Formulation and process for co2 capture using micro-particles comprising biocatalysts

专利摘要:

公开号:DK201400144U1
申请号:DK201400144U
申请日:2014-10-23
公开日:2014-11-14
发明作者:Fradette Sylvie；Gingras Julie；Voyer Normand；Carley Jonathan；Ceperkovic Olivera
申请人:Co2 Solutions Inc；
IPC主号:

专利说明:

i DK 2014 00144 U1 pmmmB før mz capture umm compkisinø
SfØCATÅiYSTS
FULD OF TUF iNVENTPN
The present invention refalés generally to C02 capiure and more pafticulariy to a s processfor C02capture isslag micro-parficles eomphsing biocatalysts
BAøtØsRØOMD
Increassngly dlre waniings øf the dangers øf ciimaie change by the worid’s scieotiic community cornhined wsth greater public awaréness and eoncern over the issus has prompfed snereased momentøm towards global reguistlon aimed at reducing marvmade to greenhouse gas (GHGs) emissions, most notabiy carbon dloxlde. Ultlmately, a significant cut in Nørth American and global 0(¼ emissions will reqoire redu etions tom the eleotnøity prøduetfon sector, the single largest source of C02 worldwide. Accordsng to the international Energy Agenoy’s (IEÅ) GHG Program, as of 2006 fhere were neariy 5,000 fossri fttet pøwtr plants wøridvddé generating neariy 11 billion tons of C02> 15 repmserttihg nearly 40% of totai global anthrøpogenie COs emissions. Of the se emissions from the powøf generation ssetør, 81% were from coai fired pianis, Although the long-term agenda advéeated by governments is repiaeement of fossil tue! generation by mnewahieS; growing energy demand, combined wlth the enormoøs dependence on fossi i ømmm in the near tø medium term dictates thai this fossil base remain 20 operailonal. Thus; to implemant an effeetive GHG recuotion system wlil require that the CO<; emissions generaied by this sector be mitigated. with carbon captnre and storage (CCS) providlng ond of the Pest snown solutions.
Tris CCS proces» remaves 002 from s C02 contssning flue gas, eoabies produistion of a highly ooncentrated COs gas stream which is compressed and transported to a 35 sequesfration site. This site may be a depiated oil fietd or a saltos aquffer; Seqoesirsfion in ocean and mineral carbanation are Orø aiiernate ways fo seqoester fhat am in the research phase, Daptured CO; can also be used for enhanced oii recovery.
Current technologies for CO* capture are based primarily on the use øf amine spfetions which are drculated through two main distinet units: an absorption tower coupled to a 30 desorption for stripplogl tøwer.
Biocatalysts have baen used for CO£ absorption appiicai;one. Epr exampie, C02 transformation rrsay be catalyged by the ensyme earboniO ahhydrase as fbildwsi DK 2014 00144 U1 zmitmtv irnå&dr®*« w. . _..
*-----------------t$f>
Under optimum oonditions* ttie oalalyzed turnover rate of this reaction may mach 1. x 10* rnoiecMies/second.
Thore ar© seme known ways of providihø carbønio anhydrase irt C02 oapture reactors. One «y is by immoMpsing tb© enzym© on a solid paeking materiai in a paoked tower readter, Anothor way is by prevsding the enzyrna in a søluble staf© tn a solution within or flbyrog through a reactcr, Beth of ihese methods provide benefits but aiso some limitations, Enzyme immobized on a solid packing materiai limits the enzym© benefit sine® it has a iimited presønoe in the thin reaetive iiquid film at the gasdiquid interface whiqh has a thlekness of about 10 pm; enzyme on padang is sevarai mililmetres from the gas-itguid interface, Seluble enzyma brings the optimal enzym© impaei however it cannot be easily separated from tha solution and tf the enzym© is nst robust to intense cqndltlons such as ihose use# in desorpbon operations, tt witl be denatured and the process wpi regysre high ieyeie øf eonfinuous enzyme replaeernerst
Thara is a haed for a technology that overcomes some of these problems and chaiianges of the known fachniques for providing biocataiysts such as carbenlo anhydras® in Gpg oapture reactors.
sytytstARY of the invention
The present iiwaritlon réspsnds fd the aboye mentioried neéd by providing a proesss for CQa oapture ussng micro-partlcles comprising biocelalysts.
Nor© particularty, the -present invention provides a prooeas for oapfuring CO* from a COs"COhtainsng gas compdking eoniaetlng the CCT-oonfaining gas wif.h an absorption mixture within a packed rsaefoc the absorption mixture oompdsing a liquld solution and mibra-pariioles, the rnicro-partieies comprielng a support malaria) and bioøataiysts supported by the support materiai and belng sized and provlded in a concentratjon such that the absorption mixture fiows through the packed reaefor and that the mierø-parfiefes ar© enrrsed with the ilquki solution to promote dissolution and transformation of CO, info bioarfeohate and hydrogen ionsptheroby produeing a COgrdepteted gas and an lomrich mixture compnsing the micro-particSes.
In one opiional aspect, the prøeess comprises mmoving the mi#o»partiq|©s bom tbe ion-hch mixture to produoe an son~neh solution. In arrøther optionsi aspeci, the romoving of 3 DK 2014 00144 U1 the micfoisadfoles is performeei by filtrallon meehanism, magjh&tfo s&pé&fåm, ^ntnfbømtioii* betone, sedimsotstipo isr a combinaiioo tiereof.
In another eptSoaai aspset, the process oompbses performlng desorptfon ør mineral oarbonatfon on the lønfoch solution tø produce an ion-depieted .solution, The ion-hob s mixture may oompdae precipitates and the precipitates may be remeved from the Ion-hob mixture prtpr lp performsng the desorption or the mineral cafbønetion.
in anotner optional asped, the proeess qømprises adding an ampynt of the micro-patilcies to the ion-depieted solution befare recycllng the ion-depieted solution før funder eontactini the C02-eontaihfog gas.
i o in another optional aspact, the process composes feeding the ion-hob mixture into a desorption reactor, the micro-particies being stabffiaed by the support matenal and Peing siæd and provided in a søneentratfon in the désøFptfon reacior euoh ttit the micro-pariicles are carrled with the ion-rich mixture to promote transformation of the bicarbøhafe and hydrogen Ions into CO gas and Mer, thereby produclng a CO gas is stream and the ion-depieted solution.
In another optional aspeef, the micrø-psrtkdes may be sfoedto faøilitat© separation of the micro-particies from the lorMich mixture. For instanoe. the miøro-pahicies may be sized to have a diameter ahove abøui 1 pm or above' abouf 5 pm.
In anotber Optional aspect, tbs micro-partloies, may be sked to have a caiaiyiic surface 2« area com prising the biocataiysts having an aotivlty density so as to provide an activity level equlvafent to a corresponding activity level of solubie biocataiysts above about 0.05 g biocatalysf IL, optionaly botween about 0,05 g biooatalyst /1 and about 2 g biocatalysf /L, and prøforebiy betyyeén afooot 0.05 g biocaiaiyst /L and:about 0.5 g blocataiyst /1, for tb@ case of biooatalysts havfog a mfoimufo activity of about 250 WA units/mg, 25 in another optfonal aspeef, the absorption mixture and the CD form a reactive liqukl film having a tbiobness and the mforo-particiM ara srød so as to be; within an order of magnitude of the tbickness of the reactive Ifouid film. In anofhér optional aspact, the absorption mixture and ihe CO form a reactive liquid Ira havfog a ihickness and the mforø-partioies are seed so as to be smaller than the thickness of the reabiive liquid film, 30 The ihickness of the reactive iiquid Mm may be about 10 pm;
In another optional aspeci the micn>padidles aro sizod between about 1 pro and about 100 μ ro.
4 DK 2014 00144 U1 in anoiheroptiOriai aspéot, precipitatas may be formad in thé ion-deh mlxfure and the micro»parSciés may be sixed to bo laffer or heavier than the predpitates.
in another pptiøoai aspeoi the mlen>partictes havo an aotivity density of at ieast about 0.08 WA'mm2, optionaliy oi aboui 0.5 WA/mm2 or moro.
5 in another ophonal aspecf, the micro-particies ara providedin iheabsorption mixture at a maximum partide coneenirafion of about 40% w/w, In some øpiiona! aspects, the maximum micro-particie concentrafion may be 38% w/w. 30% w/w, 25% w/w, 20% w/w, 15% w/w, 10% w/w, or 5% w/w.
In another optiona! aspe!, the support materiai fe at least partiaity composed of nylon, tø cellulose, siilea, siiica gei, chltøsan, polystyrene, iraagnetkx materiai, or a eombinsiiøn theteof. The support may preferably beeompøsed of nylon
In another optional aspect, the density of tris support materiai may be between about 0.8 §/mi and about 3 g/rol.
in another øpbnal aspect, the absorption mixture composes water and an absorption 15 compound, The absorption compound may compose primary, sscondary and/or tertiary amines; primary, secondary and/or tertiary alkanoiamsnes; primary, secondary and/ør tertiary aminoacids; and/or csrbonaies. More pariiøuiariy, the absorption compound may comprise piperidlne, piparaxine, derivatives of piperidine dr piperaziné which are substituted by at ieasf one aikano! group, monosthanøjamirie {MEA), 2~am!nø-2-methyi-20 1-propanøi (AbtP), 2-{2~amino8thyiamino)ethanoi (AEE), 2~amino-2-hydroxymethyi~1:3-prøpanediOl (Trip)* hl-methyldiefbanoiamine (yDEA), dimethyimonoefhanolamine (DMMEA), dlethyimonoéthanoiamine (DEMEA), frifedpropandsmine (TIPA)·; irioirianoiamine, dsaikyiethér of poiyaikyiene giycøfe, diaikylether or dimeihytether of pøiyeihyiene giycot ammo adds comprising giydne, proline, arginine. Nstid'ine, lysine, 25 aspartie sold, giiftamie add, methionlne, sarins, fhféørime, giufamine, øyslelne, asparagine, vaiine, ieudne, feoleuoine, aianine, valide;. tyrdsine, tryptophari, phenylaianine, and derivatives soch as taurihe* N,oyd©hexy! 1,3-pFopanediamlne, M-seeondary butyl glydne, N-methyi N-seccndary butyi giycine, , dSiéthyiglyesne, dirnethyigiycine, , sarpdsine, , methyi taurine, methyN^amlhopropipnic acid, 3ά étimxydaufine, N-Cp-aminoetbyi)tåurine, M-methyi aianine, 8-aminohexanoic acid and potassium or sodltim aalts of the amino aélck;.:^a$sium carbonate, sodium carbonate, DK 2014 00144 U1 .ammonium oarbønate;, promoted potaaeium carbønata solutions | carfeonate solutions or promoted ammonium carbonates; or mixtures t in another optionat yp afthydrase; sodsum
siocatalysts are enzymes. The enzymes ars s parbonio arshydfase may ba immobslizad on a sutface of the ufs micro-papoléS:, ehtrapped within the support matersa! of the micro-pariicies, pr a combination thereof, in another spffonai aspect the earbonsc anhydrase may also tae prbvlded as cross-ilnked enzyme aggregates (CLEAs) and the support maferial comprises a portion of the carbonic anhydrase and crossisnker. In stili another optionai aspect, the earbonsc anhydrase is provided as cross-linked enzyma
support imaterial comprises a portion of the carbonic in another optionai aspect, the process composes seiecting a desired biocatalytic acfivlfy level; determinlng s maximum afiowable particle conpehtration for the paoked reacfor; determinlng a total surtace area required to reach the biocatalytic activity level; determinlng a total volume of the micro-partides to reach the maxlmum; and determinlng a maxlmum size of the miero-partibies to aehieve the Pipcatalytic activity level wsih the maximum aliowabie partide conoentration.
The invention also pro vides a process for capiunng C€b from a COrContalning gas oomprising contacting the COrcontafhlng gas wfth an absorption mixture cømpnsing a isquid solution and mloro-particies, the micro-partides cornprising a suppen materiel and biocataiysts supported by the support matenai and brnng sizad and provided ih a ©oncentration such tliat the absorption mixture is pumpabie and thai the micro-particlea ara carded with the iiquid solution to promote dissolution and transformation of CQa ioto bicarbønate and hydrogen ions, thereby produdng a CDsydepleted gas and an iønuich mixture cornprising the mioro-partieies.
In ene optional aspect bf this prooess, contacting the absorption mixture with the OQr oontaining gas is performed in an absorption stage comprlslrig et least one reacfor seieeted from a pscked tower, a spray tower, a fiuidizeti bed reactor and a øomhihatlori thereof.
in various other optionai asiets of this prooess, the features as mentioned in the previous paragraphs may aiso be used.
DK 2014 00144 U1 <*
The Invention also provines a pmcsess desorhlng Gøg ges from en iøn*rfeh aqueous mixture cømprising bicafbonaie and hydrogen ions, comprising: prøvidinig micro-partides In the føfHich aquéøus feixtpæ; feedtég the ion-rieh aqueous mixture into a desørptfen reacior; the miero-partldes comprissng e support materie! and biocatalysts supported S and stabifeed by tha support maieria! and belng sixed and provided In a concantration In the desorption reactcr such thai the micro-partides are carried wifh the iøn-rich aqueous mixture to promote traosfermetion ot the bicarbonafe and hydrogen søns into CG gas and watøfi thereby produdng a €02 gas stream and an ;on~depieted solution,
The present In^ntion afso provfdes micro-partides for irriroduction into a liquid solution Id for cøpturing CO . from a OOrContaining gas. The micro-partides may have options! features and uses as described før the optiona! aspects øf the proeess herein.
The present invention sisø provides s system for capiuring CG2 from a COr6on^iining gas. The system composes an absorption unit eomprislng a gas iniet fer the CO*· containing gas, a iiqusd iniet for providing an absorption mixture compnsing a liquid 15 solution and mscro-partides eomprislng a support materia! and bieeafalysts supported ihereby, The system oomprises a reaction charaber før alløwing the micrO' partictes fe be carried yyifh fe® liquid solution to enahle dissolution and transformation of C02 Into biearbooate and hydrogen ions, ihereby produeing a COrdep!eted gas and an ion-rich mixture: containing the mloro-particies. The system composes a gas øutiet fer expefifng 20 the COsfePPi^d gaf and a liquid outiet fer expeing the iomrich mixfum ooritainihg the røloro-partiefes· Optiønaiiy, the system may compose a removal unit fer removlng the micro-particies from the ion-depieted mixture and produdng en ion-rich solution; a regeneration unit før receiving; the ion-rich soSution and ailowing desorption or mineral carbonetion by releasmg the bicamonate ions fera the ion-rich solution to pføduce an 25 ion-depieted solution; ond an addition unl fer adding the mioro-partfeies to the ion-depSeted solution before the same is recyded back into the liquid intet of the absorption unit. The system may have optibnal features es described for the optiona! aspects of ih® process heroin, yaneging and coordinating the size, concentration and biocatalytio aotiyity of the micro-30 peitioles ailows advantageous operation in C02 oaptuns processes.
7:' DK 2014 00144 U1 brief mmnmwm of the brawings
Pig 1 is a proces® diagram øf an embodimeni of the present invention, wherein feiocatei>1fe micro-parttcfes flow in the absorption solution.
Flg 2 is a process diagram of another emhodiment of the present invention, whereln an 5 absorption unit is ooupied to a desorption unit and bioeaiaiyiic micro-particles flow in the absorption solution.
Flg 3 Is a sehematic representation of fhe gasdiquid interface in absorption.
Flg 4 is a graph showing evolution of residua! activity of enxyme micro-particles exposed to MQBh 2b'1 at 40'C, iustrating stabiiity effeet. to
OESORIPTION ØF PREFERREO EfSSBØBSMBCrS
Pigs 1 and 2 respsctively showiwo different embodiments of the process and systern of the present invention, ft shouid aiso bo ynderstøod thai embodiments ©f the micro-particles of the present invention may be ueed in conjuoefion wlth the process and 15 system.
In general the process takes acfvantage of biocatalysts for gas scrubblng espedaily for C02 removal from a eo2tepntelbing' ^b«nt in ene embodimenl the process enables the use of imrnobiiixed biocatalysts, such øs carbon se anhydrase, for Ctb ram oval In a pac&ed column. The carbohio anhydrasa may be supporfed on the micro-particles within 2ø the termulation, by belng dlréotfy bonded to the surface of the partlcle support material, emrappad inside or fixed to a porous support material matrix, enlrapped inside or fixed to a porous coating material that is provtded around a support partide that is itseif porous or nøn-pørous, or presérit as cniss linked emryme aggregates· (ClEÅ) or cross linked enx.yme crysials (€L£C) whérein the snnar “support materier itseif composes an 25 aggregatecf enernesend arty other agents that may be used In the formation of CLEAs orCLECs, such as a erosslinker. The ehayme may be provided in CLEA or CLFC teen, Vihioh may be provsded on or around a dffferehi support material which may be magnetic or not, it shouid be understood that a combination of the above fmmøbilissfian techhiques may be used to allow the biocataiytic micro- particles to flow ih the absorption 3 o solution through the ieactør, e.g, on. through and/or around packing material ofa psckod column.
DK 2014 00144 U1 8 8
The present invention provides s prøeess fer eapturing CO from a CCVcontalning gas. in orm embodsment of ihe prøcess, ihe first step eompnsfs eonfecting ihe CCV cørstaMng gas with an absorption mixture compris'sng a Iiquid solution and miero-partieles. The mioø-partfcfes compose a support maienai and hloeataiysis supported 5 thereby The micre-partieles ars provided such that the absorption mixture is pumpabie. Preferably, the step of contaoting the gas and iiquid phases is conducted suoh that the mæm-particfes flow with the iiquid solution, møve within the iiquid solution and møve in and out pf the bulk fiowT to imprøve rapid corweetive mass transfer of the CO reactant and the hydrogen and bicarbonate ion products, is This absorption step may be perfemied in a vanety of reactors. Preferabiy, the absorption step is pertermad in a paeked tower reaetor. it may also be done in a spray tower or another fypeof reaetor, in the case of a paeked tower, the micro-particles flow døwnward by tlowing with the Iiquid solution while coilidfeg against and ricocheting off the packing. Whlia the bulk flow of the miero-partiefes foliows thai of the Iiquid solution 15 through the reaetor the coiiisiøns oause some inicro^partioles to øhange direction and speed sq as to not move with the feoai fiow of the Iiquid solution. This movement wiibio the Iiquid solution may have linear and/or spinning oomponents and enables rapid obhysdlive mass transfer øf CCMø access the hiocatalysts m the micra-particias. in addition, ihe micro-particies ara preferabiy sized (aløng with density and sbape) to 20 eoabfé them to be earried with the bulk flow øf ihe iiquid solution and to be present in the thin reactive: film between gas and Iiquid phases. It shouid be understood that suoh mloro^particles may cempletely or partially break free of the bulk tlow. Suoh broken-fee mibrp»particiies may have a particularly thin Iiquid film coating enabling rapid penetration by CC, Tbese miero-partlcies aiiow the bicarbonate and hydrogen ions formad In the 25 fhih Iiquid film to rapidly disperse into the bulk Iiquid solution.
In another embodimeni the rector may be a spfey feaetør. The micro-particies may be defiected or caused to move out of the bulk ^ow due to the erøss-curreht cmmurteniof oounter-ourrent flow, incident spray nozzles, other micro-partlcies and pure iiquid dropsets, the side waiis of the reaetor, other objects fhat may be provided In reaetor, etc,, 3ø as desired, The spray reaoiør may be a verticai spray tower or a horizonfei duet type. The spray reaetor may be baffled or free of obstructions between the spray nozzles and a demsster at the opposed end. It wili be understood thai the bulk flow of the Iiquid solution may be refaliveiy large droplets or conglomeratlons of drdplets sprayed or DK 2014 00144 U1 so thai at leas a film of liquid g and denaturtng ih©' bidcataiysts, lo in the spray tower. The reactor is surrounds tn© røfom-patfleles to avoid di
when the reioro-parfctes ar© sprayed intø sueh a reaetor, som© micro* may fee pr©sent is single free particles wfth a thin llquid flim whiie øthers ar© present as a piurølity øf parfioles wilhlh indlviduai drøpleis, depeoding on the size of the Miet ndszies, the Slz© of the micro-p^rticles, the llquid and gas fiow conditions, amøng other operating parameters. The this llquid film surraunding the mfpro-parlictes allows rapid diffhslon of the 002 to access the biocatalysts as well as llquid repiacement tom movsment through the humid reactor and colilslons wtn droplefs and other miero* particles. The reactor raay de design ed to have various nozzles for ©prayfng, The micro* rticles tised in spray reactors enable incraased surface area and rapid mass tr as ths mlero-partides niece through tb© humid mist environment The micro-psrtides may be sizect for exampS©, to be earnacl witbln the absorption mixture in th© fbrm of en stomizeb mist. Th© size, density, ©hap© er porosity of the mlcrø-particies may be managed to heip increase surface area, Increase bioeataiyst ac&Sy, ensure the biocatalysts sfay molst or improve the movement of the micro-particie© reiatlve to tha COs*ccntalnlng gas to increase mass transfer
In another embobiment; the reactor may be a fiuidized bed reactor. Th© micro-pørticies may be provided in order fe flow through the fluidized bed to avold being refained
The size of the composite micro-padicies may depend en the type of reseter, the prceess condions, the density and shap© of ih© suppert materiel The density may be ohosen based en the desired caialytio aotivsty dr the separation of the micre-partieles from th© solution, er both. The density may be afeøui 5.8 to absuf 3 g/mt For instans©, nylon supports may hav® a density of about 1.1, cellulose supports may have a density of abcut i.S and magnetic supports may have © density ©f about 2,5. The density of the rhicrd*partid!©s may also be seleeted depeodtng on the type øf separatibn teehniqu© fbat is used to rernove the mlcro*partici©s atter th© absorption stage;, as the oase may be. for instance, if the micro-particies ara danser than water, then certaln separation methods may be adyentegaous, The density of the micro-particies may also hø seleofed to ©chance the absorption proces© Jtseff depanding on the operating conditions and the: type of reactor fhat is used. For exemple, if ibis desired fo avotd éshking the micro* DK 2014 00144 U1 m mixture, as desifod, The ef&ct of densky wiil aiso be appredated in fight øf sortie ©f the exathfjfes presented herøinhelow, The shape of the micro-partidas may also ba chøsen i^sedferi the. Hisd'pgical'feffiedla at$ thfé ava kable surfape aras of the msdFO-partidas, as Wfll ialso bé appreøiated in iight of some of the examples presented hereinbeiow.
In øoe optionaf aspeet of the present Invention, the particle conænffatipo and partide size are managed along with the enzym© activity in a; given solution, The paiticle conpanifation raqyirad to røach a given level oi enzym© activity Ih a solution is a parametar that Impacta the perfide siae, If the partide pohoaptration ir too high, it may result In an absorption mixture thai is diffiouit ør impossible to pe pumped through a gacked bed or spray master system, ih this røgard, to have in the soiuion the same enzyme activity as 1 g/L of solubfe earbonic anhydase (CA), results have derøonstrated that for 35§ pm polynwte micro •'partioles with OA fixed at their aurfaoa, with an activity density pf 0,51 WilPur-Anderson.unrt/mm2 (WA/nmh), the cPrresponding partide concenfration is about 80% (w/w), which is tao high to be pumpeel, in order to reduoe the partide ccncentration ynder a preferred ievei of 30% (w/w), which is eqyivaient to 300 gå. for partides Wh density near 1, the 350 pm micro-partides musf be eSher mpdified such that ihey prpvide a higher activity density or redueed in size. For exarnpfe given the sarné activity density of 0,51 unit WA/mm2 and the same activity equivaient to 1 g/L soiuble GÅ, using micrøxparticias with a diameter of 50 pm wøufd resuit in a partide Poncentrøtion of 90 g/L (or ø% w/w|, a pumpafele absorption mixture, Mørø regérdlng the partide size and cbhøentratlon wll be disøusaed hereinfeeiow with ragard to a øalculation mefhod and the impact bf vanens parsmaters.
in anothar øpiional aspoci of the present invention, fhe perfide size of the micro-perticies Is øhosen aeeordlng to fhe Ihiøkness øf the røaotive filrn in the given solution, The thldiness of the reactjve limdepends on certaio factors ihduding fhe type of absorption sotytion and the gas teing absorbed. In am. aspect, censiderfng most øommonly used C02 absorption solutions, fhe reactlve film has afhickness ofabout 10 pm.
Referring to Fig 3, a schematto represeniafionof the gas iiquid interface in an absorption unit Is shøwn, in this absorption unit, the gas phase fiows upward and iiguid phase downward. Mass transfer beiween the two phases fakes pface in the gas film (thickmoss of 5g) and the liquld film (thickness øf PI), For COa absorption, resisiance to mass transfer is In the iiquid phase. In conventionai absorption solutions, the thickness øf Iiquid fim at the surface of the packing is several miiiimefers, However, the thickness of DK 2014 00144 U1 Η the reaotive Hqtikl fim where the mass transfer and reacions betwean £1¾ and the solution take plsee (SJ)is about 10 um Thus. to take the bast advantage of the enzyme. It is preferabiy present in this reaeffee ligaid; film. Possible ways to reacb this la by using soiuble enzym© or by øsing enzyme mlefo-partlclas with small diamaters. For comparison, emyme immobilized tolarge fked paeking, which is at the surfaee of tha packsng matenal; is sevetal millimeters away from ti reactive iiguid film and its itopaci is thus relatlvely lowar.
To tak® advantage øf the effeots associated with" such reactive fim thicknesses, the micro-particles may be sized such tbat the diameter is wlthln about an order øf tø magnitude as the film thickness. preferabiy smaller than the fim thickness. in one irisfanee wherethe reactive fim has a thickness of about 10 pro, the micrp-partscles may bé sized heiweett about 1 pm end about 100 pm, preferahly between about 1 pm and about 10 pm, stiti preferably below about 10 pm, preferably below about 5 pm. In another embodlmani, tha fower limit of the micm-paftlcfe size is ohosen based upøn the 15 desired micro-partlele separation method, such as filtratlon. Micro-partieles of a certain size may be mere eaaiiy separated from the ion-rtch mixture uslng some separation methods wbile remainihg small enough to achieve the desired cataiytic aetiaity:
•Øm embodimen! of the process and system is shown so Fsg 1 and wlll be descnbed in further detail hereafter. First, the bioeataiytic micro-particles ars mixed in the lean absorption solution in a mlxing chambsr The lean absorption solution refers to Ihe absørpion solution ehøraeterizsd bya løw ooncentratlen of the species tø be absefeed. This solution ia-eliher fheéh -sajiition w cemééTirem fhe mineral carbonatlon prdoees or the COa desorption pfocess |li)). The absorption solution with bioéataiytic parfiofes (11), aiso referred to as the absorptiori mixture, is then fed to the top of a packed column (ΕΊ) with a pump (E~7). The paeking møtehei may be made of conveotionai material like polymers, metal and ceramic. The geometry of the paeking may be ohosen commemiaily avasiabie, li is aiso possible to chose or arrange the paeking to ceitaln defleqtions and coilisfens with the mlcm-parddes, or to avoid aræumulatton of the micro-particles within the reactor. For instance. the paeking preferabiy has Jmited ooncaylies fo avoid the acoumøiatløn of: mioro-pertioies therein, Also > c the paeking supports are mueh larger than the mioro-particies. Also y, the micro-partscies and paeking am ehosen so thal the micro-partyes oan flow: through the rsaeiot without øfeggirsg. Counter-currenlly, a C02 ccntaini 30 12 DK 2014 00144 U1 (12) is fød to thø packad column (E-1) and fiows on, through and/or around thø paoking (9) from the bottom tø the top of thø column. The absorption solutions and biocataiytic micro-partsetes flow on, through and/or around fhé packicg materlai (9) from thø top of the column to the boltern, ,As the absorption solution" and biøcøialytie mierø-particteø 5 progress through the absorber, the absorption solution becømes ficher in the compound fbatis being absorbectBiocataiytic micro-particles, present near the gas-figuid interface, enhance COs absorption by immediateiy cataiyiaing the CO* hydratson reaction tb produce bicarbohatø ions and protons and thus maximmng the COs concentration gradient across the interface. Åt the exit of the column, the rich absorption solution and id bio^talyhc mier o- partioi^i (13} are pumped (E-5) to a partioie separation unit (E-3). Rich absorption solution refers to the absorption solution characterized by a concentration of absorbed compoond whioh is higher than that of the lean solution. The separation unit may compose a filtratipo unit Csuch as a langenii.al filtration unit), a centrifuge, a cyclone, a sedimentation tank or a magnetic separator and any other units or equipments known ts for padicie dr soild separation. The separation unit also ensbles a certain q usnify of solution to he retained wifh the micro-particles so fhe partioie do not dry out whlch can denature the biocataiysts. in one optional aspot, the quantity of retained solution enahles the mscro-partictes to be pumped to a storage unit or direetly back tø a mixing bhamber (£~4) for addition irito thø absorption unit. In another optional asped:, the micro-SO particles wifh retaihed solution møy be gravity fed ihto the mixing chamber (E-4), whioh may bé enabled by performlng separation ahovø the mixing unit, for examplé. Thø separation may be cooducted in coniinyous or in pafch mode, and may l^ nianagød tb ensom fhe proper amount of solution is retained to ensure ømryrne activity. il; may aiso be preferred that the mia o-particles are provided such that they may be easily separated 25 .from any solid precipifates (e g. bicarbonafe precipifates} thai may be entrained in the iomrich solution, ft need be. The absorption solution wrthout mscre pametes (15) is then pumped (1-9) to another unit whioh may hø a CO desorption unit or a mineral carhonation unit (10). Biocataiytic miero-pariicies (16) are mixed wifh the CO* lean absorption solution. This suspension is then fod once agsin lo the absorption column (E-30 1).
in another erohodimenf, the absbrpÉon unit is couplød to a desorption unit as shown in further detail in Figure 2. in this embodiment, the absorption solution ridi in CO* withouf biocataiytic micro-particles (15) is pomped |E~0) through a heat exohahger (E-Tø) where ft is heated and then to the desorption column (E-11). In the desorption unit, the solution 13 DK 2014 00144 U1
Is fyrther hesfed In ordet thaithe COs Is rsleased from the solution in a gaseous -State. Because of reiatively high temperatur© used during desorption, water eSsq vaporlzes. Part of the absorption solution (18) Is directed torvard a rebeller (£-1.2) where 11 is heated to a temperature enablmg COs desorption. Gase-sus C02 fogathar wlth water vapour are oooied down, water eondenses end is fed back to tha desorption unit 119). Dry gaseous C02 (20) Is then dlrected tøward a oompresston and transponation prooess for further processing. The ilquid phase, contain;ng Sess C03, and referred to as the lean absorption solution |T7) is then pumped (E-14) to the heat exchanger (E-18) to be oooied down and fed to the m ising chamher (E-4). The temperature of the iean absorption solution (17) ahouldba lovv enough not to den ature the enzyme il present.
The blocatatysts dan be supported on the support materiel ih any af the ways heretnabove and suoh mloro-partfeies ar© mixed in the absorption solution and flow downward on, through and/or around the packing of Ide paeked column. Counter-curreniiy, the gas containfng CO» ffows on, through and/or eround the packing and contacis the absorption solution the biocatalytfe mlcrarpartloles.
In one optionat asped: of the invention,: an advantage of having mierø-paridies wlth blocataiysfe in the absorption solution is that the enzyms is broyght into olose oontact wifb the gas phase, thus roafemiaing the CG* eoncentration gradient across the gas and Isqutd phases and consequently the (¾¾ absorption rate. An advantage af this prooess is thai thelmpaet of immøbsiized biocaialysts oan be greeter teoause ihay are etaser to the gas llquirf Interfeoe The performanee is irnproved eoropared to a packed column wlthout enzyms and with biocaialysts immoblsed on the packing ifeeif
In andther optional aspest øf the Invention, an advantage of providing miem-parficles fe thai the guantlty and activlty of the enzyme may be designed and controlied for a given pfecess, reactor, pumping reguirsments, or set of conditlons.
In another optional aspeot of the invention, an advantage Is that immobilization of the biocatalysts as part of micro-partioles may provsde snereased stability to the enzyme. IVløfe regarding stabiiity wiii be described beiow. The micrø-partictes with immobiilsed biocataSysts may have a longer sheif iife for storage, shipping, realisation, and recycling withih the prooess as the biøcataiysts are sfabiiised on the support material. In søms embodiments. the immoblzed biocataiysts may bscome stable to operation cønditions in prooess units other than the absorption unit, such as the desorption unit, and consequenily miero-partietes oould be used in the absorption and desorption units DK 2014 00144 U1 m withqut the peed'ts remove . prior to the desorpSon unit. In sech a
fa have a separation unit such as a filter enzymatic micro-particles through the rebeller and thermoresistanoe of the on the proeess eønfiguraiicn the enzymatic mioro-partictes may have an Impaci in the absorption, onit by inoreasing Ihe 0O2 absorption rate but aiso in the Resorption unit since carbonic anhycrase is aiso known to inerease rate of blearfeonete ion transformation into CO:> (WhipiT Is one of the reactions that woufd fake plaee in the desorption unit). In this configuraflori, the rernova! unit (E~3) wouid be required to remove micrp-parlioies: and unit (£*4) to add fresh enzymaite miero-f: However. !f may 11) and (E-12) I r eonfad staiysts an advantage is that the micro-partioles een be easily feplfced or ref urbis hed, The rolxing chamber (E-4) prefemhiy composes an Iniet for receiving recycied rnicro-parbcies from the separation unit (E»3) and also an iniet/outlet for both removtng a ffaetion of used micro-particles and repiaeing thernlwith new micro-particles, thersby" fefurbishing the overall batoh of mfero-padleies in the
In another eptlonaS aspect of the invention, an advantage of the proeess and system is that the mlefo-partioiss can be ramovad from the ion-hob mixture far easiar tbari cbnventidnal free enzymes. By way df exampfe, human carbonic anhydrase type ii is an ellipsoid witb dimensions of 39 Å x 42 A x 55 Å and is difficutt to separate from solution. Thus, the micro-particles can foe sized to enable boih high aheorptson rate and easy removal for recyellng, in this way. the enzymes can avoid being present in the desorption unit which can invoiv© high temperatures and ofher cenditions that can denetyre some types of enzymes and enzyme variants, in søme emfeodimente, the btooataiytic mioro-particles are fiitered, cendfuced, cycioned, sedimented or separated magneiloaiiy in a firsi separation uni and other small partisiet sueh as precipitates oan be separated in a preceding or subsequent separation unit.
The prpesss/system may compose a separation unit for removal øf the micro-partldes. These micro-partioles ate then preferabiy purnped back to the iniet of the absorption ligUid in the pasked column. Tha seteetion ef the separation unit depends on the size of micro-particles, density, cosi and on iheir nature (e.g. magnetic or non magnetic 15 DK 2014 00144 U1 parllete$)Th® pmm9-,rmy afso· compose a Resorption onit In order to tegeners!© tfie ionmeh solution.
tn' om ©mboRimenf the mioro-psrticies arp used in pon|unetion wtth an absorption compound in the solution. The absorption compound may he primary, secøndary and/or tertiary aminas (ioclucting alkanoiamines); primary, secondary and/or tertiary amino acids; and/or carhonates The absorption compound may more particularfy inciude amsnes (e.g, pipehRine* plperazine and derivatives thsreof which are subitiiuteR by at ieast one alkanol group). aikanolamines fe. g. moncethanolamine (MEA), 2-amino~2~ methyi-1-propano
2-f2~aminoethyi3minp|ethanoi lamme 2-amino~2~ dimeihyimoooetbanoiarøine (DMMEA), Rleihyfmønoethanoiarmna (DEklEAJ. tnisøpropanoiamine (TiRA) and triethanøiamine), diaikytether of pofyaikyiene giyeois (&φ diaikyietliéror dimethyletbef of potyetbylene gfycot); amino acids wbieb may inciude pofasstum or sodiom salts # amino acids: gtycine, proiine, argimne, histidine, fysine, aspadlc acid, gtutamic aeid, methionine. senne, threonine: giutamine, cysieipe, asparagine, vaiina, leucine, fsoieuøine, afanine, vailne.
tyrosine, phenylaianins. and derivatives such as taurine, N.cyclehexyl t ,3-propanediamine, N-seconRary butyl giyoine N«methyi M-seoondary butyi giycine, , diethyigfyoine.
ifycine, ethoxy)taiirines N-fp-amincethyhtsunne, N~metbyl atanine. 6-aminohexanoic acid ; and which may includ® pptassium oarboriate, sødium earbooate, ammonium barbonate, prørneted potassium carbonate solutions and promoted sodium oarbonate solutions or promoted ammonium earbonates; pr mixtures thereof. Absorption compounRs are added to the soiutlon tø aid in tha CQa absorption and to combine with the cataiyfic effects of the carboreo anttydrase. Due to the structure pr high coneentration of same absorption cømpounds, the activity or iongevity of the carbonlc anhydrase can bs bireateried. For Insiance, fme ensymes may be more vuinerable to denaturing oaused by an absorption øøfnpdund with high ionip stretigih sych aa earbonates, trnmobilising the carbonlc the carbonic anhydrase immobised pr otherwise suppcrtBd by miero-parficies, the procoas can yieid high 0O2 transfer rates in the presence of absorption compobnds whiie mitlgating the negative effects such compounds could otherwise have pti free enzymes.
DK 2014 00144 U1 Μ
EXAMFLBS
Exarooie 1
The mseroisariicie support matenaf may ha made of nylon, slca, sife gel, chstosan, polystyrene, poiyméthy i metaeryiaie, cellulose, magnetic partsdes, arsd other rnsferiai kmmn to b® used tor bioeataiysts immobiSizatloa The micro-particles may also be oomposed of a combinatlon øf different matertafs, for Ipstance, the support may have a core composeet of a matenal having different daneity or other propertses compared to a dsffereni surface materiel which Is prøvsded for immobilizafiøn or am ra pment cl the emyrnes, for exampiéUbe core of the support may be corøposod of a magnetic matenai to enable magnetic separation and the surface material :may be polymoncauch as nylon for supporting the enzym®, As noted above, in one ømbodlment ih® support material may bo an aggregats of enzymes to ferm dl BA or ClEC. The mlcro-particies may asen defins an integral solid volume (e,g, a feead-iike shape) or may compose one or more apertur®® traveming t.ho main voiume of fee parfeié fe-g- a pipe or donut shape), 8y way qf exampi®, the mipro-partides may be ovoid, spherical cylindsical. etc.
The mlorO'particles may be sized In accordance with the requirements of given process condioas, Før higher slzes, the compounds, materiale and prooess eguipment ehould fe® sfiosen to allow sufficient flow and pumpabitity of the absorption mixture. More regsrding . sizing will be discussed harainbelow.
Exarrtdla 2
An expedment «as conducted tn art absorption packed ccfurøn. The absorption solution is ab agueous solution of mathyldlethanolarntne (MDEA) This absorption solution is oontacted countancurranly with a gas phase with a CD2 coneentratfesi of 130,000 ppm. Liquld flow rate was 0,65 g/fnin and gas flow rate wss 65 g/min correspondiog fo UG of 10 (g/'g). Gas and absorption solution were at room temperature. Operating pressure of the absorber was set at VM.psig, The column has a ,S om diameter and a SO cm beight Packing material is polymeric Easchig rings 6 ,25 inch, Three tests were performed; the finst with no acflvator, the second with earbonic anhydrase immobiilmd to packing support and the thife using carbohlo anbydrase frée ih solution at a concebtratlon of 0,5 g per ilter øf solution.
The fesuits øbtained showod that C02 transfer rate or CO, removal rate mereased from 6 fe 14 nimol COs/m ih with carbon Ib anhydrase immObiilzed onto fhe surface of Raschig DK 2014 00144 U1 17! 7 rings.,. In the presene© ofte© enerne Ivev isarnonte anhydrase fine fidwing In the solution, thi transfer rate jneroased to 29 mmoi/mln. These results dornonstrate the positive impact of addlng the enzyme in a packed column and thai micro-partidtes compdsing erøymes. dan ©noble tmproyements.
Similar tests were aiso performeo with solutions of pøtaselum carbonate (20% w/w -1.45 M}) and sodtum oarbonate %5 & 1 The impact of free aré immobilszed enzyme foliows the same trend as for fVfQEA 4 å/f
Ta further determine the impact of enzymaiic micrc-particies on C02 absorption rate, tests were oonducted in a hydration ceil. This hydraiion cell reactor was designed and operated at set condilions to oontroi the area of ihe Interface between a gas phase, CQ2, and a iiqusd phase in an absorption process. This device was used to evaluate impaet øf enzymatlc micro-pariicles on the CQ2 absorption rate ih a givm absorption solution.. Tests were conducted as follows: a known voiome of the unioaded absorption solution Is sntroduoed Ih the reactor; then a known mass of micro-partictes is added to the
absorption soiution (mioro-particies may or may not coniain enzyme); a C02 stream is flowed through ihe head spage bf the reactor end agitation is stsrted; pH of the soiution is méasursd as a funetion o time; theft pH vaiues are converied into carbon oonæntrstion in g C/L usihg a carbon concentration-pH corraj etion previousiy determined for the οΐ^οφίίο^ rates ars determined from a plot of G
csneehtrltiQn as a funetiph of time. The impact of the enzym® as a raiatlve absorption rate le reported; ratio of absorption rate in the presenes of the enzyms micro-partieles fo absorption rate in the presenes of minro-particles without enzyms, it shouid be fhat results obialned in hydratlgn ceil reactor cannol be direotly compared to obtained in a packed column because hydrodynamio oonditions and mass transfer ooeffioiehts er®
Tests vvere conducted with the enzyme human carbofsic anhydrase type li (HCAii) immohilisad at; file surface of nyion micro-particles, li shculd be ncteci that these tests used a non optimised mimobliizafion protceol and thus the actiyity df the enzymes could be inereaséd by adjusting the Imrndbfeation protocoi. Nylon micro-particies size ranges tom 50*160 pm. Absorption solutions that were tested were 14$ M KjCCh and 0,S M
DK 2014 00144 U1 w
NfeCOs. Testing temperature was 20'C. Methodoiogy was as descrlhed ih Exampie 3. Results indioata thai C02 absorption rate was increased by 20-30% for bøtb solutions m ipénjparéil n© enzymes.
Examoie 5
Tests wem conducied with HCAii Immobsllsad alths surface af nylon micro-partictøs. (ussng a don optimized Imrnohsilzstion protocoi) Nylon mtorø-padioles size ranges torp S0»160 pm> Afesorptidd Sdlylipn was 2M MDEA, Testing temperature was 20 C- Enzyrne conceoiiaiions ranged'fdm 0.1 to 0.5 ø/L, Meihodoiogy was as described in Exampie 3. Results indleate that enzyms on nylon micro-partides snereases C02 absorption rate for all tested opnditlons (®øe Tafele 1), Absorption rate increased between 40 and 120 %.
Table 1 iffeiative C% tensfer rates so presene© of ©nzyme immobilized on nylon ffilcro-parddies In 2$i SffiEA solution ielative trawsfer rate 1 4 ......1.4 ................... Z2 ....................
Enzyms mmmtfMim ia/i) : cm _ 0 26 .........o's ............................
Tests were eondusted with HCAII immobilised af the surfase of cellulose mioro-padicles (using a non optimized immohiiization protocol). Cellulose micro-pasticle size is 50 pm. Absorption solution was 2M MDEA, Testing temperature was 20C. Enzyrne concentrations in tbe solution ranged from ø l fo 0.5 g/L. Methodofogy was as described in Exampie 3. Results imJlcaté-#taf' enzyrne on cellulose micro-particles inoreases "CO* «ÉwrølkiftTilft fer eræyiTie conoentration Ngbertban ø l gtt (see Tabie 2} onder tested conditions.
Tabte 2; Relative C02 transfer rates In presene© of enzym© immøbitlzed en cellulose micro-particles in a 2M ϋΟΕΑ solution
Enzyrne ooncentrafioo Cgftfef solution Refative transfer rate 0.1 1.0 0.25 11 0.5 1.8
Exampie 1 DK 2014 00144 U1
B
Tests were oorsducted with HQ&tt immobiiised at the surface of nylon miero-piticles iusirig a non optimtead immobitization protocoi). Nylon partide size ranges between 50 and 180 pm, Absorption solutions were 0,5 M øf the potassium salt of tha follewidg arninø acids; g!yetne: metbionsne, teorine and Μ,Ν-dsmethyiolycine. Testing temperatur« s was 20'G, Enzyme eonoentraiion is O S g/L. Méfhodotogy is as desenbéd In Example 3-Resyits indlcate that enzyme on nyion micro-particies incraases C02 absorption rate for alt tested amme aeid salts (sea Table 3), However, the impact of the enzyme was iess importen! fer NsN^imethylglyctne, a tartiary amino acid.
Tabla O^ Roiatfea CGg tranafer rates in presenes of enzyme tmmebiHzeb on nylon B røiero-partsoios m ø.S 1$ poiassiam salt of amsno aoids at an enzyme coneentrafion
ef iJg/L
Amino acid Relative transfer rate 1 Glycino 1.4 yethionine j 1.5 Tauhne i 1.6 N,N~dimethylglycine 1.1
Tests were conduoted with cross iinked enzyme aggregates (CtEA) of carbonic is an hydra se (using a non éptimized protocoi). The enzyme used Is a thefmoresistant variant of enzyme HCAtl, designatéd as SX> GLEA eøntains 26% (ψΝή of the SK enzyme. fterticle size ranges between 4-9 pm, Absorption sol ut son was 1,45 M KjCQs, Testing temperature was 20"€. Enzyme concentraiion was 0,5 g/L Methodoiogy is as described in Example 3, Tests weæ condueted with CLEAs and fhen with deaotsyated 20 CLEAs as a neforence to enable determination of the enzyme impøeh Results indlcate thai CLEAs increases C02 absorption rate by a factor of 3,2,
Example 9
Tests were condueted with cross linMeb enzyma aggregafes (CLEÅ) of earbonie annydrase (using a non opiimized protocoi), The enzyme used is a ihermoresistant 25 variant of ehzyme HCAil> designated as 5X GLEA contains 28% (w/w) of the SX enzyme. FartlÉe size ranges between 4-S pm. Absorption solution was; fli MDEA Testing temperature was 25'C, Enzyme cont^nfration was 0.5 g/L, CO-, absorption tests were perforrned in a stlrred cab a simple device thaf can be used tb evaiuate C02 absorption rates under diferent conditions. The stir red cel! contains the absorption DK 2014 00144 U1 m solution (and: the enaryme when mqyimd). A koøv«n pressum of pure Gøs is appiied to the soiutfon, in these tests, initial CO pressure is 1 000 mhar, Then the pressure deorease is monstored and usad to calculate CO£ transfer rate irs tha absorption. Tests were condudted with particfes whh CLEÅs and witheui ClEAs to enabte determination of the enzym® impaet Results are evprossed as a ratio of ih® COs transfer rato wtth CLEAS to the CGS transfer rate in the absence of ClEAs Results Indleate that ClEAs increase C02 absorption rate % a factor of 1,3 toi J tn the y DEA.
Tests were con duefed wilh HCAII Immoblsed at the surface of magnetic sisica coated i ro n o)dda microisadidles (using a non optsmizod immobilkaiion protocoi). Fsrtfcle ska is 5 pm. Absorption solution was 1.45 M HC€0:i. Testing temperature was 2()¾ Enerne poncenfeatidn !a 0.2 g/L, yetbødology is as desprlbed in Exampt® 3, Results iodicatethat enerne on magnetic mkro-pafedes inereases.00¾ absorption rate by a factor af 1.8, proyibes celeulatians tor the rninimurn aciivity density fora given micro- process.
partide ske« for an >
Data:
Activitylevel to be reenhed In the absorption solution; 5 x 1øs units/L :feormspondihi to 1g/L soiuble earbonic anhydrase).
toateHal density: 1.1 g/mt for nyion partsdes (- 1 190 g. yaximum allowabte partide concentratson: 300 g/L
diametanvio pm,
Calcufaiions; 1. Surface of ai 10 pm partiel®
Af« ™ 4tt (radius)2 ~ 4π (Sf « 314 prn2 2. Volume of a 10 pm pariide
Vp ~ 4/3 π (radius)^4/3iT (δ)®* 524 pro1
Total i yplume of partides per liter i© reash the maximum ailowable partfele concentrafson: 21 DK 2014 00144 U1 , . i vir um fmrticte mass ver Hier
Tuml vvltmm ®f p&rUd$$yT} ~-------------.........-............
VT « 300 g /(1,100 g/L)» 0272 L {oørrøspøndihg lo 2.72 x 1pm3) 4, Number of particfes (rp) In 1 L of solution; iv ^" % r%~ 2.72 x 10M pm3/524 μι«3* 6.21 x 10t 6. Total micro-partides surface area (Å<) AT * rV'Åp * 5.21 x 1011 * 314 ~ 164 x 101< pmz (164 x 10® mnf) 6. Minimum activity density
Activity darmiiy ™ Aotivity itvel/Ατ * 5x106/1.64 x 103=0;03.Un|t WA/mm2
Thus, for 10 pm mlcro-particles, the minimum activity density fe nsach an activity level of S x 10δ units. WA/L, is 0,03 unit WA/mm2,
Thus, if thø activity density is. higher than 0.03 unit WÅ/mrh2« a partiole concentration lowerthart 300 g/L wøuicf ba rseeded Additionai examples are shown in Tabte 4 heføw.
22DK 2014 00144 U1
E D i C I
>* S «5 ψ p 1 i J | O· 73 >
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Exaroole 11
This example provines eaiculatiam for the maximum parttete size for a given partiel© concentratson, for an embodtaent of the proces®.
Data:
Aotivity lava! to be reaøhod in the absorption solution: 5 x 10* units/ (oorraspondlng to 1 g/L solubie carbonlc anhydrås«),
Acttv% density øn parttetes: 0,51 unit/mm2.
ivtateriat density: 1,1 g/mL for-nylon partiet©© 1 100 g/L), 'Maximum aitowabie partide conæntration: 300 g/L,
Caicuiations;
Total surfaoa area ragufred to reaoh the actsvity tevéi: s«, d s -.lesasl &mmty dmst'ty
Aj - 5 x 1Q1 units/L /(0.51 uret/oim2) « 9 803 922 mm2 2. Total votums of partidas per Ilter to reach ti© møxlmurn atewabte partiel© concéniration:
Total -mimmø &f-p®rti£les ii-V') åføsfftwm panicle mass per rtpgr pæn tde dm si Sy
Vt * 300 s m 100 g/L) ~ 0.272 L (correspondlng fo 272 727 mms) So, a volume ©f 272 727 mrn2 3 of partides »uld b© present per Ister of mixfcur©.
* Yp - 4/3 π (radius)® 2
Maximum radius of a partiel®: For spharicsi partides: 3 * Ap « 4ir (radius)2 24 DK 2014 00144 U1
Thus; __3 14 r «<J{ ;.ί.ν
And;
72 9 803 92 0 J13 mm (03 v i£crøfis)
Thus, the maximum size of a partida would have a diameter of shoul 16β pm. So. if micro-partides are of a smaller diameter, ih® resulting mixture or absorption solution wili
This method can be used to evaluaie the maximum paitic-le size aiowsbie for many oondlfioris of aciivity level, aotlvity density, partiets density and maximum ailowable partide conoenifation. Tabte 5 below shows different scenarios and correspondsng particle sizes.
25 DK 2014 00144 U1 ε o
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C3 "S Φ <& 5 05 <ØS o· S te θ' 0 € cs ·**+ &v £ S 1 © so 115 N uø 327 «5 os 05 O ίΧί] iO Oi Oi CO te Oi te < 4· 77 xr α -¾ 5 |gOi t1 i Oi Oi04 Oi Oi Oi Oi Ute .v,ws| O 0 Oi G 9 o q O 9 q G 0 G q q 0 .VJl El ώ UJ ώ, iii ui Ui Ui ώ UJ! Ui UJ ώ Ui ώ ih t; ·χ*$ P: & o* UD: CO os »r* te eø te te O” <8 ί9 'te <0 '— UO K tø te te r** O ir tø 0 «> eo 0 O- cd χ* te te oi te * νΛ te £ te -te te ute oi
Tabte 5: Examptes ol maxsmum partkslesize scenarios E ^0 § f^· r>. o> O O 0 f^· O O; © 9 te c« O1 0 4ϊ Oi C'J Cvi 0 O 0 C·^ O Oi te O te -Ute* 0 i Φ O c i N· Ufi te te 10 OS tø 0 te te 0 X "*4 £ oi C-·; i·^ o- CN Γ-- 0 te 0 te tiO se δ C" >.v. C'" te £0 so <0 0 te o te te C<4 'o > o, | £N te 'r™· N 'T*' •iT*'; te os rv o· s «3 5 CO i <0 C ,S S Æ ® ø: sj s* V "' x Jjj 85 o. °
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Bi....... ,¾ * C £1 te te te te S Φ ’D >i, o o oi o o o <L -δ —~s:1 I
!Ui~- o >s cs -9 > ,4'' 0 ::s O Vi N 7> v>' » SS ! te Ov. o O O Os ... ... .... , -r 4“ 4* i 4’ 4* 4* · 4* uj uj m yj m m m m g 4* se δ Si S S ^ o o o, o © os o o o o o, o s o q q|.q q o te te te; te te tot te te te r" v i— ~~ x~ i ug o i« ιλ un te § o o djd d o! tø <0 te to 000 -4 4 -4 LU UI UJ O O O q © o te te te tøs O O o ·£ 'f· Hr Ui Ui UJ o o o q q qj te te te i Φ B o o φ Φ o s>l V VW1 >wiq uj ' . s* 2 φ < > U OJ 5 ^ w δ #
OS
os o DK 2014 00144 U1 Μ
Whllé the calcuiaiicns in the above Exampies ar® for sphencat mlcro-partieles, correeponding oalcuiatiøns or astimations may jbe performed for biher micro-partiele
Ah ekpenment wm conductad in an absorption packed column. The absorption solution is an aqueous solution of potassium carbonate (K^COs) 1.46 M. Ibis absorption solution Is eenfaoted cmmier-eurrently wlth a gas phase wlth a C02 concenirafion of 130,000 ppm. Liquid flow rate was 0,60 g/min and gas flow rate was 60 g/mio corresponding to L/G of 10 (g/g), Gas and absorption solution mm af room temperature. Operating pressure of the absorber was set at 1.4 psig. The column has a 7.3 em diameter and a 60 cm height. Paeking materiel Is polymeric Raschig rings 0.25 inch. Two tesis were performed: the firsf wlth no activatcr, the seeørsd wlth ClEAs containing 26% (w/w) of the enzyme. Psrfieie sfee ranged between 4-8 pm. The enzyme conceniration in the absorption solution was 0.1 g/L.
The results obtained showed that C02 transfer rate was increasedby a factor of 2.7as the GQs: rpmoyal rate went from 11 to 30 mmoi/min wsth the CLEAs.
Examoie 13
This exampia provides data to demonstrate that enzyme immabifizaiion inereases ertzyme otabity. Data are shown for enzyme immobitized on nylon mioro-partlcles, To eyaluafe tha impaci bf irnmpbilkatiOn on enzyme stsbiiify, the stabiiliy of imrøobized ehzymes was evaiuatéd and cornpared to the stabl lity of the same enzyme in a soly ble fbcrm The micro-partlefes were preparad through the followlng non-optimlzed steps: - Surføqe tréafmenf of nylon miord-partldes with gtutaraidehyde * Addition of polyeihyienelrnine
Addition - Enzyme
Aldehyds greup blOGking with poiyeihyieneifhine
Foilowing immobiiizaiion. the enzyme micro-partlcies and solubié enzyme were exposed fé PDEA af 40/C. At specific exposure times, samples wer& wnfxlravvn and aetivliy was measurecl. Results are expressed as residual activity. which is the ratio of the aptiyity. of the enzyme at a given exposure time t to the enzyme activity af time 0. Rgure 4 mest rates the results.
DK 2014 00144 U1
ResdftMhøyy that.fr®© enerne fosas alf aciivHty wsth 10 days« whereas micro-particfes •"still retain 40% reslduaf adivl^ after 56 days, From this result, il m pies that immopizsion .increases enzyma staPifity under tbese condihons.
Tb&m msuits show the potential of Irnmobizaibn ta incnea&e the stablfity ©f carbonic anhydrase at hlgtw temperature condions thai ars found in a C02 captura proeess. In optaai aspects of the present inveniion«:ifie mlcro-parilsSes enshfe increased stablifty øf
around or abeve the stabiity inerease iiSystrated in li shouff alsø be noted that the absorption and of the present invention car conditions. The units may reactor, spray master,; fiyidlsed
fsed with on various lé, rn the form of a reaetør, etc., rna y nave donhgy rations aoch as vertfeaf« horizontai, etc. « and the overall system may use multiple units in parallel or in series, as the case may be.
ii shoyfd ha understood that the embodmients described and iiiustraied above do not residet whaf has adualiy been invented.

权利要求:
Claims (118)
[1] 1. A system for capturing C02 from a C02-containing gas comprising a packed reactor configured for contacting the C02-containing gas with an absorption mixture there-vvithin, the absorption mixture comprising a iiquid solution and micro-particles, the micro-pariicles comprising a support materiai and biocataiysts supported by the support materiai and being sized and provided in a concentration such that the absorption mixture flows through the packed reactor and that the micro-particles are carried with the iiquid solution to promote dissolution and transformation of C02 into bicarbonate and hydrogen ions, thereby producing a C02-depleted gas and an ion-rich mixture comprising the micro-particles.
[2] 2. The system of claim 1, comprising a separation unit for removing the micro-particies from the ion-rich mixture to produce an ion-rich solution.
[3] 3. The system of claim 2, wherein the separation unit comprises a filtration unit, a magnetic separator, a centrifuge, a cyclone, a sedimentation tank or a combination thereof.
[4] 4. The system of claim 2, comprising a desorption unit for performing desorption or a mineral carbonation unit for performing mineral carbonation on the ion-rich solution to produce an ion-depleted solution.
[5] 5. The system of claim 4, wherein the ion-rich mixture comprises precipitates and the system further comprises a precipitate separation unit for removing precipitates from the ion-rich mixture prior to performing the desorption or the mineral carbonation.
[6] 6. The system of claim 4, comprising an addition unit for adding an amount of the micro-particles to the ion-depleted solution before recyciing the ion-depleted solution for further contacting the C02-containing gas in the packed reactor.
[7] 7. The system of claim 4, comprising an inlet for feeding the ion-rich mixture into the desorption unit, the micro-particies being stabilized by the support materiai and being sized and provided in a concentration in the desorption unit such that the micro-particles are carried with the ion-rich mixture to promote transformation of the bicarbonate and hydrogen ions into C02 gas and water, thereby producing a C02 gas stream and the ion-depleted solution. 2 2DK 2014 00144 U1
[8] 8. The system of ciaim 1, comprising a desorption unit for performing desorption or a mineral carbonation unit for performing mineral carbonation on the ion-rich solution to produce an ion-depieted solution, and a removal unit for removing the micro-particles from the ion-depleted solution.
[9] 9. The system of any one of ciaims 1 to 8, wherein the micro-particies are sized to facilitate separation of the micro-particies from the ion-rich mixture.
[10] 10. The system of any one of ciaims 1 to 9, wherein the micro-particies are sized to have a diameter above about 1 pm.
[11] 11. The system of any one of ciaims 1 to 10, wherein the micro-particies are sized to have a diameter above about 5 pm.
[12] 12. The system of any one of ciaims 1 to 11, wherein the micro-particies are sized to have a catalytic surface area comprising the biocatalysts having an activity density so as to provide an activity level equivalent to a corresponding activity levei of soluble biocatalysts present in a concentration above about 0.05 g/L wherein the solubie biocatalysts have a minimum activity of about 260 WA units/mg.
[13] 13. The system of any one of ciaims 1 to 12, wherein the micro-particies are sized to have a catalytic surface area comprising the biocatalysts having an activity density so as to provide an activity equivalent to a corresponding activity level of soiuble biocatalysts present in a concentration between about 0.05 g/L and about 0.5 g/L wherein the soluble biocatalysts have a minimum activity of about 260 WA units/mg.
[14] 14. The system of any one of ciaims 1 to 13, wherein the absorption mixture and the CO2 form a reactive liquid film having a thickness and the micro-particies are sized so as to he within an order of magnitude of the thickness of the reactive liquid film.
[15] 15. The system of any one of ciaims 1 to 13, wherein the absorption mixture and the C02 form a reactive liquid film having a thickness and the micro-particies are sized so as to be smaller than the thickness of the reactive liquid film.
[16] 16. The system of ciaim 14 or 15, wherein the thickness of the reactive liquid film is about 10 pm. 3 3DK 2014 00144 U1
[17] 17. The system of claim 1, wherein the micro-particies are sized between about 1 pm and about 100 pm.
[18] 18. The system of any one of cSaims 1 to 17, wherein precipitates are formed in the ion-rich mixture and the micro-particies are sized to be iarger or heavier than the precipitates.
[19] 19. The system of any one of claims 1 to 18, wherein the micro-particies have an acfivity density of at least about 0.06 WA/mm2.
[20] 20. The system of any one of claims 1 to 19, wherein the micro-particies are provided in the absorption mixture at a maximum particie concentration of about 40% w/w.
[21] 21. The system of any one of claims 1 to 19, wherein the micro-particies are provided in the absorption mixture at a maximum particie concentration of about 30% w/w.
[22] 22. The system of any one of claims 1 to 21, wherein the support is at least partially composed of nylon, cellulose, silica, silica gel, chitosan, polystyrene, polymethylmetacrylate, magnetic material, or a combination thereof.
[23] 23. The system of claim 22, wherein the support is composed of nylon.
[24] 24. The system of any one of claims 1 to 23, wherein the density of the support material is between about 0.6 g/ml and about 3 g/ml.
[25] 25. The system of any one of ciaims 1 to 23, wherein the density of the support material is above about 1 g/mi.
[26] 26. The system of any one of claims 1 to 25, wherein the absorption mixture comprises water and an absorption compound.
[27] 27. The system of claim 26, wherein the absorption compound comprises primary, secondary and/or tertiary amines; primary, secondary and/or tertiary alkanoiamines; primary, secondary and/or tertiary amino acids; and/or carbonates.
[28] 28. The system of claim 27, wherein the absorption compound comprises piperidine, piperazine, derivatives of piperidine or piperazine which are substituted by at least one aikanol group, monoethanolamine (MEA), 2-amino-2-methyi-1-propano! (AMR), 4 4DK 2014 00144 U1 2-(2-aminoethyiamino)ethano! (AEE), 2-amino-2-hydroxymethyi-1,3-propanediol (Tris), N-methyldiethanolamine (MDEA), dimethylmonoethanolamine (DMMEA), diethylmonoethanolamine (DEMEA), triisopropanolamine (TIPA), triethanolamine, dialkylether of polyalkylene glycols, dialkylether or dimethylether of poiyethylene glycol, amino acids comprising glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, leucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine, and derivatives such as taurine, N.cyclohexyl 1,3-propanediamine, N-secondary butyl giycine, N-methyi N-secondary butyl glycine, , diethyiglycine, dimethylglycine, , sarcosine, , methy! taurine, methyl-a-aminopropionic acid, N-0-eihoxy)taurine, Ν-{β-aminoethyl)taurine, N-methyl alanine, 6-aminohexanoic acid and potassium or sodium salts of the amino acids; potassium carbonate, sodium carbonate, ammonium carbonate, promoted potassium carbonate solutions and promoted sodium carbonate solutions or promoted ammonium carbonates; or mixtures thereof.
[29] 29. The system of any one of claims 1 to 28, wherein the biocatalysts are enzymes.
[30] 30. The system of claim 29, wherein the enzymes are carbonic anhydrase.
[31] 31. The system of claim 30, wherein the carbonic anhydrase is smmobifized on a surface of the support material of the microparticies, entrapped within the support materiai of the microparticies, or a combination thereof.
[32] 32. The system of claim 30, wherein the carbonic anhydrase is provided as cross-iinked enzyme aggregates (CLEAs) and the support material comprises a portion of the carbonic anhydrase and crosslinker.
[33] 33. The system of claim 30, wherein the carbonic anhydrase is provided as cross-iinked enzyme c rystals (CLECs) and the support material comprises a portion of the carbonic anhydrase.
[34] 34. The system of claim 1, wherein the micro-particles are sized according to a sizing protocol comprising: selecting a desired biocataiytic activity level of the micro-particles; selecting a maximum allowable particle concentration for the packed reactor; 5 5DK 2014 00144 U1 determining a tota i surface area required to reach the biocataiytic activity level; determining a total volume of the micro-particies to reach the maximum allowabie particle concentration; and determining a maximum size of the micro-particies to achieve the biocataiytic activity level with the maximum allowabie particle concentration.
[35] 35. A system for capturing C02 from a C02-containing gas comprising an absorption stage configured for contacting the C02-containing gas with an absorption mixture comprising a liquid solution and micro-particies, the micro-particles comprising a support material and biocataiysts supported by the support material and being sized and provided in a concentration such that the absorption mixture is pumpabie and that the micro-particles are carried with the iiquid solution to promote dissolution and transformation of C02 into bicarbonate and hydrogen ions, thereby producing a C02-depleted gas and an ion-rich mixture comprising the micro-particies; and a pump for receiving and pumping the ion-rich mixture.
[36] 36. The system of claim 35, wherein the absorption stage comprises at least one reactor selected from a packed tower, a spray tower, a fluidized bed reactor and a combination thereof.
[37] 37. The system of claim 35, comprising a separation unit located downstream from the pump and configured for removing the micro-particles from the ion-rich mixture to produce an ion-rich solution.
[38] 38. The system of claim 37, wherein the separation unit comprises a filtration unit, a magnetic separator, a centrifuge, a cyclone, a sedimentation tank or a combination thereof.
[39] 39. The system of claim 37, comprising a desorption unit for performing desorption or a mineral carbonation unit for performing mineral carbonation on the ion-rich solution to produce an ion-depieted solution. 6 6DK 2014 00144 U1
[40] 40. The system of claim 39, wherein the ion-rich mixture comprises precipitates and the system further comprises a precipitate separation unit for removing precipitates from the ion-rich mixture prior to performing the desorption or the mineral carbonation.
[41] 41. The system of claim 39, comprising an addition unit for adding an amount of the micro-particles to the ion-depleted solution before recyciing the ion-depleted solution for further contacting the C02-containing gas in the packed reactor.
[42] 42. The system of claim 39, comprising an inlet for feeding the ion-rich mixture into the desorption unit, the micro-particles being stabilized by the support material and being sized and provided in a concentration in the desorption unit such that the micro-particles are carried with the ion-rich mixture to promote transformation of the bicarbonate and hydrogen ions into C02 gas and water, thereby producing a C02 gas stream and the ion-depleted solution.
[43] 43. The system of claim 35, comprising a desorption unit for performing desorption or a mineral carbonation unit for performing mineral carbonation on the ion-rich solution to produce an ion-depleted solution, and a removal unit for removing the micro- particles from the ion-depleted solution.
[44] 44. The system of any one of claims 35 to 43, wherein the micro-particles are sized to facilitate separation of the micro-particles from the ion-rich mixture.
[45] 45. The system of any one of claims 35 to 44, wherein the micro-particles are sized to have a diameter above about 1 pm.
[46] 46. The system of any one of claims 35 to 45, wherein the micro-particles are sized to have a diameter above about 5 pm.
[47] 47. The system of any one of claims 35 to 46, wherein the micro-particles are sized to have a catalytic surface area comprising the biocatalysts having an activity density so as to provide an activity level equivaienf to a corresponding activity leve! of solubie biocatalysts present in a concentration above about 0.05 g/L wherein the soiuble biocatalysts have a minimum activity of about 260 WA units/mg.
[48] 48. The system of any one of claims 35 to 47, wherein the micro-particles are sized to have a catalytic surface area comprising the biocatalysts having an activity density 7 7DK 2014 00144 U1 so as to provide an activity equivalent to a corresponding activity level of soluble biocatalysts present in a concentration between about 0,05 g/L and about 0.5 g/L wherein the soluble biocatalysts have a minimum activity of about 260 WA units/mg.
[49] 49. The system of any one of ciaims 35 to 48, wherein the absorption mixture and the C02 form a reactive liquid film having a thickness and the micro-particles are sized so as to be within an order of magnitude of the thickness of the reactive liquid film.
[50] 50. The system of any one of ciaims 35 to 49, wherein the absorption mixture and the C02 form a reactive liquid film having a thickness and the micro-particles are sized so as to be smaller than the thickness of the reactive liquid film.
[51] 51. The system of claim 49 or 50, wherein the thickness of the reactive liquid film is about 10 prn.
[52] 52. The system of claim 35, wherein the micro-particles are sized between about 1 pm and about 100 pm.
[53] 53. The system of any one of ciaims 35 to 52, wherein precipitates are formed in the ion-rich mixture and the micro-particles are sized to be larger or heavier than the precipitates.
[54] 54. The system of any one of ciaims 35 to 53, wherein the micro-particles have an activity density of at least about 0.06 WA/mm2.
[55] 55. The system of any one of ciaims 35 to 54, wherein the micro-particles are provided in the absorption mixture at a maximum particle concentration of about 40% w/w.
[56] 56. The system of any one of ciaims 35 to 54, wherein the micro-particles are provided in the absorption mixture at a maximum particle concentration of about 30% w/w.
[57] 57. The system of any one of ciaims 35 to 56, wherein the support is at least partially composed of nylon, cellulose, silica, silica gel, chitosan, polystyrene, polymethylmetacrylate, magnetic material, or a combination thereof.
[58] 58. The system of claim 57, wherein the support is composed of nylon. 8 8DK 2014 00144 U1
[59] 59. The system of any one of claims 35 to 58, wherein the density of the support materiai is between about 0.6 g/ml and about 3 g/mi.
[60] 60. The system of any one of claims 35 to 58, wherein the density of the support materiai is above about 1 g/ml.
[61] 61. The system of any one of claims 35 to 60, wherein the absorption mixture comprises water and an absorption compound.
[62] 62. The system of claim 61, wherein the absorption compound comprises primary, secondary and/or tertiary amines; primary, secondary and/or tertiary alkanoiamines; primary, secondary and/or tertiary amino acids; and/or carbonates.
[63] 63. The system of claim 62, wherein the absorption compound comprises piperidine, piperazine, derivatives of piperidine or piperazine which are substituted by at ieast one alkanoi group, monoethanoiamine (MEA), 2-amino-2-methyi-1-propano! (AMR), 2-(2-aminoethylamino)ethano! (AEE), 2-amino-2-hydroxymethy!-1,3-propanedio! (Tris), N-methyldiethanolamine (MDEA), dimethylmonoethanoiamine (DMMEA), diethylmonoethanoiamine (DEMEA), triisopropanoiamine (TSPA), triethanolamine, dialkylether of polyalkylene glycois, dialkyiether or dimethylether of polyethyiene glycol, amino acids comprising glycine, proline, arginine, histidine, iysine, aspartic acid, glutamic acid, methionine, serine, threonine, giutamine, cysteine, asparagine, leucine, isoleucine, aianine, vaiine, tyrosine, tryptophan, phenyiaianine, and derivatives such as taurine, N,cyclohexyl 1,3-propanediamine, N-secondary butyi glycine, N-methyl N-secondary butyl giycine, , diethylgiycine, dimethyiglycine, , sarcosine, , methyl taurine, methyl-a-aminopropionic acid, N-(3-ethoxy)taurine, Ν-(β-aminoethyl)taurine, N-methyl aianine, 6-aminohexanoic acid and potassium or sodium salts of the amino acids; potassium carbonate, sodium carbonate, ammonium carbonate, promoted potassium carbonate solutions and promoted sodium carbonate soiutions or promoted ammonium carbonates; or mixtures thereof.
[64] 64. The system of any one of claims 36 to 63, wherein the biocatalysts are enzymes.
[65] 65. The system of ciaim 64, wherein the enzymes are carbonic anhydrase. 9 9DK 2014 00144 U1
[66] 66. The system of claim 65, wherein the carbonic anhydrase is immobiiized on a surface of the support material of the microparticies, entrapped within the support materia! of the microparticies, or a combination thereof.
[67] 67. The system of claim 65, wherein the carbonic anhydrase is provided as cross-linked enzyme aggregates (CLEAs) and the support material composes a portion of the carbonic anhydrase and crosslinker.
[68] 68. The system of claim 65, wherein the carbonic anhydrase is provided as cross-linked enzyme c rystals (CLECs) and the support material comprises a portion of the carbonic anhydrase.
[69] 69. The system of claim 35, wherein the micro-particles are sized according to a sizing protocol comprising: selecting a desired biocatalytic activity level of the micro-particles; selecting a maximum allowable particie concentration for the packed reactor; determining a total surface area required to reach the biocatalytic activity level; determining a total volume of the micro-particles to reach the maximum allowable particie concentration; and determining a maximum size of the micro-particles to achieve the biocatalytic activity level with the maximum allowable particie concentration.
[70] 70. A system for desorbing C02 gas from an ion-rich aqueous mixture comprising bicarbonate and hydrogen ions, comprising: a desorption reactor for receiving the ion-rich aqueous mixture; micro-particles provided in the ion-rich aqueous mixture, the micro-particles comprising a support material and biocataiysts supported and stabilized by the support material and being sized and provided in a concentration in the desorption reactor such that the micro-particles are carried with the ion-rich 10 10DK 2014 00144 U1 aqueous mixture to promote transformation of the bicarbonate and hydrogen ions into C02 gas and water, thereby producing a C02 gas stream and an ion-depieted soiution,
[71] 71. The system of ciaim 70, wherein the ion-rich mixture comprises precipitates.
[72] 72. The system of ciaim 70 or 71, wherein the desorption reactor comprises a packed reactor.
[73] 73. The system of any one of ciaims 70 to 72, wherein the micro-particles are sized to have a diameter above about 1 pm.
[74] 74. The system of any one of ciaims 70 to 72, wherein the micro-particles are sized to have a diameter above about 5 pm.
[75] 75. The system of any one of ciaims 70 to 72, wherein the micro-particles are sized to have a catalytic surface area comprising the biocatalysts having an activity density so as to provide an activity leve! equivalent to a corresponding activity level of soluble biocatalysts present in a concentration above about 0.05 g/L wherein the soluble biocatalysts have a minimum activity of about 260 WA units/mg.
[76] 76. The system of any one of ciaims 70 to 72, wherein the micro-particles are sized to have a catalytic surface area comprising the biocatalysts having an activity density so as to provide an activity equivalent to a corresponding activity level of soluble biocatalysts present in a concentration between about 0.05 g/L and about 0.5 g/L wherein the soluble biocatalysts have a minimum activity of about 260 WA units/mg.
[77] 77. The system of any one of ciaims 70 to 76, wherein the micro-particles have an activity density of at least about 0.06 WA/mm2.
[78] 78. The system of any one of ciaims 70 to 76, wherein the micro-particles are provided in the absorption mixture at a maximum particle concentration of about 40% w/w.
[79] 79. The system of any one of ciaims 70 to 78, wherein the micro-particles are provided in the ion-rich soiution at a maximum particle concentration of about 30% w/w. 11 11DK 2014 00144 U1
[80] 80. The system of any one of claims 70 to 79, wherein the support is at least partially composed of nylon, cellulose, silica, silica gel, chitosan, polystyrene, polymethylmetacrylate, magnetic materlal, or a combination thereof.
[81] 81. The system of claim 80, wherein the support is composed of nylon.
[82] 82. The system of any one of claims 70 to 81, wherein the density of the support materia! is between about 0.6 g/ml and about 3 g/ml.
[83] 83. The system of any one of claims 70 to 82, wherein the density of the support materia! is above about 1 g/ml.
[84] 84. The system of any one of claims 70 to 83, wherein the ion-rich aqueous mixture comprises primary, secondary and/or tertiary amines; primary, secondary and/or tertiary aikanoiamines; primary, secondary and/or tertiary arnino acids; and/or carbonates.
[85] 85. The system of claim 84, wherein the ion-rich aqueous mixture comprises piperidine, piperazine, derivatives of piperidine or piperazine which are substituted by at least one alkanol group, monoethanolamine (MEA), 2-amino-2-methyl-1-propano! (AMR), 2-(2-aminoethylamino)ethanol (AEE), 2-amlno-2-hydroxymethyi-1,3-propanedioi (Tris), N-methyldiethanolamine (MDEA), dimethylmonoethanoiamine (DMMEA), diethylmonoethanolamine (DEMEA), triisopropanoiamine (TIPA), triethanoiamine, dialkylether of polyalkylene glycols, diaikylether or dirnethylether of polyethyiene glycoi, amino acids comprising glycine, proline, arginine, histidine, lysine, aspartic acid, glutamic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, ieucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine, and derivatives such as taurine, N.cyclohexyl 1,3-propanediamine, N-secondary butyl glycine, N-rnethyl N-secondary butyl glycine, , diethylglycine, dimethylglycine, , sarcosine, , methyl taurine, methyl-a-aminopropionic acid, N-(3-ethoxy)taurine, Ν-(β-aminoeihyl)taurine, N-methyl alanine, 6-aminohexanoic acid and potassium or sodium salts of the amino acids; potassium carbonate, sodium carbonate, ammonium carbonate, promoted potassium carbonate solutions and promoted sodium carbonate solutions or promoted ammonium carbonates; or mixtures thereof.
[86] 86. The system of any one of claims 70 to 85, wherein the biocatalysts are enzymes. 12 12DK 2014 00144 U1
[87] 87. The system of ciaim 86. wherein the enzymes are carbonic anhydrase.
[88] 88. The system of ciaim 87, wherein the carbonic anhydrase is immobilized on a surface of the support material of the microparticles, entrapped within the support mate ri al of the microparticles, or a combination thereof.
[89] 89. The system of ciaim 87, wherein the carbonic anhydrase is provided as cross-linked enzyme aggregates (CLEAs) and the support material comprises a portion of the carbonic anhydrase and crosslinker,
[90] 90. The system of ciaim 87, wherein the carbonic anhydrase is provided as cross-linked enzyme c rystals (CLECs) and the support material comprises a portion of the carbonic anhydrase.
[91] 91. A system for capturing C02from a C02-containing gas comprising: micro-particies comprising a support materiai and biocatalysts supported by the support material, the biocatalysts promoting dissolution and transformation of C02 into bicarbonate and hydrogen ions; an absorption unit configured for contacting the C02-containing gas with an absorption mixture comprising a iiquid solution and the micro-particies, and producing a C02-depleted gas and an ion-rich mixture comprising the microparticles; a separation unit configured for receiving the ion-rich mixture and removing the micro-particies iherefrom to produce an ion-rich solution; a desorption reactor for receiving the ion-rich aqueous mixture to enable transformation of the bicarbonate and hydrogen ions into C02 gas and water, thereby producing a C02 gas stream and an ion-depleted solution; and an addition unit configured to receive micro-particies from the separation unit and adding micro-particies back into the ion-depieted solution for recycling back into the absorption unit.
[92] 92. The system of ciaim 91, wherein the absorption unit comprises a packed reactor. 13 13DK 2014 00144 U1
[93] 93. The system of claim 91, wherein the absorption mixture comprises an absorption compound selected from piperidine, piperazine, derivatives of piperidine or piperazine which are substituted by at ieast one aikanoi group, monoethanolamine (MEA), 2-amino-2-methyl-1-propanoi (AMR), 2-(2-aminoethylamino)ethano! (AEE), 2-amino-2-hydroxymethyi-1,3-propanediol (Tris), N-methyldiethanolamine (MDEA), dimethylmonoethanolamine (DMMEA), diethylmonoethanolamine (DEMEA), triisopropanolamine (TIPA), triethanolamine, dialkylether of polyalkylene giycols, dialkylether or dimethyiether of poiyethyiene giycoi, amino acids comprising glycine, proline, arginine, histidine, lysine, aspartic acid, glutarnic acid, methionine, serine, threonine, glutamine, cysteine, asparagine, leucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenyiaianine, and derivatives such as taurine, N.cyclohexyl 1,3-propanediamine, N-secondary butyi giycine, N-methyl N-secondary butyl glycine, , diethylglycine, dimethylglycine, , sarcosine, , methyl taurine, methyl-a-aminopropionic acid, N-(3-ethoxy)taurine, N-(3-aminoethyl)taurine, N-methyi alanine, 6-aminohexanoic acid and potassium or sodium salts of the amino acids; potassium carbonate, sodium carbonate, ammonium carbonate, promoted potassium carbonate solutions and promoted sodium carbonate solutions or promoted ammonium carbonates; or mixtures thereof.
[94] 94. A C02 capture formulation for capturing C02from a C02-containing gas, the formulation comprising: an aqueous mixture comprising: water; and an absorption compound selected from: primary, secondary and/or tertiary amines; primary, secondary and/or tertiary aikanoiamines; primary, secondary and/or tertiary amino acids; and carbonates; and 14 14DK 2014 00144 U1 microparticies comprising a support materiai and biocatalysts supported by the support materiai, the biocatalysts promoting dissolution and transformation of C02 into bicarbonate and hydrogen ions, the micro-particies being sized within an order of magnitude of a thickness of a reactive iiquid fiim formed between the absorption mixture and the C02.
[95] 95. The formulation of ciaim 94, wherein the micro-particies are sized so as to be smaller than the thickness of the reactive Iiquid film.
[96] 96. The formulation of ciaim 94, wherein the micro-particies are sized between about 1 pm and about 100 pm.
[97] 97. The formulation of any one of claims 94 to 96, wherein the micro-particies have an activity density of at least about 0.06 WA/mm2.
[98] 98. The formulation of any one of claims 94 to 97, wherein the micro-particies are provided in the absorption mixture at a maximum particle concentration of about 40% w/w or at a maximum particle concentration of about 30% w/vv.
[99] 99. The formulation of any one of claims 94 to 98, wherein the support is at least partially composed of nylon, cellulose, silica, silica gel, chitosan, polystyrene, poiymethylmetacrylate, magnetic materiai, or a combination thereof.
[100] 100. The formulation of any one of claims 94 to 99, wherein the density of the support materiai is between about 0.6 g/mi and about 3 g/mi.
[101] 101. The formulation of any one of claims 94 to 100, wherein the biocatalysts are carbonic anhydrase.
[102] 102. The formulation of ciaim 101, wherein the carbonic anhydrase is immobiiized on a surface of the support materiai of the microparticies, entrapped within the support materiai of the microparticies, or a combination thereof.
[103] 103. The formulation of ciaim 101, wherein the biocatalysts are entrapped inside or fixed to a porous coating materiai that is provided around a support particle.
[104] 104. A system for capturing C02 from a C02-containing gas comprising: 15 15DK 2014 00144 U1 micro-particies comprising a support materiai and biocatalysts supported by the support maleria!, the biocataiysts promoting dissolution and transformation of C02 into bicarbonate and hydrogen ions; an absorption unit configured for contacting the C02-containing gas with an absorption mixture comprising a liquid soiution and the micro-particies, and producing a C02-depieted gas and an ion-rich mixture comprising the micro-particies; and a desorption reactor for receiving the ion-rich aqueous mixture comprising the micro-particies to enable transformation of the bicarbonate and hydrogen ions into C02 gas and water, thereby producing a C02 gas stream and an ion-depieted soiution.
[105] 105. The system of ciaim 104, wherein the micro-particies are stzed so as to be within an order of magnitude or smaller than a thickness of a reactive iiquid fiim formed between the absorption mixture and the C02 in the absorption unit.
[106] 106. The system of ciaim 104, wherein the micro-particies are sized between about 1 pm and about 100 pm.
[107] 107. The system of any one of ciaims 104 to 106, wherein the micro-particies are provided in the absorption mixture at a maximum particle concentration of about 40% w/w or at a maximum particle concentration of about 30% w/w.
[108] 108. The system of any one of ciaims 104 to 107, wherein the support is at least partially composed of nylon, cellulose, siiica, silica gel, chitosan, polystyrene, polymethylmetacrylate, magnetic materiai, or a combination thereof.
[109] 109. The system of any one of ciaims 104 to 108, wherein the density of the support materiai is between about 0.6 g/ml and about 3 g/ml.
[110] 110. The system of any one of ciaims 104 to 109, wherein the biocatalysts are carbonic anhydrase. 16 16DK 2014 00144 U1
[111] 111. The system of clairm 110, wberein the carbonic anhydrase is immobiiized on a surface of the support material of the microparticles, entrapped within the support material of the microparticles, or a combination thereof.
[112] 112. The system of any one of daims 104 to 111, wherein the biocatalysts are entrapped inside or fixed to a porous coating material that is provided around a support partide.
[113] 113. The system of any one of claims 104 to 112, wherein the absorption unit is a packed reactor and the micro-particles are sized and provided in a concentration such that the absorption mixture flows through the packed reactor.
[114] 114. The system of any one of claims 104 to 113, further comprising an addition unit for adding an amount of the micro-particles to the ion-depieted solution before recyciing the ion-depleted solution for further contacting the C02-containing gas in the absorption unit.
[115] 115. The system of any one of claims 104 to 114, wherein the absorption mixture comprises water and an absorption compound.
[116] 116. The system of claim 115, wherein the absorption compound comprises piperidine, piperazine, derivatives of piperidine or piperazine which are substituted by at ieast one aikanol group, monoethanoiamine (MEA), 2-amino-2-methy!-1-propano! (AMP), 2-(2-aminoethylamino)efhanol (AEE), 2-amino-2-hydroxymethyl·1l3-propanedioi (Tris), N-methyidiethanolamine (MDEA), dimethylmonoethanolamine (DMMEA), diethylmonoethanoiamine (DEMEA), triisopropanoiamine (TIPA), triethanoiamine, diaikylether of polyalkylene giycois, diaikylether or dimethylether of poiyethylene giycoi, amino acids comprising glycine, proiine, arginine, histidine, lysine, aspartic acid, giutamic acid, methionine, serine, threonine, giutamine, cysteine, asparagine, ieucine, isoleucine, alanine, valine, tyrosine, tryptophan, phenylalanine, and derivatives such as taurine, N.cyclohexyl 1,3-propanediamine, N-secondary butyl glycine, N-methyl N-secondary butyi glycine, , diethylglycine, dimethylglycine, , sarcosine, , methyi taurine, methyi-a-aminopropionic acid, N-(|3-ethoxy)taurine, N-(p-aminoethy!)taurine, N-methyi alanine, 6-aminohexanoic acid and potassium or sodium salts of the amino acids; potassium carbonate, sodium carbonate, ammonium carbonate, promoted potassium carbonate solutions and promoted sodium carbonate solutions or promoted ammonium carbonates; or mixtures thereof. DK 2014 00144 U1 17
[117] 117. The system of ciaim 115, wherein the absorption compound comprises potassium carbonate.
[118] 118. The system of any one of clairns 104 to 117, further comprising a pump for receiving and pumping the ion-rich mixture to the desorption unit, and wherein the micro-particies are further sized and provided in a concentration such that the ion-rich mixture comprising the micro-particles is pumpable.

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公开号 | 公开日

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

WO2004007058A1|2002-07-11|2004-01-22|Co2 Solution Inc.|Triphasic bioreactor and process for gas effluent treatment|

---

CA2414871A1|2002-12-19|2004-06-19|Sylvie Fradette|Process and apparatus using a spray absorber bioreactor for the biocatalytic treatment of gases|

---

CA2535521C|2005-02-07|2013-07-09|Co2 Solution Inc.|Process and installation for the fractionation of air into specific gases|

---

WO2008137846A2|2007-05-04|2008-11-13|Akermin, Inc.|Immobilized enzymes and uses thereof|

---

法律状态:
2016-08-12| UYA| Request for examination filed (utility model)|Effective date: 20160715 |

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2016-09-23| UYM| Decision on examination: utility model maintained as unamended|Effective date: 20160915 |

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2020-09-24| UUP| Utility model expired|Expiry date: 20200804 |

优先权:

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申请号 | 申请日 | 专利标题

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EP10805915.5A|EP2461894B1|2009-08-04|2010-08-04|Process for co2 capture using micro-particles comprising biocatalysts|

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EP10805915|2010-08-04|

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DK201400144U|DK201400144Y4|2010-08-04|2014-10-23|CO2 CAPTURE SYSTEM USING PACKAGED REACTOR AND ABSORPTION MIXING WITH MICROPARTICLES COMPREHENSIVE BIO-CATALYST|

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DK201400144|2014-10-23|DK201400144U| DK201400144Y4|2010-08-04|2014-10-23|CO2 CAPTURE SYSTEM USING PACKAGED REACTOR AND ABSORPTION MIXING WITH MICROPARTICLES COMPREHENSIVE BIO-CATALYST|

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DKBA201400177U| DK201400177Y4|2009-08-04|2014-12-08|CO2 CAPTURE SYSTEM USING PACKAGED REACTOR AND|