CN103429318A - C02 treatments using enzymatic particles sized according to reactive liquid film thickness for enhanced catalysis - Google Patents

C02 treatments using enzymatic particles sized according to reactive liquid film thickness for enhanced catalysis Download PDF

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CN103429318A
CN103429318A CN2012800073355A CN201280007335A CN103429318A CN 103429318 A CN103429318 A CN 103429318A CN 2012800073355 A CN2012800073355 A CN 2012800073355A CN 201280007335 A CN201280007335 A CN 201280007335A CN 103429318 A CN103429318 A CN 103429318A
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particle
described method
enzyme
liquid film
thickness
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海尔特·弗雷德里克·沃斯蒂格
西尔维·弗拉代特
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Co2 Solutions Inc
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    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
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    • B01D2255/00—Catalysts
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

Techniques for absorbing or desorbing CO2 include sizing enzymatic particles in accordance with the reactive liquid film thickness ([delta]rf) of the reaction medium to increase enzymatic catalysis of the CO2 hydration or dehydration reaction. Absorption may include contacting a CO2 containing gas with an aqueous absorption mixture and determining ([delta]rf) of the C2O2 hydration reaction, wherein ([delta]rf) = ([delta]1)/ Ha where Ha2 = (k1.DCO2/(kL)2, Ha > 2 and k1 = k2Cab, k2 being the CO2 hydration kinetic constant in the mixture and Cab being the concentration of the absorption compound. The mixture may be under conditions that provide ([delta]rf) that is smaller than the liquid film thickness ([delta]1) through which mass transfer of the CO2occurs. The size ratio of the enzymatic particles and ([delta]rf) enhances enzymatic catalysis. Various implementations including processes, systems, formulations and kits are provided.

Description

Use is used for strengthening the CO of catalytic action according to the enzyme particle of reactive thickness of liquid film sizing 2Process
Invention field
The present invention relates to CO 2The absorption and desorption field, especially by containing CO 2The gas treatment of gas and CO 2Catch.
Background of invention
Whole world scientific circles are to the more and more urgent warning of climate change danger and to the more public awareness of this problem be concerned about and promoted to it should be noted that the power of the increase of the global regulation that carbon dioxide is target most to reduce artificial greenhouse gases (GHGs) discharge.Finally, North America and global CO 2The remarkable reduction of discharge need to be from power generation industry (whole world CO 2Maximum single source) reduction.According to the GHG plan of International Energy Agency (IEA), till 2006, there are nearly 5,000 fossil-fuelled power-plants in the whole world, produces nearly 11,000,000,000 tons of CO 2, accounting for the total people in the whole world is CO 2Nearly 40% of discharge.In these discharges from power industry, 61% from coal-fired power plant.Although the long-term agenda that government advocates is to replace the fossil fuel generating by regenerative resource, ever-increasing energy requirement is in conjunction with a middle or short term the huge dependence of thermal power generation having been determined to this power plant based on fossil fuel still moves.Therefore, for realizing that effective GHG reduction system will need to reduce the CO that industry produces thus 2Discharge, provide one of solution be widely known by the people most and carbon is caught and store (CCS).
The CCS method is from containing CO 2Flue gas is removed CO 2, can produce highly concentrated CO 2Gas flow, described CO 2Gas flow is compressed and be transported to and seal place up for safekeeping.This place can be discarded oil field or brine layer.In ocean, seal up for safekeeping with mineral carbonation be in conceptual phase to sealing CO up for safekeeping 2Two kinds of alternative.The CO caught 2Can also be for improving petroleum recovery.
Some are for CO 2The technology of catching is for example, use based on amine (alkanolamine) and carbonate aqueous solution mainly, and described solution circulation passes through two main different units: the absorption tower be connected with desorb (or stripping) tower.
Biocatalyst is also for CO 2Absorb application.For example, CO 2Conversion can be by carbonic anhydrase following catalysis together with the aqueous solution:
Figure BDA00003606685400021
Under optimum condition, the catalytic conversion rate of this reaction can reach 1 * 10 6Molecule/second.Utilize by this way carbonic anhydrase to allow CO 2Catching method accelerates significantly, reduces the size of required container for capturing and the capital cost that minimizing is followed.In addition, by utilizing this acceleration mechanism, can adopt aqueous solvent that energy is useful as tertiary amine and bulky amine and carbonate-bicarbonate solution to reduce the energy consumption of correlated process, and these solvents and solution usually will be too slow and can not be effectively used by this way.
Exist some at CO 2The known way of carbonic anhydrase is provided in the capture reaction device.A kind of mode is by enzyme immobilization on the solid packing in the packed column reactor.Another kind of mode is in reactor or flows through the enzyme that solvable state is provided in the solution of reactor.These two kinds of methods all provide useful effect but have also had some restrictions.Because immobilized enzyme is attached to the surface of solids, they less are exposed to liquid-vapor interface than the independent enzyme molecule of free floating.Be immobilized in the beneficial effect that enzyme on solid packing may limit enzyme, because its existing in the reactive liquid film at liquid-vapor interface place is limited, described reactive liquid film, for regular and/or huddle filling, allegedly have the approximately thickness of 10 μ m; Enzyme on filler is apart from liquid-vapor interface number millimeter.Soluble enzyme has brought best enzyme effect, yet, and if it can not easily separate enzyme with solution unstable to violent condition (such as those conditions of using in the desorb operation), it will need high-caliber continuous enzyme to change sex change and this process.
Be provided for reaction (as at CO 2Those in the capture reaction device) enzymatic biocatalyst exists some problems and challenge as the known technology of carbonic anhydrase.
Summary of the invention
Thereby the present invention is by enzyme delivery technique response the problems referred to above and the challenge of the efficiency of the enzymatic that provides enzyme particle according to the reactive thickness of liquid film sizing of specific reaction medium to provide to have raising and raising method.
The invention provides a kind of from containing CO 2GAS ABSORPTION CO 2Method, described method comprises:
Will be containing CO 2Gas absorbs mixture with the water-based that comprises water and absorption compound and is making CO 2The condition that occurs in the following manner of quality transmission under contact:
At first by air-film thickness (δ g) occur; And
Afterwards by thickness of liquid film (δ l) generation, wherein δ l=D CO2/ k L, k wherein LMass transfer coefficient and the D in liquid CO2CO 2Diffusion coefficient;
Determine CO 2Reactive thickness of liquid film (the δ of hydration reaction Rf), δ wherein Rf=(δ l)/Ha, wherein Ha 2=(k 1.D CO2)/(k L) 2, Ha>2 and k 1=k 2C Ab, k wherein 2To absorb CO in mixture 2The kinetic constant of hydration reaction, and C AbThe concentration that water-based absorbs absorption compound in mixture; And
Provide enzyme particle in water-based absorbs mixture, wherein by enzyme particle according to reactive thickness of liquid film (δ Rf) sizing to be to improve CO 2The enzymatic of hydration reaction.
The method can comprise by regulating concentration, the temperature of method, the mass transfer coefficient (k of absorption compound L) or their combination control reactive thickness of liquid film (δ Rf).
The method can comprise the enzyme particle sizing and to make d/ δ to have diameter (d) Rf<6, d/ δ Rf<3, d/ δ Rf<1, d/ δ Rf<0.05 or d/ δ Rf<0.025.
The method can comprise the enzyme particle sizing, so that CO 2Week transposon (turnover factor) is with respect to the d/ δ by having at least 32.7 RfLarger enzyme particle lower all transposons that can obtain increase to few 50%.
The method can comprise by the enzyme particle sizing with obtain use and absorb that in mixture, lyoenzyme obtains resolvase week transposon at least 17%, 27% or 57% CO 2All transposons.
Reactive thickness of liquid film (δ Rf) can be 10 μ m, 5 μ m, 3 μ m, 2.5 μ m, 2.0 μ m, 1.9 μ m or 1.8 μ m at the most.
Absorption compound can comprise with the concentration of for example about 2M alkanolamine MDEA, so that reactive thickness of liquid film can be 3.2 μ m at the most, and enzyme particle can be sized to 17 μ m at the most.
Enzyme particle can comprise carrier material and carbonic anhydrase, carrier material is selected from nylon, cellulose, silica, silica gel, shitosan, polyacrylamide, polyurethane, alginates, polystyrene, polymethyl methacrylate, magnetic material, agarose, aluminium oxide, and corresponding derivative, and their combination.
Enzyme can be by being selected from the following immobilization technology with respect to the carrier material immobilization: absorption, covalent bonding, embedding, copolymerization, crosslinked and seal, and their combination.
Also provide a kind of for water-based absorption mixture CO 2The enzymatic method of hydration reaction, CO wherein 2Quality pass through thickness of liquid film (δ l) occur, wherein water-based absorbs mixture and comprises liquid solution and enzyme particle and be less than thickness of liquid film (δ in providing l) the reactive thickness of liquid film (δ for hydration reaction Rf) condition under, and comprise by the enzyme particle sizing being made it with respect to reactive thickness of liquid film (δ Rf) enough little and strengthen enzymatic.
The method can comprise enzyme particle according to reactive thickness of liquid film (δ Rt) sizing to be to have diameter (d), makes d/ δ Rt<6.The method can comprise the enzyme particle sizing so that d/ is δ Rt<1.The method can comprise the enzyme particle sizing so that d is less than δ RtAbout one, two, three or four order of magnitude.The method can comprise the enzyme particle sizing so that d is less than δ RtAbout two orders of magnitude.
Water-based absorbs mixture can comprise absorption compound and δ RtCan be 10 μ m, 5 μ m, 3 μ m, 2.5 μ m, 2.0 μ m, 1.9 μ m or 1.8 μ m at the most.
Absorption compound can comprise primary amine, secondary amine, tertiary amine, primary alkanol amine, sec alkanol amine, tertiary alkanolamine, primary amino radical acid, sour, the tertiary amino acid of secondary amino group, or carbonate compound, or their combination.More specifically, absorption compound can comprise at least one in the following: piperidines, piperazine, the piperidines replaced by least one silane alcohol base or the derivative of piperazine, MEA (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(2-aminoethylamino) ethanol (AEE), TRIS (TRIS), N methyldiethanol amine (MDEA), dimethyl MEA (DMMEA), diethyl-monoethanolamine (DEMEA), triisopropanolamine (TIPA), triethanolamine, the dialkyl ether of ployalkylene glycol, the dialkyl ether of polyethylene glycol or dimethyl ether, glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, valine, leucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine, and their derivative, taurine, N, cyclohexyl 1,3-propanediamine, N-sec-butyl glycine, N-methyl N-sec-butyl glycine, diethyl glycine, dimethylglycine, methyl amimoacetic acid, N-methyltaurine, methyl-α-aminopropionic acid, N-(β-ethyoxyl) taurine, N-(beta-aminoethyl) taurine, the N-methylalanine, 6-aminocaprolc acid and its potassium or sodium salt, (promoted) solution of potassium carbonate of potash, sodium carbonate, ammonium carbonate, activation and the sodium carbonate liquor of activation or the ammonium carbonate of activation, or their combination.
Absorption compound can comprise alkanolamine, and it can be tertiary alkanolamine and N methyldiethanol amine (MDEA) more specifically.MDEA can provide with for example about 2M concentration, and the condition that also can provide water-based to absorb mixture makes δ RtFor 3.2 μ m at the most and enzyme particle is sized to 17 μ m at the most.
In addition, δ RtCan be based on Hatta number (Hatta number) (Ha) and also can be based on thickness of liquid film (δ l).The method can comprise according to following formula determines reactive thickness of liquid film (δ Rf):
(δ rf)＝(δ l)/Ha
Wherein Ha is defined as Ha for first kernel response 2=(k 1.D CO2)/(k L) 2.Ha can be greater than 2.
Enzyme particle can comprise carrier material and carbonic anhydrase.Carrier material can be made by the compound outside carbonic anhydrase.Carrier material can comprise nylon, cellulose, silica, silica gel, shitosan, polyacrylamide, polyurethane, alginates, polystyrene, polymethyl methacrylate, magnetic material, agarose, aluminium oxide, and corresponding derivative or their combination.Carrier material can have about 0.6g/ml to the density of about 5g/ml, or higher than the density of about 1g/ml.
Can be by carbonic anhydrase with respect to carrier material by being selected from the immobilization technology immobilization of the following: absorption, covalent bonding, embedding, copolymerization, crosslinked and seal, and their combination.Carrier material can comprise core and be provided at the immobilization material on core, and carbonic anhydrase is by described immobilization material immobilization.Each particle can have a corresponding core.Carbonic anhydrase can also pass through the immobilization technology stabilisation.Carbonic anhydrase can be used as that crosslinked enzyme aggregate (CLEA) provides and carrier material comprises a part of carbonic anhydrase and crosslinking agent.Carbonic anhydrase can be used as that crosslinked enzyme crystal (CLEC) provides and carrier material comprises a part of carbonic anhydrase and crosslinking agent.
By the enzyme particle sizing with have in or lower than about 17 μ m, approximately 10 μ m, approximately 5 μ m, approximately 1 μ m, approximately 0.1 μ m, approximately 0.05 μ m or the about diameter of 0.025 μ m.Particle also can have the distribution of different size.
The method can comprise the enzyme activity level of selecting required enzyme particle; Select the maximum particle concentration that allows; Determine and reach the required required total surface area of enzyme activity level; Determine that the cumulative volume of particle is to reach the maximum particle concentration that allows; Obtain enzyme activity level with the full-size of definite particle with the maximum particle concentration that allows of use.
Enzyme particle can be provided in the maximum particle concentration of about 40%w/w water-based and absorb in mixture.Maximum particle concentration can be about 30%w/w.
Can be by the particle sizing and so that the pumpable concentration of resulting suspension provides.
The method can also comprise to be made containing CO 2Gas and water-based absorb mixture and contacts in reactor with from containing CO 2Gas removes CO 2Thereby at least a portion and produce CO 2The gas of dilution and the rich solion that contains enzyme particle.Absorbent solution and containing CO 2Gas is convective flow relative to each other.
The method can also comprise from rich solion and removes enzyme particle to produce the rich solion of enzyme particle fraction and particle dilution.The further sizing of enzyme particle can be removed from rich solion being conducive to.Removing of enzyme particle can be undertaken by least one in the following: filter mechanism, magnetic separates, centrifugal, cyclone separator, sedimentation, film separates or their combination.Removing of enzyme particle can be undertaken by the selected removing method of existing of the size according to enzyme particle, density and magnetic.Remove and can be undertaken by the following: clarifier, thickener, vacuum or filter-press, intermittence or continuous filter, Horizontal-type filtering filter press, tubular filter, centrifugal discharge filter, drum filter, scraper discharging filter, rolling discharging filter, disc filter, sedimentation centrifuge, decanting centrifuge, filtration sedimentator, basket sedimentator, cyclone hydraulic separators, hydrocyclone, ultrafilter, micron filter part, nanofiltration device, or their combination.
The method can also comprise that the rich solion to the particle dilution carries out desorb or mineral carbonation to produce the solution of ion dilution.At least a portion of the solution of ion dilution can recycle to form at least a portion that water-based absorbs mixture.At least a portion of enzyme particle fraction can combine to form at least a portion that water-based absorbs mixture with the recycle sections of the solution of ion dilution.Rich solion can comprise sediment, and sediment was removed from rich solion before carrying out desorb or mineral carbonation.
The method can be included in rich solion and forms sediment and enzyme particle is provided and promotes the feature of enzyme particle from sedimentary separation.
The method can be included in the situation that does not remove enzyme particle carries out desorb or mineral carbonation to produce the solution of ion dilution to rich solion.Enzyme particle can allow the catalysis of desorb or mineral carbonation.Enzyme can be by the enzyme particle stabilisation in the desorb reactor.Can be by the particle sizing and to use the concentration through the rich solion load of desorb reactor to provide to promote bicarbonate ion and hydrogen ion to CO 2The conversion of gas and water, thus CO produced 2The solution of gas flow and ion dilution.
The method can comprise with respect to CO 2The reactive thickness of liquid film of dehydration by the further sizing of enzyme particle to increase CO 2The enzymatic of dehydration.Sizing is considered to count CO 2Absorption and desorption step in capture systems.Rich solion can comprise sediment and sediment can be removed from rich solion before carrying out desorb or mineral carbonation.
In addition, water-based absorbs mixture and contains CO 2The contact of gas can be carried out at the absorption level that comprises at least one reactor in being selected from packed column, spray column, fluidized-bed reactor and their combination.
Also provide a kind of for CO 2The enzymatic method of the dehydration from the rich ion aqueous mixture that comprises bicarbonate ion and hydrogen ion and enzyme particle, CO wherein 2Quality pass through thickness of liquid film (δ Ld) occur, wherein rich ion aqueous mixture is less than thickness of liquid film (δ in providing Ld) the reactive thickness of liquid film (δ for dehydration rfd) condition under, and comprise by the enzyme particle sizing being made it with respect to reactive thickness of liquid film (δ Rf) enough little and strengthen enzymatic.
What note is with enforcement and the aspect of absorption process cited below, can use with the enzymatic Combination of Methods for dehydration of just describing in the above before.
Also provide the preparation that comprises liquid solution, preferably CO 2Catch preparation, described liquid solution comprises water and compound of reaction and makes reaction CO 2+ H 2O ← → HCO 3 -+ H +Can occur, wherein CO 2Quality pass through thickness of liquid film (δ l) occur and wherein liquid solution be adjustablely to provide, to be less than thickness of liquid film (δ l) for the reaction reactive thickness of liquid film (δ rfd); And the enzyme particle in liquid solution has with respect to reactive thickness of liquid film (δ Rf) enough little size is with the enzymatic of intensified response.
Above being also noted that and following enforcement and the aspect that absorbs the absorption process that mixture and enzyme particle mention about water-based, for example, can be used in combination with the preparation of just describing in the above.
Also provide a kind of for passing through with carbonic anhydrase reaction CO 2+ H 2O ← → HCO 3 -+ H +Enzymatic and process the system of fluid, described system comprises reactor, described reactor has the reative cell of accepting fluid and is configured to be provided for making CO 2Quality pass through thickness of liquid film (δ l) condition that occurs and provide and be less than thickness of liquid film (δ l) for the reaction reactive thickness of liquid film (δ rfd); And enzyme particle, described enzyme particle is present in reative cell and comprises carbonic anhydrase, and wherein enzyme particle has with respect to reactive thickness of liquid film (δ Rf) enough little size is with the enzymatic of intensified response.
Reactor can be constructed so that enzyme particle flows through it together with fluid.
What note is with enforcement and the aspect of the following absorption and desorption method and formulation of mentioning about water-based absorption mixture, enzyme particle and other features, can use with above-described system in combination before.This system can be for absorption or desorb and should be therefore adaptive.For example, the reative cell of this system can and can have structure and the operating characteristic of describing for absorption reactor thermally as this paper for absorption reactor thermally.The reative cell of this system can and can have structure and the operating characteristic of describing for the desorb reactor as this paper for the desorb reactor.Therefore, reaction CO 2+ H 2O ← → HCO 3 -+ H +Can be considered to react forward or backwards, no matter system is to absorb or the desorption type system.In the situation that desorb, therefore fluid is, from it, ion is converted into to CO by reverse dehydration 2The rich ionic liquid of gas, to produce poor solion and CO 2Gas flow.Fluid can be containing CO for contact 2Gas is so that the CO dissolved 2Gas can experience the absorbent solution of forward hydration reaction, to produce rich solion and the CO with minimizing 2The gas flow of processing.Should be noted that it is possible similarly implementing about method described herein, preparation and kit.
Also provide at CO 2The kit of catching middle combination and preferably using, described kit comprises for being added to water and makes reaction CO with formation 2+ H 2O ← → HCO 3 -+ H +The compound of reaction of the liquid solution that can occur, wherein CO 2Quality pass through thickness of liquid film (δ l) occur and wherein liquid solution be adjustablely to provide, to be less than thickness of liquid film (δ l) for the reaction reactive thickness of liquid film (δ rfd); And, for being added to the enzyme particle of liquid solution, described enzyme particle has with respect to reactive thickness of liquid film (δ Rf) enough little size is with the enzymatic of intensified response.
What note is that the enforcement of method cited above and below, system and preparation and aspect can be used in combination with the kit of just describing in the above.
In addition, be provided for by with carbonic anhydrase to the reaction CO 2+ H 2O ← → HCO 3 -+ H +Enzymatic and process the method for fluid, described method comprises: provide fluid in reaction zone, wherein CO under the existence of the enzyme particle that comprises carbonic anhydrase 2Quality pass through thickness of liquid film (δ l) occur; With at reaction zone, provide condition to be less than thickness of liquid film (δ to provide l) for the reaction reactive thickness of liquid film (δ rfd), make enzyme particle and reactive thickness of liquid film (δ rfd) size than the enzymatic of intensified response.
Again note, can use with the Combination of Methods of just describing in the above with enforcement and the aspect of method cited below, system and preparation before.
Following aspect also is provided:
-in some implementations, exist a kind of for from containing CO 2Gas entrapment CO 2Method, described method comprises to be made containing CO 2Gas contacts in reactor with the absorption mixture, described absorption mixture comprises liquid solution and particle, described particle comprises carrier material and by the enzyme of described carrier material load, and be dimensioned and provide with certain concentration, so that described particle is less, preferably be less than substantially the thickness of reactive membrane, and described particle carries to promote CO by described liquid solution 2To bicarbonate radical and hydrionic dissolving and conversion, produce thus poor CO 2Gas and the rich ion mixture that contains described particle.
-in some implementations, there is a kind of method of processing fluid for the carbonic anhydrase catalytic reaction (I) by by reactive membrane, wherein reaction (I) is as follows:
Figure BDA00003606685400081
-in some implementations, during the method comprises fluid is fed to reaction zone under the existence of enzyme particle, described enzyme particle comprises carbonic anhydrase and sizing so that less than the thickness of reactive membrane, preferably little many; Allow reaction (I) to occur in reaction zone, to produce gas flow and liquid stream; With discharge gas flow and liquid stream from reaction zone.
-in some implementations, fluid is to contain CO 2Emission gases; The method comprises absorbent solution is fed in reactor and contains CO with contact 2Emission gases so that from containing CO 2Emission gases dissolve CO 2To absorbent solution; Reaction (I) is the CO that catalysis is dissolved 2Forward reaction to bicarbonate ion and hydrionic hydration; And gas flow is CO 2The gas of dilution and liquid stream are to comprise bicarbonate ion and hydrionic rich solion.Absorbent solution and contain CO 2Emission gases convective flow relative to each other.
-in some implementations, fluid is to comprise bicarbonate radical and hydrionic rich solion; And reaction (I) is that the catalysis bicarbonate ion is to gaseous state CO 2The back reaction of desorb; Gas flow is CO 2Stream and liquid stream are the solution of regeneration.
-in some implementations, the method comprise that design, control or conditioned reaction device parameter and operation comprise hydromechanical condition in case the thickness that affects quality transport membranes and reactive membrane with the function of the enzyme particle that is conducive to have intended size.
-in some implementations, particle can comprise the carrier material consisted of the compound outside dezymotizing, comprise: nylon, cellulose, silica, silica gel, shitosan, polyacrylamide, polyurethane, alginates, polystyrene, polymethyl methacrylate, magnetic material, agarose, their derivatives separately, or they constitute.
-in some implementations, absorb mixture and comprise water and absorption compound.In another alternative embodiment, absorption compound comprises primary, secondary and/or tertiary amine; Primary, secondary and/or tertiary alkanolamine; Primary, secondary and/or tertiary amino acid; And/or carbonate.In another alternative embodiment, described absorption compound comprises piperidines, piperazine, the derivative replaced by least one alkanol groups of piperidines or piperazine, monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(2-aminoethylamino) ethanol (AEE), TRIS (TRIS), N methyldiethanol amine (MDEA), dimethyl monoethanolamine (DMMEA), diethyl monoethanolamine (DEMEA), triisopropanolamine (TIPA), triethanolamine, the dialkyl ether of PAG, the dialkyl ether of polyethylene glycol or dimethyl ether, amino acid, comprise glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, valine, leucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine, and derivative is as taurine, N-cyclohexyl-1, the 3-propane diamine, N-sec-butyl glycine, N-methyl-N-sec-butyl glycine, diethyl glycine, dimethylglycine, methyl amimoacetic acid, N-methyltaurine, methyl-α-aminopropionic acid, N-(β-ethyoxyl) taurine, N-(beta-aminoethyl) taurine, the N-methylalanine, 6-aminocaprolc acid and described amino acid whose sylvite or sodium salt, potash, sodium carbonate, ammonium carbonate, the ammonium carbonate of the solution of potassium carbonate of activation and the sodium carbonate liquor of activation or activation, or their mixture.
-in some implementations, carbonic anhydrase is immobilized on the surface of carrier material of described particle, be embedded in the carrier material of described particle, or their combination.
-in some implementations, carbonic anhydrase is provided as crosslinked enzyme aggregate (CLEA), and carrier material comprises a part of described carbonic anhydrase and crosslinking agent.
-in some implementations, carbonic anhydrase is provided as crosslinked enzyme crystal (CLEC), and described carrier material comprises a part of described carbonic anhydrase and crosslinking agent.
-in some implementations, the method comprises from rich ion mixture and removes particle to produce rich solion.
-in some implementations, particle remove by filter mechanism, magnetic separate, centrifugal, cyclone separator, sedimentation, film separates or their combination is carried out.The selection of particle removing method can depend on existence and/or other character of granularity, particle density, magnetic.The possible unit that removes is clarifier, thickener, vacuum or filter-press, intermittence or continuous filter, Horizontal-type filtering filter press, tubular filter, centrifugal discharge filter, drum filter, scraper discharging filter, rolling discharging filter, disc filter, sedimentation centrifuge, decanting centrifuge, filtration sedimentator, basket sedimentator, ultrafilter, micron filtration and/or nanofiltration device.
-in some implementations, the method comprises carries out desorb or mineral carbonation to produce the solution of ion dilution to rich solion.Should be appreciated that the solution that " solution of ion dilution " means ion is removed at least in part from it and the solution that is not limited to not have fully ion.
-in some implementations, rich ion mixture comprises sediment and sediment was removed from rich ion mixture before carrying out desorb or mineral carbonation.
-in some implementations, the method is included in the recirculation of the solution of ion dilution for further contacting containing CO 2Before gas, a certain amount of particle is added to the solution of ion dilution.
-in some implementations, the method comprises rich ion mixture is fed in the desorb reactor, enzyme provides in the desorb reactor by the carrier material stabilisation and by the particle sizing and with finite concentration, makes and with rich ion mixture, carries to promote bicarbonate radical and hydrogen ion to CO on particle 2The conversion of gas and water, thus CO produced 2The solution of gas flow and ion dilution.
-in some implementations, the method comprises carries out desorb or mineral carbonation with the solution that produces the ion dilution and afterwards particle is removed from the solution of ion dilution rich solion.
-in some implementations, by the particle sizing to be conducive to the separation of particle from rich ion mixture.
-in some implementations, by the enzyme particle sizing to have in or to be less than the approximately diameter of 15 μ m.Optionally, by the particle sizing to have in or to be less than the approximately diameter of 10 μ m.Optionally, by the particle sizing to have in or to be less than the approximately diameter of 5 μ m.Optionally, by the particle sizing to have in or to be less than the approximately diameter of 1 μ m.Optionally, by the particle sizing to have in or to be less than the approximately diameter of 0.5 μ m.Optionally, by the particle sizing to have in or to be less than the approximately diameter of 0.2 μ m.Optionally, by the particle sizing to have in or to be less than the approximately diameter of 0.1 μ m.In some preferred embodiments, depend on the thickness of the reactive membrane of given process operation parameter and condition, by the particle sizing to there is following diameter: about 0.001 μ m, 0.005 μ m, 0.01 μ m, 0.05 μ m, 0.1 μ m, 0.15 μ m, 0.2 μ m, 0.25 μ m, 0.3 μ m, 0.35 μ m, 0.4 μ m, 0.45 μ m, 0.5 μ m, 0.55 μ m, 0.6 μ m, 0.65 μ m, 0.7 μ m, 0.75 μ m, 0.8 μ m, 0.85 μ m, 0.9 μ m, 0.95 μ m, 1 μ m, 1.05 μ m, 1.1 μ m, 1.15 μ m, 1.2 μ m, 1.25 μ m, 1.3 μ m, 1.35 μ m, 1.4 μ m, 1.45 μ m, 1.5 μ m, 1.55 μ m, 1.6 μ m, 1.65 μ m, 1.7 μ m, 1.75 μ m, 1.8 μ m, 1.85 μ m, 1.9 μ m, 1.95 the diameter between any two of μ m or 2 μ m or value above-mentioned.At some in optional embodiment, the particle sizing is less than to reactive membrane thickness approximately one to the about diameter of four orders of magnitude to have.Preferably by the particle sizing so that about two orders of magnitude of the thickness that at least is less than reactive membrane.
-in some implementations, the particle sizing is long-pending to have catalytic surface, described catalytic surface is long-pending comprises the biocatalyst with certain active density in order to the activity level of the corresponding activity level equivalence of the solvable biocatalyst existed with concentration with higher than about 0.05g/L is provided, and wherein solvable biocatalyst has the minimum activity of about 260WA unit/mg.Activity can also be expressed as mg CO 2/ mg E.s or mol CO 2/ gE.s, its to may be that more practical reaction rate is relevant in some cases.
-in some implementations, the particle sizing is long-pending to have catalytic surface, described catalytic surface is long-pending comprises the biocatalyst with certain active density in order to the activity with the corresponding activity level equivalence of the solvable biocatalyst existed to the concentration of about 5g/L with about 0.01g/L is provided, and wherein solvable biocatalyst has the minimum activity of about 260WA unit/mg.
-in some implementations, the method is included in rich ion mixture and forms sediment and wherein particle provided and is beneficial to the characteristic of separating from sediment.
-in some implementations, particle has at least about 2.67x10 -7WA/mm 2Active density.
-in some implementations, the maximum particle concentration with about 40%w/w in absorbing mixture provides particle.Optionally, in absorbing mixture, the maximum particle concentration with about 30%w/w provides particle.
-in some implementations, the density of carrier material is that about 0.6g/ml is to about 5g/ml.In other optional embodiment, the density of carrier material is higher than about 1g/ml.
-in some implementations, described method comprises the required biology catalytic activity level of selecting described particle; Select maximum for described filling reactor and allow particle concentration; Determine and reach the required total surface area of described biology catalytic activity level; Determine and reach the cumulative volume that described maximum is allowed the particle of particle concentration; And the full-size of definite particle, to allow under particle concentration the described biology catalytic activity level that obtains in maximum.
-in some implementations, absorb mixture and contain CO 2The contact of gas is carried out in the absorption level that comprises at least one reactor that is selected from the following: packed column, spray column, fluidized-bed reactor and their combination.
-in some implementations, the invention provides a kind of for from comprising bicarbonate radical and hydrionic rich ion aqueous mixture desorb CO 2The method of gas, described method comprises: in rich ion aqueous mixture, provide the enzyme particle that comprises carbonic anhydrase or its analog; Rich ion aqueous mixture is fed in the desorb reactor; By the particle sizing so as to be less than the thickness of desorb reactive membrane and with the load of rich ion aqueous mixture to promote bicarbonate radical and hydrogen ion to CO 2The conversion of gas and water, thus CO produced 2The solution of gas flow and ion dilution.
-in some implementations, provide a kind of comprise water, enzyme particle and, optionally, the CO of absorption compound 2Catch preparation, described enzyme particle is dimensioned in order to be less than the thickness of reactive membrane.Said preparation can be the form of premixed composition or for before using or the kit of the chemical constituent that combines of use procedure.
-in some implementations, particle is provided to carry out required catalytic reaction together with enzyme and/or its analog.Should be appreciated that enzyme can be naturally occurring, modification or the carbonic anhydrase of evolving and its analog can be naturally occurring or synthetic abiotic little molecules to obtain or the effect of analogue enztme.
-should be noted that each gas-liquid reactor has its own specific quality and transmits thickness, each reactor and absorbent solution have its own reaction thickness and enzyme particle therefore be adjusted to by reactor and absorb or desorption system in the chemistry enhancing the used dimension and the standard that apply.
-in some implementations, can provide a kind of for from containing CO 2Gas entrapment CO 2Method, described method comprises: make containing CO 2Gas contacts in reactor with the absorption mixture, described absorption mixture comprises liquid solution and particle, described particle comprises carrier material and by enzyme or its analog of carrier material load, and is dimensioned to make particle to be less than the thickness of reactive membrane, and this particle promotes CO 2To bicarbonate radical and hydrionic dissolving and conversion, thereby produce CO 2The gas of dilution and rich ion mixture.
-in some implementations, can provide a kind of from containing CO 2Gas entrapment CO 2Method, described method comprises: make containing CO 2Gas contacts in reactor with absorbing mixture, and described absorption mixture comprises liquid solution and particle, and wherein the operation of reactor forms and has for catching CO 2The reactive membrane of thickness; Make to absorb mixture flow by reactor, particle uses the liquid solution load to promote CO 2To bicarbonate radical and hydrionic dissolving and conversion, thereby produce CO 2The gas of dilution and the rich ion mixture that contains particle; Wherein particle comprises carrier material and by enzyme or its analog of carrier material load, and is dimensioned to make particle to be less than the thickness of reactive membrane.
-in some implementations, can provide a kind of for fluid the method by the processing of the catalytic reaction (I) with the carbonic anhydrase of reactive membrane, wherein reaction (I) is as follows:
Figure BDA00003606685400141
The method comprises: during fluid is fed to reaction zone under the existence of the enzyme particle that comprises carbonic anhydrase or its analog, described particle has the size of the thickness of the reactive membrane of being less than; Allow reaction (I) to occur in reaction zone, to produce gas flow and liquid stream; With discharge gas flow and liquid stream from reaction zone.In one aspect, fluid is to contain CO 2Emission gases; The method comprises absorbent solution is fed in reactor and contains CO with contact 2Emission gases so that by CO 2From containing CO 2Emission gases be dissolved in absorbent solution; Reaction (I) is the CO that catalysis is dissolved 2Forward reaction to bicarbonate ion and hydrionic hydration; And gas flow is CO 2The gas of dilution and liquid stream are to comprise bicarbonate ion and hydrionic rich solion.On the other hand, fluid is to comprise bicarbonate radical and hydrionic rich solion; And reaction (I) is that the catalysis bicarbonate ion is to gaseous state CO 2The backward reaction of desorb; Gas flow is CO 2Stream and liquid stream are the solution of regeneration.
-in some implementations, can be provided for from containing CO 2Gas entrapment CO 2Method, described method comprises: the parameter of design, control or conditioned reaction device and operating condition are to affect the thickness of quality transport membranes and reactive membrane, in order to be conducive to have in quality transport membranes and reactive membrane the function of the enzyme particle of intended size.Reaction film can in or be thinner than approximately 15 μ m, in or be thinner than approximately 10 μ m, in or be thinner than approximately 5 μ m, in or be thinner than approximately 1 μ m, in or be thinner than approximately 0.5 μ m or in or be thinner than approximately 0.2 μ m.
-in some implementations, can provide a kind of for from comprising bicarbonate radical and hydrionic rich ion aqueous mixture desorb CO 2The method of gas, described method comprises: in rich ion aqueous mixture, provide the enzyme particle that comprises carbonic anhydrase or its analog; Described rich ion aqueous mixture is fed in the desorb reactor, by the particle sizing so that the thickness that is less than the desorb reactive membrane is to promote bicarbonate radical and hydrogen ion to CO 2The conversion of gas and water, thus CO produced 2The solution of gas flow and ion dilution.
-in some implementations, the method can have with optional chemical absorbing enhancing and/or the gas-liquid reactor of enzyme particle, its design, adjust, provide, construct and/or operate, so that enzyme particle can sufficiently exist with accelerated reaction in reaction film.With optional chemical absorbing, strengthen and/or the gas-liquid reactor of enzyme particle can design, adjusts, provides, constructs and/or operate so that enzyme particle so that enzyme can be sufficiently with the particulate forms stabilisation and sufficiently be present in reaction film with accelerated reaction
-in some implementations, the invention provides for from containing CO 2Gas entrapment CO 2Method, described method comprises: make containing CO 2Gas contacts and is formed for catching CO with the absorption mixture in gas-liquid contact reactor 2The rate-limiting reaction film, absorb mixture and comprise liquid solution and enzyme particle; By the enzyme particle sizing in order to fully have to promote CO in the rate-limiting reaction film 2To bicarbonate radical and hydrionic conversion, thereby produce CO 2The gas of dilution and rich ion mixture.The method can comprise absorption stage and desorption phase, and enzyme particle can exist in both and be dimensioned in order to be less than the rate-limiting reaction film of absorption and the rate-limiting reaction film of desorb in the absorption and desorption stage.
-enzyme granularity can be determined according to any one or combination of method described herein.Reactive thickness can be determined according to any one or combination of computational methods described herein.
-in some implementations, the invention provides a kind of CO 2Catch preparation, described preparation comprise water, sizing in case be less than reactive membrane thickness enzyme particle and, optionally, said preparation also comprises absorption compound.
-in some implementations, the invention provides a kind of premixed composition, described premixed composition comprise water, sizing in case be less than reactive membrane thickness enzyme particle and, optionally, absorption compound.
-in some implementations, the invention provides the kit of chemical constituent, described kit comprise water, sizing in case be less than reactive membrane thickness enzyme particle and, optionally, absorption compound.
-in some implementations, the invention provides a kind of method of enzyme particle of the processing for the preparation of fluid, carbonic anhydrase catalytic reaction (I) in the reactor that uses absorbent solution for described enzyme particle, wherein reaction (I) is as follows:
Figure BDA00003606685400161
The method comprises: according to the character of the operating condition of reactor and absorbent solution, determine, estimate or design reactive thickness; And prepare enzyme particle so that the enzyme particle of q.s has the size that is less than reactive thickness.
Should be noted that " enzyme " or " biocatalyst " comprises its analog and variant.Carbonic anhydrase can be carbonic anhydrase naturally occurring, modification or that evolve; Its analog can be natural existence or synthetic abiotic little molecule to obtain or the effect of analogue enztme.
The accompanying drawing summary
Embodiment of the present invention and aspect can further be understood and understand according to the following drawings:
Fig. 1 is the artwork of one embodiment of the invention, and wherein the living things catalysis particle flows in absorbent solution.
Fig. 2 is the artwork of another embodiment of the invention, and wherein absorptive unit is connected with the desorb unit and the living things catalysis particle flows in absorbent solution.
The schematic diagram of liquid-vapor interface when Fig. 3 is absorption.
Fig. 4 is the figure of differentiation that is presented at the residual activity of 40 ℃ of enzyme particles that are exposed to MDEA2M, and this figure has illustrated stabilizing effect.
Fig. 5 is presented in 2M MDEA solution, and at 25 ℃, granularity is to being fixed on carbonic anhydrase on particle to CO 2The figure of the impact of the contribution of hydration rate.
Describe in detail
Provide and use the enzyme delivery technique for CO 2Gas treatment or the method for catching, system and technology, by the enzyme particle according to the reactive thickness of liquid film sizing of specific reaction medium is provided, thereby allow to improve enzymatic raising method efficiency.
The thickness of reactive liquid film depends on some factor, comprises type, absorbent solution and the absorbed gas of solution-air contact reactor.With reference to Fig. 3, shown the indicative icon of gas-liquid interface in the absorptive unit.In this absorptive unit, gas phase upwards flows and liquid phase flows downward.Quality between two-phase is delivered in air film, and (thickness is δ g) and liquid film (thickness is δ l) the middle generation.For CO 2Absorb, resistance to mass tranfer is in liquid phase.At some in conventional absorption process, at the thickness of the surface of filler liquid film, be several millimeters.Yet, in some absorption process, at CO 2And the thickness (δ of the reactive liquid film of quality transfer reaction occurs between solution Rf) be less than 10 μ m, for example in many cases at about 0.1 μ m to approximately between 9.9 μ m.Enzyme preferably is allowed to be present in this reactivity liquid film δ RfIn.The possible mode that reaches this purpose is to use lyoenzyme or use to have the enzyme particle of minor diameter.For relatively, be fixed in the large fixedly enzyme of filler (it is in the surface of filler) apart from gas-liquid interface and reactive liquid film number millimeter far, so it affects less.
It should be noted in the discussion above that only near liquid gas-liquid interface will be effectively for chemical conversion for wherein chemical reaction rate and quality transfering rate method more faster.In addition, usually said fast and in the immediate reaction zone, from the reaction of gas phase will be near gas-liquid interface or, sometimes in the interface part, transform fully.This means except this very little zone of near interface, will there is no that in liquid unconverted reactant exists.The estimation of the size of quality transmission region can obtain by the application membrane modle, obtains δ=D/k L.For different gas-liquid reactor, k LValue usually 10 -4-10 -5Between m/s, change and diffusivity D is approximately 10 -9m.s -2, the quality that obtains 10-100 μ m is transmitted thickness.In other absorption process, CO occurs 2And the film thickness (δ of the reactive liquid film of the quality transfer reaction between solution Rt) be less than 10 μ m.
Utilize the effect relevant to this reactive membrane thickness, in some implementations, for water-based, absorb mixture CO 2The enzymatic method of hydration reaction comprises: by the enzyme particle sizing being made it with respect to reactive thickness of liquid film (δ Rf) enough little and strengthen enzymatic.
The method can comprise to be made containing CO 2Gas absorbs mixture with the water-based that comprises water and absorption compound and is making CO 2The quality transmission at first by air-film thickness (δ g) occur; And afterwards by thickness of liquid film (δ l) contact δ wherein under the condition that occurs l=D CO2/ k L, k wherein LCO 2Mass transfer coefficient in liquid and D CO2CO 2Diffusion coefficient.The method can also comprise determines CO 2Reactive thickness of liquid film (the δ of hydration reaction Rf), δ wherein Rf=(δ l)/Ha, wherein Ha 2=(k 1.D CO2)/(k L) 2, Ha>2 and k 1=k 2C Ab, k wherein 2The CO absorbed in mixture 2The kinetic constant of hydration reaction and C AbThe concentration that water-based absorbs absorption compound in mixture.Method can also be included in water-based and absorb in mixture enzyme particle is provided, wherein by enzyme particle according to reactive thickness of liquid film (δ Rf) sizing to be to improve CO 2The enzymatic of hydration reaction.
The method can comprise by regulating concentration, the temperature of method, the mass transfer coefficient (k of absorption compound L) or their combination control reactive thickness of liquid film (δ Rf).
Enzyme particle can be sized to and be less than reactive membrane thickness, as at about 0.001 μ m to approximately between 10 μ m.
The preferable range of enzyme particle diameter will depend on several factors, comprise absorption compound and CO in strength of fluid, gas concentration, solution 2The operating condition of capture reaction device.The thickness of reactive membrane is along with absorption compound and CO 2Reaction rate change.Faster absorbent solution, reactive membrane thickness is thinner.The solution that comprises primary, secondary alkanolamine and the solution based on ammonia are considered to quick absorbent solution and expection causes thinner reactive membrane.
For example, the method can comprise the enzyme particle sizing to have diameter (d), so that d/ is δ Rf<6, d/ δ Rf<3, d/ δ Rf<1, d/ δ Rf<0.05 or d/ δ Rf<0.025.Reactive thickness of liquid film (δ Rf) can be 10 μ m, 5 μ m, 3 μ m, 2.5 μ m, 2.0 μ m, 1.9 μ m or 1.8 μ m at the most.
Reactive membrane thickness is according to CO 2And the reaction rate between absorption compound changes.For example, for MDEA, reaction rate is:
R＝k?C MDEA*C CO2
Wherein R is reaction rate, and k is reaction constant, C MDEAMDEA concentration and C CO2CO 2Concentration.Increase absorption compound concentration and bring the reduction on the thickness of increase on reaction rate and reactive membrane.Relation between solution concentration and film thickness will depend on compound, because each compound has different k-factors.Reaction rate is not identical with the solution for chain triacontanol amine solution and other types for carbonate solution for the dependence of compound concentration yet.
According to embodiments more of the present invention,, that estimate or approximate liquid quality transport membranes thickness sizing that calculate for given absorbent solution and method condition by the particle basis.For example, with reference to figure 3, liquid quality transport membranes (δ l) can determine by following formula:
δ l＝D CO2/k L
K wherein LMass transfer coefficient and the D in liquid CO2CO 2Diffusion coefficient.Coefficient k LAnd D CO2Existing form from handbook, experience estimation or handbook data and calculating or their combination in many ways determined.Can use above formula to obtain δ by the absorbent solution for given and operating condition lEstimated value, and afterwards according to estimated δ lManufacture or adopt enzyme particle.The method can also comprise continuously or be updated periodically δ lAnd δ RtMonitoring and calculate to determine preferred sizing and the concentration of enzyme particle, but for the macroeconomic of optimized reactivity, activity pumping, efficiency and process.The method can also comprise periodically or continuously control method condition and hydrodynamics with ACTIVE CONTROL δ lAnd δ RtMake the enzyme particle used in reactor can have that they are required functional.
In addition, reactive membrane (δ Rt) and quality transport membranes (δ l) ratio show roughly by usually said Hatta number (Ha), wherein Ha is defined as for first kernel response:
Ha 2＝(k 1.D CO2)/(k L) 2
And, for the value of Ha>2, can be estimated as:
(δ rf)＝(δ l)/Ha
Therefore, can use Ha to calculate the thickness of reactive membrane for given absorption system (absorbent solution, type of reactor and hydrodynamics), and determine preferred enzyme particle size for given application afterwards, wherein Ha is preferably greater than 2.
In some embodiments of the present invention, also by the particle sizing and so that the pumpable concentration of resulting suspension provides.
An embodiment of method and system is presented in Fig. 1, and will be described in further detail hereinafter.At first, by the living things catalysis mix particles in the poor absorbent solution in mixing chamber (E-4).Poor absorbent solution refers to take the absorbent solution that the species to be absorbed of low concentration are feature.This solution is fresh solution or from mineral carbonation process or CO 2Desorption process (10).To feed into the top with the packed column (E-1) of pump (E-7) also referred to as the absorbent solution with living things catalysis particle (11) that absorbs mixture afterwards.Filler (9) can be made as polymer, metal and pottery by conventional material.The geometry of filler can be selected from commercially available those shapes.Can also select or arrange described filler with facilitate specific distortion and with the collision of particle, or avoid particle gathering in reactor.For example, described filler preferably has limited concave surface upward to avoid particle to gather therein.Also preferred, filler carrier is more much bigger than particle.Also preferred, select particle and filler so that particle can flow through reactor and can not block.Will be containing CO 2Gas phase (12) feed into upstream packed column (E-1) and upper at filler (9), by filler (9) and/or at filler (9) on every side from the flows of tower to top.Absorbent solution and living things catalysis particle are gone up at filler (9), by filler (9) and/or at filler (9), are flowed to bottom from the top of tower on every side.Along with absorbent solution and living things catalysis particle move ahead by absorbent, absorbent solution becomes and more and more is rich in absorbed compound.Near the living things catalysis particle existed liquid-vapor interface passes through catalysis CO immediately 2Hydration reaction is to produce bicarbonate ion and proton and therefore to make the CO across this interface 2Concentration gradient maximizes, thereby strengthens CO 2Absorb.In the outlet of tower, by rich absorbent solution and living things catalysis particle (13) pumping (E-5) to separate particles unit (E-3).Rich absorbent solution refers to take the absorbent solution that the concentration of absorbed compound is feature higher than the concentration in barren solution.Described separative element can comprise filter element (as the tangential flow filtration unit), centrifuge, cyclone separator, settling tank or magnetic separator, and any other unit or the equipment that become known for particle or solid separation.Described separative element can also make a certain amount of solution retain together with particle, and described like this particle can not dry up and make the biocatalyst sex change.One optional aspect, a certain amount of reservation solution can make particle be pumped (E-6) to storage element or directly be back to mixing chamber (E-4) to be added in absorptive unit.In another optional aspect, the solution gravity of particle and reservation can be fed in mixing chamber (E-4), for example, can realize by being separated above mixed cell.Described separation can be carried out with continuous or batch mode, and can manage to guarantee to retain the solution of Sq to guarantee enzymatic activity.Depend on the circumstances, can also preferably provide particle to make can easily separate they and any solid sediment (for example, bicarbonate sediment) that may carry in rich solion.Absorbent solution (15) pumping (E-9) that will not contain particle afterwards is to another unit, and described unit can be CO 2Desorb unit or mineral carbonation unit (10).By living things catalysis particle (16) and poor CO 2Absorbent solution is mixed.Afterwards this suspension is fed into again to absorption tower (E-1).
In another embodiment, as be described in further detail in Fig. 2, absorptive unit is connected with the desorb unit.In this embodiment, will be rich in CO 2Containing absorbent solution (15) pumping (E-9) of living things catalysis particle by heat exchanger (E-10), it is heated in heat exchanger, deliver to afterwards desorber (E-11).In the desorb unit, this solution is further heated so that by CO 2With gaseous state, from solution, discharge.Owing to using relatively high temperature during desorb, water also is evaporated.To partially absorb solution (18) and guide reboiler (E-12) into, and at this, be heated to and can carry out CO 2The temperature of desorb.By gaseous state CO 2Cooling together with steam, water condenses and is back to desorb unit (19) by feed.Afterwards by dry gaseous state CO 2(20) guide compression and transportation operation into for further processing.The less CO that contains that will be called as afterwards poor absorbent solution (17) 2Liquid phase pumping (E-14) to heat exchanger (E-10) so that it is cooling, and it is fed into to mixing chamber (E-4).The temperature of poor absorbent solution (17) should enough hang down to make enzyme (if existence) sex change.
Of the present invention another optional aspect, benefit be by biocatalyst on particle or within immobilization the stability of increase can be provided enzyme.More contents about stability will be described below.Because biocatalyst is fixed on carrier material or among, with the particle of immobilized biocatalyst can have longer storage life with for storing, transportation, recycle and recycle in technique.In some embodiments, immobilized biocatalyst can be stable to the operating condition in the machining cell except absorptive unit (as the desorb unit), and therefore particle can need to not remove particle for the absorption and desorption unit before the desorb unit.In this Process configuration, enzyme particle can be by improving CO 2Absorption rate exerts an influence in absorptive unit, and exerts an influence in the desorb unit because carbonic anhydrase also known raising bicarbonate ion to CO 2Conversion rate (this is one of reaction will occurred in the desorb unit).In this configuration, need to remove unit (E-3) and remove with the particle by inactivation, and need unit (E-4) to add fresh enzyme particle.Yet, there is separative element as (E-11) and the filter (E-12) may be useful (heat resistance that depends on the biocatalyst of particle) to avoid enzyme particle to flow through that reboiler and they contact with very high temperature.
Of the present invention another optional aspect, benefit is can easily change or new particle more.Mixing chamber (E-4) preferably includes for receive the entrance of the particle of recirculation from separative element (E-3), also comprise inlet/outlet, described inlet/outlet is for removing a part with the particle of crossing and they being replaced by new particle, whole batch of materials of particle in renewal system thus.
Of the present invention another optional aspect, the benefit of method and system be can by particle than conventional resolvase much easier from rich ion mixture, remove.As an example, people's carbonic anhydrase II type is to be of a size of
Figure BDA00003606685400211
Ellipsoid, and be difficult to separate from solution.Therefore, thus the particle sizing can be able to be obtained to high absorption rate and easily be removed with for recirculation.In this way, can avoid enzyme to be present in the desorb unit, described desorb unit may relate to high temperature and can make the enzyme of some types and other conditions of enzyme variant sex change.In some embodiments, the living things catalysis particle is filtered in separative element to (for example depending on size, micron filter or nanofiltration), centrifugal, cyclonic separation, sedimentation or Magnetic Isolation.Alternatively, they can be stayed to circulation during the course.Can in before or separative element afterwards, by other, little particle separates as sediment.
Described method/system can comprise for removing the separative element of particle.Preferably these particle pumpings are back to afterwards to the entrance that absorbs liquid in packed column.The selective dependency of separative element for example, in size, density, cost and their character (, magnetic or non magnetic particle) of particle.Described method can also comprise the desorb unit in order to regenerate described rich solion.
In one embodiment, particle is combined with the absorption compound in solution.Absorption compound can be primary amine, secondary amine and/or tertiary amine (comprising alkanolamine); Primary, secondary and/or tertiary amino acid; And/or carbonate.Absorption compound can more specifically comprise that amine (for example, piperidines, piperazine and the derivative replaced by least one alkanol groups thereof), alkanolamine (for example, monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(2-aminoethyl amino) ethanol (AEE), 2-amino-2-methylol-1, ammediol (Tris), N methyldiethanol amine (MDEA), dimethyl monoethanolamine (DMMEA), diethyl monoethanolamine (DEMEA), triisopropanolamine (TIPA) and triethanolamine), the dialkyl ether of PAG (for example, the dialkyl ether of polyethylene glycol or dimethyl ether), amino acid, can comprise amino acid whose sylvite or sodium salt, glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, valine, leucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine, and derivative is as taurine, N-cyclohexyl-1, the 3-propane diamine, N-sec-butyl glycine, N-methyl-N-sec-butyl glycine, diethyl glycine, dimethylglycine, methyl amimoacetic acid, N-methyltaurine, methyl-α-aminopropionic acid, N-(β-ethyoxyl) taurine, N-(beta-aminoethyl) taurine, the N-methylalanine, 6-aminocaprolc acid, and it can comprise solution of potassium carbonate and the sodium carbonate liquor of activation or the ammonium carbonate of activation of potash, sodium carbonate, ammonium carbonate, the solution based on ammonia, activation, or their mixture.Absorption compound is added in solution to assist CO 2Absorb and combine with the catalytic action of carbonic anhydrase.Due to structure or the high concentration of some absorption compounds, may threaten activity or the life-span of carbonic anhydrase.For example, resolvase may be easier to the sex change that the absorption compound of the high ionic strength that had causes as carbonate.The carbonic anhydrase immobilization can be alleviated to the negative effect of this type of absorption compound.By providing by the particle immobilization or otherwise, by particle loaded carbonic anhydrase, described method can obtain high CO under the existence of absorption compound 2Transfer rate has alleviated this compounds otherwise the negative effect that may produce resolvase simultaneously.Preferably select the size of absorption compound and enzyme particle to optimize the macroeconomic of enzymatic activity and method.For example, the concentration of absorption compound and the concentration of enzyme particle and combinations of particle sizes design, to raise the efficiency and to reduce the cost of method.
According to embodiments more of the present invention, carbonic anhydrase is immobilized on the surface of carrier material of particle, be embedded in the carrier material of particle, or their combination.In some embodiments, particle is by carrier or provide on it by least one enzyme or encapsulating material wherein forms.Immobilization can be selected from absorption, covalent bonding, embedding, copolymerization, crosslinked and seal, and their combination.
In some implementations, the enzyme granularity based on reactive thickness of liquid film so that this size strengthens enzymatic.In other words, enzyme particle is enough little of to obtain the enzymatic relatively improved with larger particle, thereby increases the effect of enzyme.It has been found that the catalytic effect of enzyme to hydration reaction, as by the turnover factor representation, show as the catalytic action maintenance level when particle when relatively being greater than the certain size of reactive thickness of liquid film, for example, as d/ δ Rf>approximately 30 or 50 o'clock (for example in an embodiment 32.7 and 48.7).Yet, in certain granularity, for example, as d/ δ Rf<approximately 6 when (in embodiment 5.9), reaction system increases and reaches the larger enzyme catalysis by the turnover factor representation increased on maintenance level.For the MDEA system testing and provided the enzyme particle based on reactive thickness of liquid film sizing.MDEA is tertiary alkanolamine, and it should be noted in the discussion above that the other system that comprises absorption compound (it has the same or analogous effect with MDEA to absorption system) also can adopt and benefit from enzyme particle sizing technology as described herein.Further mention as top, use different compounds that different system performances will be provided, for example some compounds provide relatively " faster " absorption with MDEA as primary alkanol amine as TRIS; Therefore, reactive thickness of liquid film can be affected by different compounds, concentration and temperature, thereby and can adopt the enzyme particle sizing.
It should be noted in the discussion above that information described herein, method and calculating can be used and be suitable for different absorption systems to adopt enzyme particle sizing technology described herein.
In addition, known dehydration is the back reaction of hydration, and multiple desorption system can be used and be suitable for to information described herein, method and calculating, to adopt and to benefit from enzyme particle sizing technology as described herein.As mentioned above, can carry out the adjusting of enzyme particle size so that both enzymatics of absorption and desorption stage that to increase, for example with as shown in Figure 2 and bioreactor described herein combination.
In addition, enzyme system and the reaction outside removing carbon dioxide and corresponding hydration and dehydration can be used and be suitable for to information described herein, method and calculating, to utilize and to benefit from enzyme particle sizing technology as described herein, as long as other enzymes can comprise reactive thickness of liquid film as described herein with respect to particle immobilization and reaction system.This other enforcements can be particularly suitable for being similar to CO 2Gas-the liquid system of absorption and/or desorption system, but also can be suitable for liquid-liquid system and other phase transfers and reaction system with suitable change.
Embodiment
Embodiment 1
With the nylon particle of two kinds of different sizes, make a preliminary test: 50-160 μ m and 2-20 μ m.At 2M MDEA and 1.45M K 2CO 3In under similar operating condition, in the hydration unit, tested.
Design also operates the hydration unitary reactor to control gas phase, CO in absorption process under the condition of setting 2And the interfacial area between liquid phase.Use this device to estimate enzyme particle to CO in given absorbent solution 2The impact of absorption rate.Tested as follows: the absorbent solution of the not load of known volume is introduced in reactor; Afterwards the particle of known quality is added to absorbent solution (particle can contain enzyme, or also can not contain enzyme for comparing purpose); CO 2Stream flows through the headroom of reactor and starts and stirs; Measure the function of the pH of solution as the time; Use afterwards for the predetermined concentration of carbon of absorbent solution-pH correlation the pH value is converted into to the concentration of carbon in g C/L; Determine absorption rate by C concentration as the curve map of the function of time.The relative absorption rate that is used as of enzyme is reported as follows: the ratio of the absorption rate under the existence of enzyme particle and the absorption rate under the existence of the particle that does not have enzyme.
According to these results, for two kinds of used granularities, enzyme particle is only at 1.45M K 2CO 3(it is slower CO 2Absorbent solution) bring the absorption rate of remarkable increase in.Under test condition, do not there is the K of enzyme 2CO 3Absorption will be than approximately 10 times slowly of the absorption rates in the 2M MDEA that does not there is enzyme.What also observe in addition, is that the impact of particle for less particle is more remarkable.Viewed impact also significantly is less than the impact obtained by similar resolvase concentration.
These tests are presented in the situation that granularity is less than reactive membrane, have the effect that less particle will increase enzyme particle.
Embodiment 2
The particle carrier material can be made by nylon, silica, silica gel, shitosan, polyurethane, polystyrene, polymethyl methacrylate, cellulose, magnetic particle, aluminium oxide and the other materials that becomes known for biocatalyst immobilization and embedding.Described particle also can consist of combination of different materials.For example, described carrier can have by the surfacing from different (described surfacing is provided for immobilization or the embedding of enzyme) and compares the core that material with different density or different other character forms.For example, thereby the core of carrier can be formed and can be carried out the magnetic separation by magnetic material, and surfacing can be polymerization such as nylon for the described enzyme of load.As mentioned above, in one embodiment, carrier material can be that the aggregation of enzyme is to form CLEA or CLEC.Particle can limit complete solid volume (for example, pearl shape) separately maybe can comprise one or more holes (for example, pipe or annular) of passing through the main volume of particle.As an example, particle can be avette, spherical, cylindrical etc.
The size of particle can be determined according to the requirement of the process conditions of appointment.But should select compound, material and process equipment to allow to absorb fully flowing and pumping of mixture.
Embodiment 3
In packed column for absorption, tested.Absorbent solution is the aqueous solution of methyl diethanolamine (MDEA) 4M.Make this absorbent solution and CO 2The gas phase counter current contacting that concentration is 130,000ppm.Flow rate of liquid is that 0.65g/ minute and gas flow rate are 65g/ minute, and corresponding L/G is 10 (g/g).Gas and absorbent solution are in room temperature.The operating pressure of absorber is set to 1.4psig.The diameter of tower is 7.5cm, is highly 50cm.The polymerization Raschig ring that filler is 0.25 inch.Carry out three tests: first does not use catalyst, and second use is immobilized onto the carbonic anhydrase of filler carrier, and the 3rd use is free in concentration in solution and rises the carbonic anhydrase of solution for 0.5g/.
The result obtained shows that employing is immobilized onto the lip-deep carbonic anhydrase of Raschig ring, CO 2Transfer rate or CO 2Remove speed from 6mmol CO 2/ minute increase to 14mmol CO 2/ minute.At resolvase, in solution under the existence of free-pouring carbonic anhydrase, transfer rate increases to 29mmol/ minute.The particle that these result proofs are added the positive impact of enzyme and comprised enzyme in packed column can be realized improving.
Also use potash (20%w/w-1.45M)) and the solution of sodium carbonate 0.5M similarly test.For MDEA4M, identical trend is followed in impact free and immobilized enzyme.
Embodiment 4
Adopt the cross-linked enzyme aggregate (CLEA) of carbonic anhydrase to be tested (using not prioritization scheme).The enzyme used is the heat-resisting variant of enzyme HCAII, is labeled as 5X.The 5X enzyme that CLEA contains 26% (w/w).Particle size range is the 4-9 micron.Absorbent solution is 1.45M K 2CO 3.Probe temperature is 20 ℃.The concentration based on enzyme of CLEA is 0.5g/L.Method as described in example 1 above.Adopt CLEA to be tested, use afterwards the CLEA of deactivation as reference, thereby can determine the impact of enzyme.Result shows that CLEA has improved CO with 3.2 the factor 2Absorption rate.
Embodiment 5
Adopt the cross-linked enzyme aggregate (CLEA) of carbonic anhydrase to be tested (using not prioritization scheme).The enzyme used is the heat-resisting variant of enzyme HCAII, is labeled as 5X.The 5X enzyme that CLEA contains 26% (w/w).Particle size range is the 4-9 micron.Absorbent solution is 1M MDEA.Probe temperature is 25 ℃.Enzyme concentration is 0.5g/L.Carry out CO in stirring pool 2Absorb test, stirring pool is one can be used for estimating CO under different condition 2The simple device of absorption rate.This stirring pool contains absorbent solution (and comprising when needed enzyme).Pure CO by known pressure 2Be applied to this solution.In these tests, initial CO 2Pressure is 1000 millibars.Monitoring pressure descends and is used for calculating the CO while absorbing afterwards 2Transfer rate.Thereby employing has CLEA and do not have the particle of CLEA to be tested the impact that can determine enzyme.Result is expressed as the CO when having CLEA 2The CO of transfer rate when not having CLEA 2The ratio of transfer rate.Result shows that CLEA is with the factor raising CO of 1.3-1.7 in MDEA 2Absorption rate.
Embodiment 6
The HCAII on iron oxide particles surface that employing is immobilized in the silica-coating of magnetic is tested (using the immobilization scheme of not optimizing).Granularity is 5 μ m.Absorbent solution is 1.45M K 2CO 3.Probe temperature is 20 ℃.Enzyme concentration is 0.2g/L.Method as described in example 1 above.Result shows that enzyme on magnetic particle improves CO with 1.6 the factor 2Absorption rate.
Embodiment 7
For an embodiment of method, the present embodiment provides the calculating of the active density of preferred minimum for given particle size.
Data:
The activity level that will reach in absorbent solution: 5x10 6Unit/L (being equivalent to 1g/L solubility carbonic anhydrase).
Density of material: for nylon particle 1.1g/mL (～1100g/L).
Maximum is allowed particle concentration: 300g/L.
Particle diameter: 10 μ m.
Calculate:
1.10 the surface area of μ m particle
A p=4 π (radius) 2=4 π (5) 2=314 μ m 2
2.10 the volume of μ m particle
Vp=4/3 π (radius) 3=4/3 π (5) 3=524 μ m 3
3. reach maximum allow the overall particle of particle concentration long-pending/liter:
Figure BDA00003606685400271
V T(1,100g/L)=0.272L (is equivalent to 2.72x10 to=300g/ 14μ m 3)
4.1L the number of particles in solution (np):
n p = V &tau; V p
n p＝2.72x10 14μm 3/524μm 3＝5.21x10 11
5. total particle surface amasss (A T)
A T＝n p*A p＝5.21x10 11*314＝1.64x10 14μm 2(1.64x10 8mm 2)
6. minimum active density
Active density=activity level/A T=5x106/1.64x10 8=0.03 WA/mm of unit 2
Therefore, for 10 μ m particles, reach 5x10 6The active density of the minimum of the activity level of the WA/L of unit is 0.03 WA/mm of unit 2.
Therefore, if active density higher than 0.03 WA/mm of unit 2, needs are less than to the particle concentration of 300g/L.Other embodiment is presented in following table.
Figure BDA00003606685400281
Figure BDA00003606685400291
Figure BDA00003606685400301
Embodiment 8
For an embodiment of method of the present invention, the particle concentration that the present embodiment is appointment provides the calculating of preferred maximum particle size.
Data:
The activity level that will reach in absorbent solution: 5x10 6Unit/L (being equivalent to 1g/L solubility carbonic anhydrase).
Active density on particle: 0.51 unit/mm 2
Density of material: for nylon particle 1.1g/mL (～1100g/L)
Maximum is allowed particle concentration: 300g/L.
Calculate:
1. reach the required total surface area of activity level:
Figure BDA00003606685400311
A T=5x10 6Unit/L/ (0.51 unit/mm 2)=9803922mm 2
2. reach maximum allow the overall particle of particle concentration long-pending/liter:
Figure BDA00003606685400312
V T=300g/ (1100g/L)=0.272L (is equivalent to 272727mm 3)
Like this, will there is 272727mm in every liter of mixture 3The particle of volume.
3. the maximum radius of particle:
For spheroidal particle:
Ap=4 π (radius) 2
Vp=4/3 π (radius) 3
Therefore:
Figure BDA00003606685400313
And:
Figure BDA00003606685400321
Therefore, the preferred maximum dimension of particle will have the approximately diameter of 166 μ m.Thereby, if particle has less diameter, the mixture obtained or absorbent solution will be pumpable.
The method can be used for estimating for activity level, active density, particle density and the maximum permissible maximum particle size of many conditions of allowing particle concentration.
Although calculate for spheroidal particle in the above embodiments, calculate accordingly or estimate and can carry out for other particle geometries.Following table provides different situations and corresponding granularity.
Figure BDA00003606685400331
Figure BDA00003606685400341
Figure BDA00003606685400351
This has shown to go back example another benefit of less particle.Wherein use the CO of particle 2Catching method and larger particle or large packing material relatively need to be in absorbent solution the mass concentration of particle lower.
Embodiment 9
In packed column for absorption, tested.Absorbent solution is potash (K 2CO 3) aqueous solution of 1.45M.This absorbent solution and CO 2The gas phase counter current contacting that concentration is 130,000ppm.Flow rate of liquid is that 0.60g/ minute and gas flow rate are 60g/ minute, and corresponding L/G is 10 (g/g).Gas and absorbent solution are in room temperature.The operating pressure of absorber is set to 1.4psig.The diameter of tower is 7.5cm, is highly 50cm.The polymerization Raschig ring that filler is 0.25 inch.Carry out two tests: first does not use activator, second CLEA that use contains 26% (w/w) 5X enzyme.Particle size range is 4-9 μ m.Enzyme concentration in absorbent solution is 0.1g/L.
The result obtained shows: owing to adopting CLEA to make CO 2Remove speed and increased to 30mmol/ minute so CO from 11mmol/ minute 2The factor that transfer rate increases is 2.7.
Embodiment 10
The present embodiment provides the proof enzyme immobilization to increase the data of enzyme stability.The data that are immobilized in the enzyme on the nylon particle have been shown.In order to estimate the impact of immobilization on enzyme stability, the stability of immobilised enzymes is estimated and compared with the stability of the same enzyme of soluble form.Prepare particle by the following step of not optimizing:
-surface treatment with glutaraldehyde to the nylon particle
-interpolation polymine
-interpolation glutaraldehyde
-immobilized enzyme (people's carbonic anhydrase II type)
-with polymine, aldehyde radical is sealed
After immobilization, enzyme particle and lyoenzyme are exposed to MDEA2M at 40 ℃.When specific open-assembly time, take out sample and measure active.Result is expressed as residual activity, and it is enzymatic activity when the open-assembly time of appointment t and the ratio of the enzymatic activity of 0 o'clock constantly.Fig. 4 illustrates result.
When result shows 10 days, resolvase has been lost whole activity, and particle has still retained 40% residual activity after 30 days, and after 56 days 25% residual activity.From this result, be clear that immobilization has increased enzyme stability under these conditions.
These results have shown that immobilization increases carbonic anhydrase at CO 2Catch the possibility of the stability under the higher temperature conditions existed in technique.In optional approach of the present invention, particle stability can be increased in embodiment near illustrated stability value added or on.
Embodiment 11
For 2 and 4M MDEA solution provide an example of the calculating of desired particle size.For this purpose, the data of dynamics, diffusion coefficient and mass transfer coefficient are available.
Be known that the CO MDEA solution from scientific literature 2Reaction is counterfeit first kernel response, and wherein W-response speed is controlled by following formula:
R CO2＝kovC CO2
R wherein CO2The CO in mol/L.s 2Reaction rate, k OvWhole counterfeit single order kinetic constant (s -1) and C CO2The CO in mol/L 2Concentration.Kinetic constant k OvBe defined as follows:
k ov＝k 2C mdea
C wherein MDEAWith mol/m 3The MDEA concentration of meter, and k 2CO 2The kinetic constant of the reaction in MDEA solution.
According to scientific literature, k 2=1.34x10 6Exp (5771/T), with m 3/ (mol.s) count
At 25 ℃, k 2Equal 0.0052m 3/ (mol.s), k so OvValue as follows:
For 2M MDEA, k Ov=10.4s -1
For 4M MDEA, k Ov=20.8s -1
The data of using in above calculating derive from document, but they can be estimated or be tested and determine by document in other cases.
Under existing conditions, by stirring pool, 25 ℃ of experiments of carrying out, determining diffusion coefficient and mass transfer coefficient.The data that obtain are as follows.
MDEA concentration (M) Mass transfer coefficient k L(m/s) CO 2Diffusion coefficient D CO2(m 2/s)
2 11.4×10 -6 10.8×10 -10
4 8.54×10 -6 6.05×10 -10
Use these data, calculated mass transport membranes (δ L) Hatta number and thickness.Determine as follows afterwards the thickness of reactive membrane:
δ l＝D CO2/k L
For the present embodiment, Ha 2=(k 1.D CO2)/(k L) 2, k 1=k Ov
And, for the value of Ha>2, can be estimated as:
(δ rf)＝(δ l)/Ha
Result provides in following table.
MDEA concentration (M) Hatta number δ L(μm) δ rf(μm)
2 10.4 95 9.1
4 13.2 71 5.4
According to these results, the enzyme particle used in MDEA solution should be designed to be less than 9.1 μ m and be less than 5.4 μ m for 4M solution for 2M solution.
Embodiment 12
As this paper clearly explains, can together with the present invention, use multiple for enzyme being fixed or caught or otherwise be provided at the method on particle.At this paper, some preferred immobilization technologies are described.About the other information of optional immobilization technology, can list of references.One optional aspect, can use a kind of immobilization technology as described in Application No. 11/411,774 (it is combined in this by reference).In addition, in above embodiment 1,3 and 10, the immobilization on nylon is according to the instruction of Application No. 11/411,774; In above embodiment 6, the technology in the immobilization of the surface of the iron oxide particles of the silica-coating of magnetic according to supplier; In the above embodiment about CLEA, particle is according to known preparation method's preparation of the CLEA used by supplier CLEA Tech..
Example according to Application No. 11/411,774:
" the methyl alcohol alcoholysis with solid carrier of Raschig ring geometric configuration (GE polymer form) is carried out 60 minutes at 50 ℃.Remaining step is carried out in room temperature.Afterwards by dechlorination water washing 5 times for carrier.The hydrolysis of carrier is carried out 1 hour with HCl solution (3.93N derives from Lab Mat).Afterwards carrier is used to dechlorination water washing 5 times and washed 1 hour with NaOH (0.1M derives from Lab Mat).Afterwards by dechlorination water washing 12 times for carrier.Carrier is passed through to dipping pretreatment in 1 hour in carbonate buffer solution (Sigma, 0.2M, pH8.5).Afterwards glutaraldehyde for carrier (Sigma) solution (2.5%, in the 0.2M of pH8.5 carbonate buffer solution) is processed 1 hour.Afterwards by dechlorination water washing 5 times for carrier.Carrier is hatched 18 hours in polymine (PEI derives from Sigma) solution (0.5%, in the 0.1M of pH8.0 PBS).Afterwards by dechlorination water washing 5 times for carrier.Afterwards ispol for carrier (L-Phe, D-Leu, L-arginine, glycine, D-and L-Aspartic acid, derive from Sigma) solution (0.5%, in the 0.1M of pH8.0 PBS) is sealed.Afterwards by dechlorination water washing 5 times for carrier.By the 0.2M carbonate buffer solution pretreatment of carrier use pH8.5 1 hour.2.5% glutaraldehyde solution carrier is used in the 0.2M carbonate buffer solution of pH8.5 is processed 15 minutes.Afterwards by dechlorination water washing 5 times for carrier.By enzyme, (carbonic anhydrase separates from human blood and derives from CO afterwards 2Solution) concentration with 1.0mg/ml in carbonate buffer solution was added to carrier in 2 hours.Afterwards by dechlorination water washing 4 times for carrier, with NaCl (Sigma) solution (1.0M), wash 1 time and with dechlorination water washing 4 times.Be immobilized in four (4) days during in complete.
The method allows carbonic anhydrase at the covalent immobilization had on the carrier of water-wet behavior, and enzyme is held on carrier by covalent bond.The method also provides than this area current known outstanding enzymatic activity and stability.”
" each step of this process for fixation is carried out in room temperature.The chemical/biological that uses learn with in example I, describe those are identical.Carbonic anhydrase is immobilized on the Raschig.TM. ring (5kg) of being made by nylon 6/6.HCl solution (3.93N) for solid carrier is hydrolyzed to 1 hour.Afterwards carrier is washed 1 time with dechlorination water washing 6 times and with NaOH solution (0.1M).Carrier is used to the dechlorination water washing 4 times again.Afterwards carrier is hatched 2 to 18 hours with PEI solution (concentration of 0.5M, in the 0.2M of pH8.3 carbonate buffer solution).By the length adjustment of hatching to required physical and chemical condition.Afterwards carrier stayed to draining and do not wash before it is hatched with glutaraldehyde.Carrier is hatched 2 hours in glutaraldehyde solution (1.0%, in the 0.2M of pH8.3 carbonate buffer solution).Afterwards carrier is hatched 2 hours in carbonic anhydrase solution (0.5mg/ml).Afterwards carrier is washed 1 time with dechlorination water washing 3 times and with NaCl solution (1.0M).Dechlorination water washing 3 times for carrier the most at last.This program can be carried out in one day, also can it be separated in two days, to be conducive to the working time in the step that adds polymine.Under latter event, can make afterwards solid carrier contact at All Through The Night with polymine.The use of the single step that glutaraldehyde adds not only contributes to the generation that reduces production time and its cost but also reduction toxic waste.”
Particle can have the enzyme immobilization system, and described system comprises the following or basically is comprised of the following: carrier; The first slider with polyamines molecule; The first connector with the first aldehyde radical and second aldehyde radical; And biologically active bodies; Wherein said carrier is connected to the polyamines molecule of described slider, and wherein said slider is connected to the first aldehyde radical of described the first connector, and wherein said biologically active bodies is connected to the second aldehyde radical of described the first connector.Also can have the second connector with the first aldehyde radical and second aldehyde radical, the first aldehyde radical of wherein said the second connector is connected to the polyamines molecule of described slider and the second aldehyde radical of described the second connector is connected to described carrier.Carrier can be made by the compound of the group of selecting free the following to form: plastics, biopolymer, polytetrafluoroethylene (PTFE) (PTFE), pottery, polyethylene, polypropylene, polystyrene, nylon, silica, carbonate, its derivative and combination thereof.The group that the polyamines molecule of slider can select free the following to form: hydrocarbon, acyclic hydrocarbons alkene, polyenoid, polyenoid, imines and polymine.The polyamines molecule of described slider can be hydrophilic.The group that the first connector can select free the following to form: glutaraldehyde (glutaraldehyde), glutaraldehyde (glutardialdehyde), 1; 3-diformyl propane, glutaraldehyde (glutaral), 1; 5-glutaraldehyde, 1,5-pentanedione and glutaraldehyde (cidex).The group that the second connector selects free the following to form: glutaraldehyde (glutaraldehyde), glutaraldehyde (glutardialdehyde), 1; 3-diformyl propane, glutaraldehyde (glutaral), 1; 5-glutaraldehyde, 1,5-pentanedione and glutaraldehyde (cidex).
Should be noted that other immobilizations can be used with small-particle of the present invention with embedding techniques together with method, for example, as the immobilization of describing in the U.S. Patent number 6,524,843 that is bonded to by reference this.
Should also be noted that the operable absorption and desorption of embodiment of the present invention unit can depend on that various parameters and operating condition are different types.This unit can be, for example, the form of filling reactor, spray reactor, fluidized-bed reactor etc., can have various structures such as vertical, horizontal etc., and whole system can depend on the circumstances and uses a plurality of unit in parallel or series connection.
It should be noted in the discussion above that and can use particular to use dissimilar biocatalyst to remove the gas of other types from effluent and other admixture of gas as enzyme.Different gas-liquid contact absorption process can be used together with the enzyme particle with enzyme, and described enzyme is designed to given reaction in the thin reactive membrane of catalysis.
Should also be noted that and be known that the quality transport phenomenon of following with one or more complexity (reversible) chemical reaction is very difficult to be described by basic principle; In addition, the analytic solution accurately of governing equation is unavailable.Therefore developed simplified model, it allows (part) of this equation to solve, as membrane modle.The present invention is based on: the particle size based on membrane modle is regulated, and it is characterized in that describing quantitatively and qualitatively CO in direct, comprehensive mode 2Catch phenomenon, and allow for given CO 2Capture systems and the useful definite granularity of operation.
Above being to be understood that, description and illustrational each embodiment do not limit the content of actual invention.
Embodiment 13
In this embodiment, use the particle immobilized enzyme carbonic anhydrase of different size.Particle is made by nylon and is had a following particle mean size (in micron): 9,17,88 and 131.Carbonic anhydrase also is immobilized onto on the 50nm aluminium oxide particles.Use stirring pool determine granularity to enzyme at CO 2Impact to the effect in the absorption in the 2M MDEA of 25 ℃.Enzyme concentration is 0.2g/l.Stirring pool is that the absorbent solution that wherein will contain the given volume of the particle with enzyme is exposed to predetermined C O 2The reaction member of dividing potential drop.Solution is stirred with dispersed particle equably.Along with CO 2Be absorbed in solution CO 2Dividing potential drop reduces until it reaches balance.Based on pressure data, can determine CO 2Speed with reactant aqueous solution.There is the reaction rate of enzyme and the ratio that does not there is the reaction rate of any enzyme by calculating, obtain all transposons (ToF).In table below of the result obtained and Fig. 5, provide.Also use experimental data to calculate the reactive membrane thickness (details is referring to embodiment 11) under free or existence that be immobilized onto the enzyme on particle.
Figure BDA00003606685400411
From these data, at first it should be appreciated that granularity is zero situation corresponding to the solvable carbonic anhydrase of use.Can also observe enzyme immobilization has been reduced to CO 2Hydration rate.What can further observe is in solution, to add free or immobilized enzyme are reduced to the thickness of reactive membrane to be less than 4 microns from 9 microns (referring to embodiment 11).Can also observe, the impact of enzyme reduces along with granularity and increases, and reaches 60% of the approaching all transposons that obtain with lyoenzyme.Result is also pointed out 15% of impact with particle impact higher than corresponding resolvase concentration, granularity should be less than approximately 6 times of reactive membrane (referring to, for 17 micro particles that improve all transposons, 5.9 times of reactive membrane thickness).Should also be noted that the particle that is less than reactive membrane thickness demonstrates with respect to the more remarkable increase of macroparticle on all transposons.

Claims (73)

1. one kind from containing CO 2GAS ABSORPTION CO 2Method, described method comprises:
Make described containing CO 2Gas absorbs mixture with the water-based that comprises water and absorption compound and is making described CO 2The condition that occurs in the following manner of quality transmission under contact:
At first by air-film thickness (δ g) occur; And
Afterwards by thickness of liquid film (δ l) generation, wherein δ l=D CO2/ k L, k wherein LCO 2Mass transfer coefficient in described liquid and D CO2CO 2Diffusion coefficient;
Determine CO 2Reactive thickness of liquid film (the δ of hydration reaction Rf), δ wherein Rf=(δ l)/Ha, wherein Ha 2=(k 1.D CO2)/(k L) 2, Ha>2 and k 1=k 2C Ab, k wherein 2The CO in described absorption mixture 2The kinetic constant of hydration reaction, and C AbThe concentration that described water-based absorbs absorption compound described in mixture; And
Absorb in mixture enzyme particle be provided in described water-based, wherein by described enzyme particle according to described reactive thickness of liquid film (δ Rf) sizing to be to improve described CO 2The enzymatic of hydration reaction.
2. method claimed in claim 1, described method comprises the temperature of the concentration by regulating described absorption compound, described method, described mass transfer coefficient (k L) or their combination control described reactive thickness of liquid film (δ Rf).
3. the described method of claim 1 or 2, described method comprises described enzyme particle sizing and to make d/ δ to have diameter (d) Rf<6, d/ δ Rf<3, d/ δ Rf<1, d/ δ Rf<0.05 or d/ δ Rf<0.025.
4. the described method of any one in claims 1 to 3, described method comprises described enzyme particle sizing with respect to by having at least 32.7 d/ δ RfLarger enzyme particle low all transposons that can obtain by CO 2All transposons increase to few 50%.
5. the described method of any one in claim 1 to 4, described method comprises described enzyme particle sizing to obtain at least 17%, 27% or 57% the CO that absorbs all transposons of resolvase that the lyoenzyme in mixture obtains by described water-based 2All transposons.
6. the described method of any one in claim 1 to 5, wherein said reactive thickness of liquid film (δ Rf) be 10 μ m, 5 μ m, 3 μ m, 2.5 μ m, 2.0 μ m, 1.9 μ m or 1.8 μ m at the most.
7. the described method of any one in claim 1 to 6, wherein said absorption compound is so that described reactive thickness of liquid film comprises alkanolamine MDEA for the concentration of 3.2 μ m at the most, and described enzyme particle is sized to 17 μ m at the most.
8. the described method of any one in claim 1 to 7, wherein said enzyme particle comprises carrier material and carbonic anhydrase, described carrier material is selected from nylon, cellulose, silica, silica gel, shitosan, polyacrylamide, polyurethane, alginates, polystyrene, polymethyl methacrylate, magnetic material, agarose, aluminium oxide, and corresponding derivative, and their combination.
9. method claimed in claim 8, wherein by described enzyme by immobilization technology with respect to described carrier material immobilization, described immobilization technology is selected from: absorption, covalent bonding, embedding, copolymerization, crosslinked and seal, and their combination.
10. one kind absorbs mixture CO for the enzymatic water-based 2The method of hydration reaction, wherein said CO 2Quality pass through thickness of liquid film (δ l) occur, wherein said water-based absorbs mixture and comprises liquid solution and enzyme particle, and in the provided reactive thickness of liquid film (δ for described hydration reaction Rf) be less than described thickness of liquid film (δ l) condition under, and comprise by described enzyme particle sizing being made it with respect to described reactive thickness of liquid film (δ Rf) enough little and strengthen described enzymatic.
11. method claimed in claim 10, described method comprises according to described reactive thickness of liquid film (δ Rt) by described enzyme particle sizing to there is diameter (d), make d/ δ Rt<6.
12. the described method of claim 11, described method comprises described enzyme particle sizing so that d/ is δ Rt<1.
13. the described method of claim 12, described method comprises described enzyme particle sizing so that d is less than δ RtApproximately one, two, three or four orders of magnitude.
14. the described method of claim 13, described method comprises described enzyme particle sizing so that d is less than δ RtAbout two orders of magnitude.
15. the described method of any one in claim 10 to 14, wherein said water-based absorbs mixture and comprises absorption compound and δ RtFor 10 μ m at the most.
16. the described method of claim 15, wherein δ Rt5 μ m at the most.
17. the described method of claim 16, wherein δ Rt3 μ m at the most.
18. the described method of claim 17, wherein δ Rt2.5 μ m, 2.0 μ m, 1.9 μ m or 1.8 μ m at the most.
19. the described method of any one in claim 15 to 18, wherein said absorption compound comprises primary amine, secondary amine, tertiary amine, primary alkanol amine, sec alkanol amine, tertiary alkanolamine, primary amino radical acid, sour, the tertiary amino acid of secondary amino group, or carbonate compound, or their combination.
20. the described method of any one in claim 15 to 18, wherein said absorption compound comprises at least one in the following: piperidines, piperazine, the derivative replaced by least one alkanol groups of piperidines or piperazine, monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 2-(2-aminoethylamino) ethanol (AEE), TRIS (TRIS), N methyldiethanol amine (MDEA), dimethyl monoethanolamine (DMMEA), diethyl monoethanolamine (DEMEA), triisopropanolamine (TIPA), triethanolamine, the dialkyl ether of PAG, the dialkyl ether of polyethylene glycol or dimethyl ether, glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, valine, leucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine and derivative thereof, taurine, N-cyclohexyl-1, the 3-propane diamine, N-sec-butyl glycine, N-methyl-N-sec-butyl glycine, diethyl glycine, dimethylglycine, methyl amimoacetic acid, N-methyltaurine, methyl-α-aminopropionic acid, N-(β-ethyoxyl) taurine, N-(beta-aminoethyl) taurine, the N-methylalanine, 6-aminocaprolc acid and sylvite thereof or sodium salt, potash, sodium carbonate, ammonium carbonate, the ammonium carbonate of the solution of potassium carbonate of activation and the sodium carbonate liquor of activation or activation, or their combination.
21. the described method of any one in claim 15 to 18, wherein said absorption compound comprises alkanolamine.
22. the described method of claim 21, wherein said absorption compound comprises tertiary alkanolamine.
23. the described method of claim 22, wherein said absorption compound comprises N methyldiethanol amine (MDEA).
24. the described method of claim 23, the condition that the concentration that wherein said MDEA has and the described water-based provided absorb mixture makes δ RtFor 3.2 μ m at the most and described enzyme particle is sized to 17 μ m at the most.
25. the described method of any one in claim 10 to 24, wherein δ RtBased on Hatta number (Ha).
26. the described method of claim 25, wherein δ RtAlso based on described thickness of liquid film (δ l).
27. the described method of claim 26, described method comprises according to following formula determines described reactive thickness of liquid film (δ Rf):
(δ rf)＝(δ l)/Ha
Wherein Ha is defined as Ha for first kernel response 2=(k 1.D CO2)/(k L) 2.
28. the described method of any one in claim 25 to 27, wherein Ha is greater than 2.
29. the described method of any one in claim 10 to 28, wherein said enzyme particle comprises carrier material and carbonic anhydrase.
30. the described method of claim 29, wherein said carrier material is made by the compound except described carbonic anhydrase.
31. the described method of claim 30, wherein said carrier material comprises nylon, cellulose, silica, silica gel, shitosan, polyacrylamide, polyurethane, alginates, polystyrene, polymethyl methacrylate, magnetic material, agarose, aluminium oxide, and corresponding derivative or their combination.
32. the described method of claim 31, wherein said carrier material has the density of about 0.6g/ml to about 5g/ml.
33. the described method of claim 31 or 32, wherein said carrier material has the density higher than about 1g/ml.
34. the described method of any one in claim 30 to 33, wherein by immobilization technology by described carbonic anhydrase with respect to described carrier material immobilization, described immobilization technology is selected from: absorption, covalent bonding, embedding, copolymerization, crosslinked and seal, and their combination.
35. the described method of claim 34, wherein said carrier material comprises core and be arranged on the immobilization material on described core, and described carbonic anhydrase is by described immobilization material immobilization.
36. the described method of claim 34 or 35, wherein said carbonic anhydrase is by described immobilization technology stabilisation.
37. the described method of claim 29, wherein provide described carbonic anhydrase as crosslinked enzyme aggregate (CLEA), and described carrier material comprises a part of described carbonic anhydrase and crosslinking agent.
38. the described method of claim 29, wherein provide described carbonic anhydrase as crosslinked enzyme crystal (CLEC), and described carrier material comprises a part of described carbonic anhydrase and crosslinking agent.
39. the described method of any one in claim 10 to 38, wherein by described enzyme particle sizing to there are approximately 17 μ m or to be less than the approximately diameter of 17 μ m.
40. the described method of claim 39, wherein by described enzyme particle sizing to there are approximately 10 μ m or to be less than the approximately diameter of 10 μ m.
41. the described method of claim 40, wherein by described enzyme particle sizing to there are approximately 5 μ m or to be less than the approximately diameter of 5 μ m.
42. the described method of claim 41, wherein by described enzyme particle sizing to there is approximately 1 μ m or to be less than the approximately diameter of 1 μ m.
43. the described method of claim 42, wherein by described enzyme particle sizing to there is approximately 0.1 μ m or to be less than the approximately diameter of 0.1 μ m.
44. the described method of claim 43, wherein by described enzyme particle sizing to there is approximately 0.05 μ m or to be less than the approximately diameter of 0.05 μ m.
45. the described method of claim 43, wherein by described enzyme particle sizing to there is approximately 0.025 μ m or to be less than the approximately diameter of 0.025 μ m.
46. the described method of any one in claim 10 to 45, described method comprises:
Select the required enzyme activity level of described enzyme particle;
Select maximum to allow particle concentration;
Determine and reach the total surface area that required enzyme activity level needs;
Determine that the cumulative volume of described particle allows particle concentration to reach described maximum; And
Determine the full-size of described particle, to allow in maximum under particle concentration, obtain described enzyme activity level.
47. the described method of any one in claim 10 to 46, wherein by described enzyme particle, the maximum particle concentration with about 40%w/w is provided in described water-based absorption mixture.
48. the described method of claim 47, wherein said maximum particle concentration is about 30%w/w.
49. the described method of any one in claim 10 to 48, wherein by described particle sizing and so that the pumpable concentration of resulting suspension provides.
50. the described method of any one in claim 10 to 49, described method comprises to be made containing CO 2Gas and described water-based absorb mixture and contacts in reactor with from the described CO of containing 2Gas removes described CO 2At least a portion, thereby produce CO 2The gas of dilution and the rich solion that contains described enzyme particle.
51. the described method of claim 50, wherein said absorbent solution and described containing CO 2Gas is convective flow each other.
52. the described method of claim 50 or 51, described method comprises from described rich solion and removes described enzyme particle to produce the rich solion of enzyme particle fraction and particle dilution.
53. the described method of claim 52, wherein by the further sizing of described enzyme particle to promote removing from described rich solion.
54. the described method of claim 52 or 53, removing by least one in the following of wherein said enzyme particle undertaken: filter mechanism, magnetic separates, centrifugal, cyclone separator, sedimentation, film separates or their combination.
55. the described method of any one in claim 52 to 54, the removing method of selecting by the existence of the size according to described enzyme particle, density and magnetic that removes of wherein said enzyme particle carries out.
56. the described method of any one in claim 52 to 55, wherein said removing by the following undertaken: clarifier, thickener, vacuum or filter-press, intermittence or continuous filter, Horizontal-type filtering filter press, tubular filter, centrifugal discharge filter, drum filter, scraper discharging filter, rolling discharging filter, disc filter, sedimentation centrifuge, decanting centrifuge, filtration sedimentator, basket sedimentator, cyclone hydraulic separators, hydrocyclone, ultrafilter, micron filter part, nanofiltration device, or their combination.
57. the described method of any one in claim 52 to 56, described method comprises that the rich solion to described particle dilution carries out desorb or mineral carbonation to produce the solution of ion dilution.
58. the described method of claim 57, wherein recycle at least a portion of the solution of described ion dilution to form at least a portion that described water-based absorbs mixture.
59. the described method of claim 58, wherein merge the recycle sections of the solution of at least a portion of described enzyme particle fraction and described ion dilution to form at least a portion that described water-based absorbs mixture.
60. the described method of any one in claim 57 to 59, wherein said rich solion comprises sediment and before carrying out described desorb or described mineral carbonation, described sediment is removed from described rich solion.
61. the described method of claim 60, described method is included in described rich solion and forms described sediment and described enzyme particle is provided to the characteristic that promotes that described enzyme particle separates with described sediment.
62. the described method of claim 50 or 51, described method comprises carries out desorb or mineral carbonation to produce the solution of ion dilution to described rich solion.
63. the described method of claim 62, wherein said enzyme particle allows the catalysis of described desorb or described mineral carbonation.
64. the described method of claim 62 or 63, wherein by described enzyme by described enzyme particle stabilisation, and provide to promote bicarbonate ion and hydrogen ion to CO by described particle sizing and with the concentration that will be carried through the desorb reactor by described rich solion 2The conversion of gas and water, thus CO produced 2The solution of gas flow and described ion dilution.
65. the described method of claim 64, described method comprises further described enzyme particle with respect to CO 2The reactive thickness of liquid film sizing of dehydration is to increase CO described in described desorb 2The enzymatic of dehydration.
66. the described method of any one in claim 62 to 65, wherein said rich solion comprises sediment, and before carrying out described desorb or described mineral carbonation, described sediment is removed from described rich solion.
67. the described method of any one in claim 50 to 66, wherein said water-based absorbs mixture and described containing CO 2The contact of gas is carried out in comprising the absorption level of at least one reactor, and described at least one reactor is selected from packed column, spray column, fluidized-bed reactor and their combination.
68. one kind for CO 2From the enzymatic method of the dehydration of the rich ion aqueous mixture that comprises bicarbonate ion and hydrogen ion and enzyme particle, wherein said CO 2Quality pass through thickness of liquid film (δ Ld) occur, wherein said rich ion aqueous mixture is in the provided reactive thickness of liquid film (δ for described dehydration rfd) be less than described thickness of liquid film (δ Ld) condition under, and comprise by described enzyme particle sizing being made it with respect to described reactive thickness of liquid film (δ Rf) enough little and strengthen described enzymatic.
A 69. CO 2Catch preparation, described preparation comprises:
Liquid solution, described liquid solution comprises water and compound of reaction and makes reaction CO 2+ H 2O ← → HCO 3 -+ H +Wherein said CO can occur 2Quality pass through thickness of liquid film (δ l) occur, and wherein said liquid solution is adjustablely to provide, to be less than described thickness of liquid film (δ l) the reactive thickness of liquid film (δ for described reaction rfd); And
Enzyme particle in described liquid solution, described enzyme particle has with respect to described reactive thickness of liquid film (δ Rf) enough little size to be to strengthen the enzymatic of described reaction.
70. one kind is passed through with carbonic anhydrase reaction CO 2+ H 2O ← → HCO 3 -+ H +Enzymatic and process the system of fluid, described system comprises:
Reactor, described reactor has the reative cell that receives described fluid, and is configured to: be provided for by thickness of liquid film (δ l) described CO occurs 2The quality transmission condition and provide and be less than described thickness of liquid film (δ l) the reactive thickness of liquid film (δ for described reaction rfd); And
Enzyme particle, described enzyme particle is present in described reative cell and comprises described carbonic anhydrase, and wherein said enzyme particle has with respect to described reactive thickness of liquid film (δ Rf) enough little size to be to strengthen the described enzymatic of described reaction.
71. the described system of claim 70, wherein said reactor structure for make described enzyme particle together with described fluid from wherein flowing through.
72. one kind at CO 2Catch the kit of middle combination and use, described kit comprises:
Compound of reaction, described compound of reaction makes reaction CO for being added to water with formation 2+ H 2O ← → HCO 3 -+ H +The liquid solution that can occur, wherein said CO 2Quality pass through thickness of liquid film (δ l) occur and wherein said liquid solution is adjustablely to provide, to be less than described thickness of liquid film (δ l) the reactive thickness of liquid film (δ for described reaction rfd); And
For being added to the enzyme particle of described liquid solution, described enzyme particle has with respect to described reactive thickness of liquid film (δ Rf) enough little size to be to strengthen the enzymatic of described reaction.
73. one kind is passed through with carbonic anhydrase reaction CO 2+ H 2O ← → HCO 3 -+ H +Enzymatic and process the method for fluid, described method comprises:
Described fluid, wherein said CO are provided in reaction zone under the existence of the enzyme particle that comprises described carbonic anhydrase 2Quality pass through thickness of liquid film (δ l) occur; And
In described reaction zone, provide condition to be less than described thickness of liquid film (δ to provide l) the reactive thickness of liquid film (δ for described reaction rfd), make described enzyme particle and described reactive thickness of liquid film (δ rfd) size than the enzymatic that strengthens described reaction.
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* Cited by examiner, † Cited by third party
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CN104607037A (en) * 2014-12-23 2015-05-13 北京化工大学 A method and a system for CO2 trapping by utilization of a pH swing principle
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CN115999357A (en) * 2022-11-30 2023-04-25 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

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2776143A4 (en) * 2011-11-11 2016-01-27 Co2 Solutions Inc Co2 capture with carbonic anhydrase and membrane filtration
EP2912172B1 (en) 2012-10-29 2018-12-05 CO2 Solutions Inc. Techniques for co2 capture using sulfurihydrogenibium sp. carbonic anhydrase
WO2014118633A2 (en) * 2013-01-31 2014-08-07 Carbon Clean Solutions Pvt, Ltd Carbon capture solvents and methods for using such solvents
CA2890582C (en) 2014-08-27 2022-07-19 Normand Voyer Co2 capture methods using thermovibrio ammonificans carbonic anhydrase
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1112853A (en) * 1994-03-04 1995-12-06 戈里特斯奇公司 Liquid-phase catalyst-assembly for chemical process tower
WO2004056455A1 (en) * 2002-12-19 2004-07-08 Co2 Solution Inc. Process and apparatus using a spray absorber bioreactor for the biocatalytic treatment of gases

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9711439D0 (en) * 1997-06-04 1997-07-30 Rogers Peter A Bioreactor for dioxide management
CA2353307A1 (en) * 2001-07-13 2003-01-13 Carmen Parent Device and procedure for processing gaseous effluents
CA2783190C (en) * 2002-12-19 2015-06-16 Co2 Solutions Inc. Process and apparatus for the treatment of co2-containing gas using carbonic anhydrase
KR20110087273A (en) * 2008-09-29 2011-08-02 아커민 인코퍼레이티드 Process for accelerated capture of carbon dioxide
AU2010281323B2 (en) 2009-08-04 2015-09-03 Saipem S.P.A. Process for co2 capture using carbonates and biocatalysts
AU2010281322B2 (en) * 2009-08-04 2016-06-16 Saipem S.P.A. Process for CO2 capture using micro-particles comprising biocatalysts
CA2777272A1 (en) * 2009-11-04 2011-05-12 Co2 Solutions Inc. Enzymatic process and bioreactor using elongated structures for co2 capture treatments
DK2632570T3 (en) * 2010-10-29 2020-07-27 Saipem Spa Enzyme Enhanced CO2 Desorption Methods

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1112853A (en) * 1994-03-04 1995-12-06 戈里特斯奇公司 Liquid-phase catalyst-assembly for chemical process tower
WO2004056455A1 (en) * 2002-12-19 2004-07-08 Co2 Solution Inc. Process and apparatus using a spray absorber bioreactor for the biocatalytic treatment of gases

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104607037A (en) * 2014-12-23 2015-05-13 北京化工大学 A method and a system for CO2 trapping by utilization of a pH swing principle
CN104607037B (en) * 2014-12-23 2021-04-23 北京化工大学 CO realization by utilizing pH swing principle2Method of trapping
CN108602047A (en) * 2016-02-12 2018-09-28 巴斯夫公司 Carbon dioxide sorbent for air quality control
CN108602047B (en) * 2016-02-12 2022-05-03 巴斯夫公司 Carbon dioxide sorbents for air quality control
CN110073194A (en) * 2016-12-22 2019-07-30 文塔纳医疗系统公司 System and method for Sample preservation
CN115999357A (en) * 2022-11-30 2023-04-25 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
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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