inc., via l,es Systbmes F, nvirobio Inc. (EP0991462;
`WO9855210; CA2291785) proposes a packed colunm for the
`treatment of carbon dioxide using immobilized carbonic
`5o anhydxase without the use of an ultrafiltration membrane.
`Carbonic anhydxase is a readily available and highly reactive
`enzyme that is used in other systems for the reduction of
`carbon dioxide emissions (U.S. Pat. No. 4,602,987; U.S. Pat.
`No. 4,743,545; U.S. Pat. No. 5,614,378; U.S. Pat. No. 6,257,
`55 335). In the system described by Trachtenberg for the car-
`bonic anhydrase treatment of gaseous effluents (U.S. Pat. No.
`6,143,556; CA2222030), to biocatalyst retention occurs
`through a porous wall or through enzyme immobilization.
`However, important dxawbacks are associated with the use of
`6o enzyme immobilization, as will be discussed below.
`Other maj or dxawbacks are associated with the use of enzy-
`matic systems. One of these stems from systems where enzy-
`matic activity is specifically and locally concentrated. This is
`the case with systems where enzymes are immobilized at a
`65 particular site or on a specific part of an apparatus. Examples
`in point of such systems are those where enzymes are immo-
`bilized on a filtration membrane (JP60014900008A2; U.S.
`
`This invention relates to the field of gas effluent treatment
`and air purification. More specifically, it concerns a triphasic 2o
`bioreactor for the biological treatment of gaseous effluent.
`The invention also concerns a triphasic process for the bio-
`logical treatment of gas effluent.
`
`BACKGROUND
`
`Contemporary industrial activities generate gaseous efflu-
`ents containing a multitude of chemical compounds and con-
`taminants which interfere with the equilibrium of elements in
`nature and affect the environment at different levels. Acid
`rain, the green-house effect, smog and the deterioration of the
`ozone layer are examples that speak volumes about this prob-
`lem. Reduction of noxious emissions is therefore not surpris-
`ingly the subj ect 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. Con-
`sequently, there is a real need for new apparatus and methods
`aimed at the biological treatment of gaseous waste or efflu-
`ents.
`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; JP2000-236870), fermentation by anaerobic bacte-
`ria (WO 98/00558), photosynthesis through either plants (CA
`2,029,101 A1; JP04-190782) 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 aque-
`ous phase, or biofilter columns comprising immobilized resi-
`dent microorganisms (Deshusses et al. (1996) Biotechnol.
`Bioeng. 49, 587-598). Although such biofilters have contrib-
`uted to technological advances within the field of 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 ($5250305; U.S. Pat. No. 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 (U.S. Pat. No. 5,130,237; U.S.
`Pat. No. 4,033,822; U.S. Pat. No. 4,758,417; U.S. Pat. No.
`
`Akermin, Inc.
`Exhibit 1001
`Page 8
`
`

`

`US 8,329,458 B2
`
`3
`Pat. No. 4,033,822; U.S. Pat. No. 5,130,237; U.S. Pat. No.
`5,250,305; JP54-132291; JP63-129987; JP02-109986;
`DE3937892) or even, at a gas-liquid phase boundary (WO96/
`40414; U.S. Pat. No. 6,143,556). The limited surface contact
`area obtainable between the dissolved gas substrate, the liq-
`uid and the enzyme’ s 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 effluent are given in the following
`documents: CA2160311; CA2238323; CA2259492;
`CA2268641; JP2000-236870; JP2000-287679; JP2000-
`202239; U.S. Pat. No. 4,758,417; U.S. Pat. No. 5,593,886;
`U.S. Pat. No. 5,807,722; U.S. Pat. No. 6,136,577; and U.S.
`Pat. No. 6,245,304.
`
`SUMMARY OF THE INVENTION
`
`An object of the present invention is to provide an appara-
`tus 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.
`In accordance with the present invention, that object is
`achieved with a triphasic bioreactor for physico-chemically
`treating a gas effluent. The triphasic bioreactor comprises a
`reaction chamber, a liquid inlet and gas and liquid outlets in
`fluid communication with the reaction chamber. A gas bub-
`bling means is also provided within the reaction chamber for
`receiving the gas to be treated. The reaction chamber is filled
`with biocatalysts in suspension in a liquid, for catalyzing a
`reaction between the gas and the liquid to obtain a treated gas
`and a solution containing a reaction product. The liquid is
`preferably an aqueous or organic solution of an appropriate
`composition with respect to the desired catalytic reaction.
`The liquid inlet is for receiving the liquid into the reaction
`chamber and filling it. The gas bubbling means is also for
`bubbling the gas to be treated into the liquid thereby both
`dissolving it into the liquid and increasing the gas pressure
`inside the reaction chamber. The bioreactor further comprises
`a retention device for retaining the biocatalysts within the
`reaction chamber while the liquid outlet allows for the pres-
`sure release of the solution containing the reaction product.
`The triphasic bioreactor of the present invention provides
`the advantages of biologically treating gaseous waste and
`effluents while simultaneously providing biocatalysts in liq-
`uid suspension, optimizing gas phase dissolution into the
`liquid phase and thereby optimizing surface contact area
`between the gas, liquid and solid phases, as well as retaining
`the biocatalysts within the reactor while allowing the pressure
`release of liquid containing a reaction product exempt of
`biocatalysts.
`In accordance with a preferred aspect of the invention, the
`bioreactor comprises a pressure regulating valve to control a
`pressure created by the gas bubbled within the reaction cham-
`ber and a sampling means for sampling and analyzing liquid
`from the reaction chamber.
`The gas bubbling means preferably comprises a gas inlet of
`the reaction chamber to receive the gas to be treated and a
`bubbler located in a bottom portion of the reaction chamber.
`The bubbler has a gas inlet connected to the gas inlet of the
`reaction chamber and a plurality of gas outlets to diffuse the
`gas in the reaction chamber. The gas bubbling means further
`
`4
`comprises a pipe to connect the gas inlet of the reaction
`chamber to the gas inlet of the bubbler.
`The biocatalysts used in the bioreactor are preferably
`selected from the group consisting of enzymes, liposomes,
`5 microorganisms, animal cells, plant cells and a combination
`
`thereof. Most preferably, the biocatalysts are entrapped in
`porous substrates pervading the reaction chamber. Alterna-
`tively, the biocatalysts may be carried by the liquid that feeds
`the reaction chamber.
`10 The retention device preferably comprises a filter having
`
`15
`
`pores with a smaller diameter than the diameter of the bio-
`catalysts. More preferably, the filter is a membrane filter.
`In accordance with a first preferred embodiment, the mem-
`brane filter is located inside the reaction chamber upstremn
`from the liquid outlet.
`In accordance with a second preferred embodiment, the
`membrane filter is located outside the reaction chamber. In
`such a case, the retention device further comprises a first
`2o piping means and a second piping means. The first piping
`means is for piping liquid, which contains biocatalysts and
`reaction products, from the liquid outlet of the reaction cham-
`ber to the membrane filter where a permeate liquid containing
`the reaction products is separated from a retentate liquid
`25 containing the biocatalysts. The second piping means is for
`piping the retentate liquid to the liquid inlet of the bioreactor.
`In accordance with a preferred aspect of the invention, the
`triphasic bioreactor is used for reducing carbon dioxide con-
`tained in a gas effluent, in such a case, the gas effluent to be
`30 treated contains carbon dioxide, the liquid filling the biore-
`actor is an aqueous liquid and the biocatalysts are enzymes
`capable of catalyzing the chemical conversion of the dis-
`solved carbon dioxide into an aqueous solution containing
`hydrogen ions and bicarbonate ions. More preferably, the
`35 enzymes are carbonic anhydrase.
`In accordance with a still further preferred aspect of the
`invention, the bioreactor comprises an additional reaction
`chamber, as defined hereinabove, in series with the reaction
`chamber, hereinafter referred to as the first reaction chamber,
`4o to further treat the previously treated gas. In such a case, the
`biocatalysts filling the first reaction chamber are preferably
`different from the biocatalysts filling the additional reaction
`chamber.
`The present invention also provides a method for the bi0-
`45 catalytic treatment of gas effluent which is basically a three-
`step process.
`First, a reaction chamber filled with biocatalysts is filled
`with a liquid thereby suspending the biocatalysts in the liquid.
`Second, a gas to be treated is bubbled into the liquid thereby
`5o dissolving it into the liquid and creating a pressure inside the
`reaction chamber. The bubbling thereby promotes the bio-
`catalytic reaction between the liquid and the gas to be treated
`in order to obtain a treated gas and a solution containing a
`reaction product. Third, the solution containing the reaction
`55 product is released by pressure from the reaction chamber
`whilst retaining the biocatalysts within the reaction chamber.
`During the second and third steps, the pressure is controlled
`within the reaction chamber and treated gas is released from
`the reaction chamber.
`
`60
`
`BRIEF DESCRIPTION OF THE DRAWINGS
`
`Other objects and advantages of the invention will become
`apparent upon reading the detailed description and upon
`65 referring to the dxawings in which:
`FIG. 1 is a cross-sectional side view ofa triphasic bioreac-
`tor according to a first preferred embodiment of the invention.
`
`Akermin, Inc.
`Exhibit 1001
`Page 9
`
`

`

`US 8,329,458 B2
`
`5
`FIG. 2 is a schematic side view of a triphasic bioreactor
`according to a second is preferred embodiment of the inven-
`tion having an external tangential flow filter.
`FIG. 3 is a schematic side view of a triphasic bioreactor
`according to another embodiment of the invention, having an
`integrated filter.
`FIG. 4 is a schematic side view of a triphasic bioreactor
`according to a further embodiment, having an integrated tan-
`gential flow filter.
`FIG. 5 is a schematic side view of a triphasic bioreactor
`according to a still further embodiment, having a filter car-
`tridge.
`FIG. 6 is a schematic side view of a series of linked tripha-
`sic bioreactors for the treatment of gas effluent.
`While the invention will be described in conjunction with
`example embodiments, it will be understood that it is not
`intended to limit the scope of the invention to such embodi-
`ments. On the contrary, it is intended to cover all alternatives,
`modifications and equivalents as may be included as defined
`by the appended claims.
`
`DETAILED DESCRIPTION OF PREFERRED
`EMBODIMENTS OF THE INVENTION
`
`Referring to FIG. 1 or 2, the triphasic bioreactor (1) is an
`apparatus for physico-chemically treating a gas (10). Mini-
`mally, it features a reaction chamber (2) filled with biocata-
`lysts (4) in suspension in a liquid (3), a liquid inlet (5) and
`liquid (6) and gas (7) outlets in fluid communication with the
`reaction chamber (2). It is worth noting that the use of the
`article %" means "at least one" and hence a triphasic biore-
`actor according to the invention may advantageously com-
`prise more than one reaction chamber, and/or more than one
`liquid and gas is outlet and inlets. The liquid inlet (5) is for
`receiving the liquid (3) and filling the reaction chamber (2).
`The reaction chamber (2) is made of an appropriate material
`that could be glass, plastic, stainless steel, a synthetic polymer
`or other suitable material.
`A gas bubbling means (8) and a retention device (9) are also
`provided. The gas bubbling means (8) is for receiving the gas
`(10), or gases, to be treated inside the reaction chamber (2)
`and for bubbling it into the liquid (3) thereby both dissolving
`the gas to be treated (10) into the liquid (3) and creating a
`pressure within the reaction chamber (2). The biocatalysts (4)
`are chosen so as to be able to biocatalyze a reaction between
`the gas (10) to be treated and the liquid (3) in order to obtain
`a treated gas (11) and a solution (12) containing a reaction
`product. The liquid outlet (6) is for releasing by pressure the
`solution (12) containing the reaction product while the reten-
`tion device (9) retains the biocatalysts (4) within the reaction
`chamber (2). The gas outlet (7) is for releasing the treated gas
`(11) from the reaction chamber (2).
`The triphasic bioreactor (1) preferably includes a pressure
`regulating valve (13) to control the pressure created by the gas
`(10) bubbled into the reaction chamber (2). The pressure
`regulating valve (13) may be located in the gas outlet (7). The
`triphasic bioreactor (1) may also include a valve (14) at the
`liquid outlet (6) and/or at the liquid inlet (5) for regulating the
`flow of liquid (3) into and out of the reaction chamber (2). As
`will become more apparent further along in the description,
`these features are used for both regulating the pressure inside
`the reaction chamber (2) so as not to exceed the pressure
`limits the apparatus may withstand, but also to better control
`the pressure release of the solution (12) containing the reac-
`tion product.
`As shown in FIG. 2, the triphasic bioreactor (1) may
`include a mixer (15) within the reaction chamber (2) to mix
`
`the liquid (3), the biocatalysts (4) and the gas (10). Any type
`of mixer known in the art could be used. For example, as
`shown in FIG. 2, the mixer (15) might include an axial pro-
`peller (16) operatively connected to a top cover (18) of the
`5 reaction chamber (2) by means of a driving shaft (17). In such
`a case, the bioreactor also comprises a suitable driving means
`for driving the shaft into rotation.
`In order to dxive forward the reaction between the gas to be
`treated (10) and the liquid (3), the biocatalysts (4) must com-
`10 prise a molecule capable of reacting with the substrates,
`nanlely the dissolved gas (10) and the liquid (3), so as to yield
`a treated gas (11) and a solution (12) containing a reaction
`product. Biocatalyst