World Resource Review

Vol. 16 No.2

CAPTURING CARBON DIOXIDE DIRECTLY ATMOSPHERE

FrankS. ZemanandKlaus S. Lackner Department Earth and Environmental of Engineering ColumbiaUniversity 918 Mudd, MC 4711 500 West 120dt Street New York, NY, 10027 USA Email: fszl@columbia.edu
Keywords: Air extraction,COb sequestration, climate change, kraft process

FROM THE

SUMMARY
The increasingconcernoverrising CO2levels in the atmosphere and their potentialclimateeffectsis fuelling research aimedat carbonmanagement. One areaof research focuseson capturingthe CO2after combustion and sequestering underground.Captureschemes it would operateat the site of generation taking advantage the elevated of concentrations CO2in the effluent. of Here,however,we proposean indirectmethodof carboncapturethatremoves CO2from the atmosphere.This process combinesexistingtechnologies with recenttechnological innovationsinto a novel carboncaptureconcept termedair extraction. The process usesdissolvedsodiumhydroxideto removethe CO2from ambientair. The resultantsodiumcarbonate solutionis causticized using calcium hydroxideto regenerate sodiumhydroxide solutionandprecipitatecalcite. the The calciteis then thermallydecomposed producelime andCO2.The lime is to hydratedto completethe process.Theselatterstages usedroutinely in the are paperindustryandthe calcinationof limestoneis centralto the cementindustry. This paperreviewsthe process highlightspertinentresearch developa and to likely cost-effective process. It is shownthatthe proposed process well defmed is and technicallyfeasible.The wide parameter space and potentialfor improvementssuggest further efficiency improvements attainable. The that are most significantimprovements be derived from efficient heatmanagement. will

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1 INTRODUCTION Recent yearshave seenattentiondrawnto issues sun-ounding changes in the global climateinducedby humanactivities. Concernoverthesepotential changes led to the formationof international has agencies, suchasthe Intergovernmental Panelon ClimateChange(IPCC),whosemissionis to consider this problem. The IPCC hasstatedthat carbondioxide (COJ is the greenhouse gascontributingthe largestportion of the anthropogenic increase global in radiativeforcing, which the IPCC defmesasan externallyimposedperturbationin the radiative energybudgetof the Earth's climatesystem. AnthropogenicCO2 producesapproximately 62% of the increase 1.46 W1m2 of a total increase or out of 2.43 W/m2(HoughtonandDing, 2001). The increasein atmospheric CO2 levelscanbe largelyattributedto the combustion fossil fuels,with a small of contributionfrom cementproductionand landusechanges.The total global emissions reached 6,611 million metric tons of carbonin 2000,which represents a 1.8%increaseover 1999(Marland,BodenandAndres,2003). Giventhe world's economicdependence fossilfuels andthe expected on increasein consumption, methodsfor mitigating the atmospheric release CO2needto be developed. of The primary targetsfor mitigationare powerplantsas theyproducelarge concentrated streamsof CO2(Herzogand Drake,1996). Thesesourcesaccount for aboutonethird of the worldwide CO2emissions. Even aftereliminating all emissionsfrom power plants,the remainingtwo thirds would still be released to the atmosphere.Roughlyhalf of all emissions arisefrom smalldistributedand oftenmobile sources. Mitigating their CO2impacton the atmosphere more is difficult. One approach to provide fuels that are carbonfree, which is the is reason muchemphasis beingplacedon hydrogenasa transportation is fuel. Here,we proposean alternativemethodfor mitigating CO2emissions from sourcesotherthan powerplants. We proposethatCO2is removeddirectly from the atmosphere a costeffective, industrialprocess in hereafter referredto as air extraction. Air extractioncanbe viewedasa variationof flue gasscrubbing where the fluid is at atmospheric temperature pressure and with a CO2concentration of 0.037%. The implementation the process of discussed hereusesa sodium hydroxide (NaOH)based,alkalineliquid sorbent removethe CO2from the to ambientair by producingdissolvedcarbonate ions. In orderto recoverthe sodiumhydroxide,the resultantsodiumcarbonate (NazCO3) solutionis mixed with calciumhydroxide (Ca(OH)Jto producesodiumhydroxideand calcium
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with calcium hydroxide (Ca(OH)2) producesodiumhydroxideand calcium to carbonate(CaCO3)in a reactionknown as causticizing. This reactiontransfers the carbonateanion from the sodiumto the calciumcation. The calcium carbonate precipitates,leavingbehind a regenerated sodiumhydroxidesorbent. The precipitateis dried, washedand thermally decomposed producelime to (CaO). This step. knownas calcination, is followed by hydratingthe lime. known as slaking, which completes process.The process recycling of the of sodiumhydroxide using calciumhydroxide hasbeenin usein the pulp and paper industrysince 1884,where it is known asthe Kraft Process (Miner and Upton, 2002). This process also involvesthe calcinationof limestone,which is at the heart of the cementmanufacturingindustry. In short. eachunit process required is known to be technicallyfeasibleand the only remaining questions surround their efficienciesand costs. This paperwill presenta re'tiew of the indi~idual components comprisingthe air extractionprocess with a view to highlighting the potential benefitsand concerns. The issuessurroundingtheir integrationinto a functional air captureS}.stem also bediscussed.The layout of the paperwill follow the will path of the C~ moleculethroughthe system. A simplified schematicof the process shownin Figure 1. is

Figure 1 Overviewof Air ExtractionProcess. Note that two reactions not shown; are !hying (d), and hydrating(h).

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2 ALKALINE SODIUM SORBENTS

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The removalof a gaseous component through contactwith a liquid is known as wet scrubbihg. Wet scrubbingcanbe divided into processes where there is a chemicalreactionbetween sorbate the sorbent wherethe the and and sorbateis physicallydissolvedinto the sorbent solution. For the air extraction process proposean alkaline sodiumsolventwhich reactschemicallywith the we entrained CO2. The chemicalreactionfor this process shownbelow as reaction is (1).

2NaOH (aq)+ CO2(g) -+ Na2CO3(aq) H2O; +

(1:

The aqueous carbonate reactioncanbe simplified by omitting the cation, resulting in the following ionic reaction.
20H-(aq) + CO2 (g)-+ CO32-(aq) H2O 0) +

(2)

6.GO -56.1 kJ/mol (Lllio= -109.4 kJ/mol) =

Note thatthe enthalpyandfree energyof the reactionare for a nominal I molar solution. The thermodynamic data,given at298K anda pressure 1 bar, of was obtainedfrom the availableliterature(Lide, 2000). As a comparison, free the energyof mixing CO2with nitrogenand oxygento form ambientair is given by
~G = RT In (P atrnlPCoJ -20 kJ/mol.

(3)

Clearly, sodiumhydroxideprovidesa sufficientdriving force to effectively collectCO2from ambientair. Eventhougha lowerbinding energy might be desirable, high binding energyof chemicalsorbents the provesuseful in absorbing CO2from streams with low partialpressures CO2(White, et al.,). As of an alternativewith a weakerbinding energy,one may considersodiumor potassium carbonate buffer solutionsasa sorbent.In this casethe absorption can be described by:
CO2(g)+ CO]2- + H2OQ) -+ 2 HCO]'

(4)

IlGO = -14.3 kJ/mol

(ilHO=-27.6 klimat)

Even in this caseit is possibleto mustera sufficientthermodynamic driving force to removeCO2from the air. For a two molar solutionof bicarbonate
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ions, the free energyof the reactionfrom ambientair is negativeif the bicarbonate concentration staysbelow0.15molar. A similar resultcanbe obtainedby calculatingthe massactionequilibriumusing empiricalvaluesfor the equilibrium constants.Reaction(4) is effectivelytrimolecularand is the result of a sequence of reactionswhich have fastkinetics at high temperatures very high carbonate or to bi-carbonate ratios. Otherwise process the occursin the diffusion regime, which is much slower(Astarita, 1967), makingthis reactionimpracticalfor air extractionasit is kinetically limited. In a recentreviewfocusedon flue gas,White et al. (2003)do not specificallydiscussabsorption sodiumhydroxide (NaOH),ratherthey consider on aqueous solutionsof sodiumand potassium carbonate.Thesesorbents were compared mono-ethanolamine to (MEA), the industrystandard, it was and concludedthat MEA providesa substantially more cost-effectivesolution(Leci and Goldthorpe,1997). At thesehigherCO2concentrations therewould be no advantage the higherbinding energyof the hydroxideandthe heatof this in reactionis in anycaseirretrievablylost. An additionalcomplicationarises because productcarbonate the cannot decomposed be with eitherheator pressure. The resultant NazCa] mustbe efficiently decomposed chemically. We proposeto accomplish chemicaldecomposition the using calciumhydroxideasan

intermediary.
A sodiumhydroxide solutionprovidesa liquid sorbentthat is more easily cycledthrougha piping system than a calciumhydroxidesuspension. binding Its energyis strongenoughand its reactionkinetics fast enough obviatethe need to for heating,cooling or pressurizing air. Because the CO2is so dilute any such actionwould result in an excessive energypenalty. The hydroxide solutionavoids all suchcomplications. Sincesodiumhydroxideis cheaper than potassium hydroxide our startingpoint for the air extraction designwill be basedon sodium hydroxide. 2.1 Experimental Investigations into SodiumHydroxide Sorbents The absorptionof CO2by NaOH solutionwas studiedin 1943by Tepe andDodge(1943). Experiments wereperformedusing a packedtower arrangement with the inlet gashavinga CO2concentration -2%. Tepeand of Dodgeinvestigated effectsofNaOH concentration, the NazCO) concentration, gas flow rate, solventflow rate,and solventtemperature the CO2uptakerate. The on effectswere quantified in terms of an over-all absorption coefficient.The rate resultsshowedthatthe rate coefficientincreased with increasing NaOH
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concentration a maximumnormality of -1.8 and thendecreased. to The rate coefficientdecreased with increasing N~CO3 concentration.The gas flow rate had no effect, while the rate coefficientincreased with increasingsolventflow rates. The temperature the solventaffectedthe rate coefficient significantly of with the rate coefficientfollowing the temperature the solventto the 6th of power. The absence sensitivityto gas flow rate and high sensitivityto temperature of suggests for theseCO2concentrations, reactionis limited by transport that the resistance the liquid phase.More recentresultson MEA solutionsalso show in that at elevated CO2concentrations absorption limited by resistance the liquid is in phase(Aroonwilas et al.,2001). Generallyin wet scrubbing, canbreakthe transport one resistance into two distinct components, air sideand liquid sideresistance.The air side the resistance dominatedby the diffusion barrier in the laminarboundarylayer. is Typically, sucha boundarylayeralsoexists onthe liquid side. In the bulk fluid, dissolvedCO2reactswith water,or hydroxideionsto form carbonate or bicarbonate ions. In contrast the reactionsof CO2with water,the reactions to with hydroxidereactionsare very fastand their reactiontime canbe ignored (Astarita,1967). However,sincediffusion coefficientsof CO2in air are roughly four ordersof magnitudelargerthan ionic diffusion coefficientsin water, it is easy to becomeratelimited on the liquid side. The experiments TepeandDodge of suggest the transportresistance dominatedby the liquid phase. that is For a onemolar carbonate concentration the liquid, the ion in concentration ratio between carbonate ions in the fluid andCO2moleculesin the gasis 66,000: I. It thus will taketime to fill up a boundarylayer on the liquid side. This suggests at sufficiently low partialpressures CO2the extraction that of processwill be limited by air~side resistance. The absorptibn CO2from atmospheric usingan apparatus of air similar to that of TepeandDodgewasstudiedby Spector Dodge (Spector Dodge, and and 1946). For ambientair, CO2absorption rateswere proportionalto G", whereG is the air flow rateandthe coefficienta.varies from 0.35 at low flow ratesto 0.15 at high flow rates. This suggests at low CO2concentrations, that 0.031%, the liquid side resistance transport to ceases be dominant. It is likely that in theseexperiments, to fluid surfaceregeneration sufficiently fastto preventa built up of liquid-side was flow resistance.The experiments showthat wet scrubbingusingNaOH can did effectivelyremoveCO2from atmospheric at a ratewherethe unavoidableair air
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sideresistance flow hasbecomeimportant. Spector Dodgeobtained to and approximately90%removal for atmospheric concentration levels. The advantage usinga stronghydroxide for CO2captureis a high load of capacityanda fast reactiontime. The resultsby Spector Dodge suggest a and that system be built that will be limited by transport can resistance the air side of the in air-liquid contactsurface. In a regimewherethe dominanttransport resistance on the air side,it is is possibleto estimate sizeof the CO2extractorby the air dragthe extractor the causes the flow. Apart from the pressure on gradientdriven momentum flow, momentum transferto the wettedsurfacefollows a similar transportequationas the CO2diffusion. As a consequence, system a that incursa pressure drop roughly equalto pV2, which extractedvirtually all of the initial momentum,will be ableto extracta substantial fraction of the CO2from the flow. To setthe scaleof the operation,at 10m/sthe air flow throughan openingof 1m2 carriesa CO2load that equalsthe CO2producedby generating kW of heatfrom coal(Lackner,Grimes 70 andZiock, 1999). A 100MW powerplant operatingat 33% efficiencywould require9,000m2 wind crosssection,if CO2collectionefficiencywould be about of 50%.

3 CAUSTICIZATION Causticization refersto the transfonnation sodiumcarbonate of into sodiumhydroxide. It is generallyperfonnedby addingsolid calciumhydroxide to the sodiumcarbonate solution. The solubility of calciumhydroxideis suchthat this fonDS emulsionaccordingto reaction(5). an

(5)
This reactioncanalsobe written in its ionic form asfollows.

(6)
dGO = -18.2 kJ/mol (L\HO= -5.3 kJ/mol)

This process step regeneratesthe sodium sorbent. The CO2 is removed as a solid through a filtration process. Zsako (1998) noted that one could also start with lime, which would slake immediately in the aqueous solution, but in air
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extraction,it is importantrecoverthe heatof the slakingreactionat elevated temperatures.Thuswe haveseparated slaking stepfrom the causticization. the Experiments have shownthatthe causiticization increases rate with temperature (DotsonandKrishnagopalan, 1990). The initial sodiumcarbonate concentration thoseexperiments -2.0 mol/l andthe samples for was were subjected constant to stirring. Reaction(5) eventually approaches equilibriumand causticizingefficiency is generallyin the rangeof 80 to 90%. Causticizing efficiency refersto the amountof sodiumcarbonate converted sodium to hydroxide. Dotson(1990)determined the rate constant the reaction(5) that for increased a factor3 asthe operatingtemperature raisedfrom 353 to 393K. by was The rate constant droppedwhenthe feed solutioncontainedsodiumhydroxide. The experimental causticizingefficiency for pure sodiumcarbonate a mixture and of sodiumhydroxide and sodiumcarbonate were -94% and -85% respectively. The rate constant the causticization drivenby the concentration for is of free Ca ions in solution. Highly alkalinesolutionswill limit the availability of dissolvedCa++ anytime and consequently at reducethe rate of conversion. Elevatedtemperatures activestirring reducediffusionalresistance thus and and will increase rate of reactions. the It was alsonotedthatthe concentrations all the calciumspecies of remain essentiallyconstant throughoutthe reactions to their low solubility. This due suggests the efficiencyandrate constants that maychange insufficientcalcium if is present. Dotsonprevented occurrence usinga 10%stoichiometric this by excessof lime. However,this excess resultsin solid calciumhydroxidebeing entrainedwith the filtrate. This would producehigherenergyconsumption the in lime kiln dueto the dehydration reactionmentionedby Zsako(1998). The concentrations the variousspecies, of both sodiumandcalcium,have a profound effect on the quality of the resultant filtrate. Konno et al. observed thatthe solid phaseof calciteis unstablein pureNaOH solutiongreater than 2 moVl and easilyconverts Ca(OH)2 to (Konno, Yasunoriand Kitamura,2002). Thesesolidsbecomestablein a I moVl NaOH solutioncontainingat least0.02 mol/l N~CO3. This latter solutionmixture suggests for an initial sorbent that concentration I mol/L, 96% of the hydroxideions wereconverted carbonate of to according reaction(2). The presence to ofN~CO3 alsoreduces solubility of the calcite. The solubility ofCa(OH)2is stronglydependent the NaOH on concentration dropsby a factor4, to 5 x 10-4 and moVl,asthe NaOH increases from 0 to 0.5 moVl. Konno alsoobserved concentrations the ofCa2+ NaOH and

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during the reaction. As expected Ca2+ the concentration droppedandthe NaOH concentration increased the reactionprogressed. as The initial Ca2+ concentration was -1 x 10-3 moM. Konno alsonotedthat Ca(OH)2 supersaturation ratio is the driving force for nucleation. In effect,theseprocesses balancethe solubility of calciumhydroxide against solubility of calciumcarbonate.The valuesfor the the dissociationconstants availablein the literature(Snoeyinkand Jenkins,1980). are [Ca~[OH-r < KoH=10-'49 mor/l
[Ca++] [CO32-] < Kco3=10-3.22 mor/l

(8) (9)

Given that the calciumconcentration the samein both (8) and (9), we is can solve for the carbonate concentration follows. as
[CO]20]= <Kco]lKo~ x [ORoP

Assuminga 1 molar sodiumsolutionwe can neglect effectof calcium the on the chargebalanceandthe sodiumconcentration mustthereforebalanceall the negativeions. Ifwe furtherdefmethe causticizingefficiency (E)asthe ratio of hydroxide ions over sodiumions we obtainthe following relationship.
-1

&=

(2~[OH-]+ KOH

The stablesolutionsuggested Konno would containapproximately1 by mol per liter hydroxide ions. This would suggest theoreticalcausticizing a efficiency of 96%, which is slightly higherthanthe experimental value of Dotson et al. (1990). The differenceis likely dueto the omissionof ionic activity in the calculations. The experimental work discussed aboveprovidesa pathwayfor recoveringsodiumhydroxide from sodiumcarbonate.In the process, carbon the dioxide has beentransferred into a solid form of calciumcarbonate, which canbe readilyremovedfrom the liquid and afterwashinganddrying it canbe thermally decomposed. The causticization takesplace in an emulsionof calciumhydroxide. Thereare a numberof options for the implementation, this unit process but is well established the pulp and paperindustry. in

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4 CALCINATION OF LIMESTONE The fmal stageof the air extraction process the recycling of the calcite is precipitate. This is accomplished throughthermalregeneration calcination. or Lime and limestoneareamongthe oldestmaterialsusedby humanitywith the fIrst recordeduse in the Egyptianpyramids. The fIrst soundtechnicalexplanation of lime calcinationcamein the 18th centuryfrom the British chemist,Joseph Black (Boynton, 1966). Therearethreeessential factorsin the kinetics of dissociation; the dissociation temperature, durationof calcination,andthe CO2in the the surroundingatmosphere. The reactionis shownbelow.
CaCO3(s) -4 CaO(s) + CO2(g);

LiliO = + 179.2 kJ/mot

12)

The fIrSt quantificationof the thennaldecomposition perfonned in was 1910andthe resultwas a decomposition temperature 1171K in a 100%CO2 of atmosphere atmospheric at pressure (Johnston, 1910). Currentpracticesuselime kilns to dissociate calcite which vary greatlyin their perfonnance.The most the importantperfonnance metric for air extraction the thennalefficiency, which is is the productof the theoreticalheatrequirement the availableoxide content and divided by the total heatrequirement.Boyntoncompares three hypothetical kilns and bases one on "the lowestfuel efficiency onrecord,that of the mostadvanced Gennanmixed-feedkiln." This advanced is reportedto obtaina thennal kiln efficiency of 85% for 93%availablelime. The thennalefficiencyrefersto the proximity to the theoreticalminimum heatrequirement defmedby reaction(12) as while the availablelime refersto the amountof inert materialpresent,in this case 7%. This translates a total heatrequirement 3 .03 MMBtu per ton of lime into of or 4.5 GJ per tonne of CO2,This latterfigure is lowerthanthe 4.8 GJ pertonne of CO2used in a previousair extractionfeasibility study(Zeman,2003). The thennodynamicminimum heatrequirement 4.1 GJ/tonne of CO2canbe calculated from the enthalpyvalue in reaction(12). The potentialcostof air extractionwill be dominatedby this reactionand any improvement regardingthe threekinetic factorslisted abovewill directly affectthe cost of the project. A lower dissociation temperature requireless will heatinput as will a shorterdurationof calcination a lower CO2contentin the and surroundings.Garcia.,Labiano al. found that calcination et rate increased with temperature a neutralenvironment decreased increasing in and with CO2partial pressure and total pressure (Garcia-Libianoet al., 2002). Khinasteta1.echoed
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similar fmdingsregardingthe effects of CO2partialpressure alsofound a but decrease reactionrateswith increasing in particlesize (Khinastet al., 1996). The effect of stearnon calcite decomposition alsoinvestigated.It was found that was stearnenhanced calcination the rate and evencompensated the presence for of CO2overthe solid (Thompson Wang,1995). Thomson'sexperiments and producedgreater than 95% conversion after 40 minutesin an environmentof 21 % stearnand 79% helium at a temperature 753 K. The positive effects of stearn of on calcinationmay be synergisticwith otheradvancements improving the in efficiency of calcination.In the caseof lime mud calcination,Theliander proposed a novel stearndrying system reduces overall systementhalpyby 33% that the (ThelianderandHanson,1993). Therearesomenovel designsfor calcination unitsaswell. The decomposition limestonewastestedin a solar reactorand of achievedan averageof -50% conversion (Imhof, 1997).

5 AIR EXTRACTION AS CARBON CAPTURE We areproposingto captureCO2directly from the atmosphere a cost in effectivemanner. As such,a brief comparison with the industrystandards will provide a benchmark future work. Stericallyhinderedamines(SHA) and for MEA areconsidered potentiallysuccessful capturetechnologies.Theyare CO2 regenerated using steamand their thermalenergyrequirements 700and 900 are kcal/kg CO2for KS-2 andMEA, respectively (Mimura et al., 1997). Thesevalues canbe converted 2.9 and3.8 GJ/tonneCO2. It shouldbe noted that Mimura et to al. captured90% of the CO2 generated the powerplants;the remainder by would haveto be mitigated by othermeans. An economicanalysisof CO2captureusing MEA obtaineda cost of $50 pertonne of CO2 avoided(Zappelli et al., 2003). Calciumbasedsorbents havealso beeninvestigated use in CO2capture. The for thermalrequirements follow the limits outlinedabove;however,the will durability of the sorbent alsoan importantcostfactor. This has beendiscussed is for dry CO2cycles.Abanades summarized several studiesof the carbonation/calcination cycle and found very good agreement (Abanades, 1998). Starting at around80% conversion, performance rapidly droppedto lessthan 20% conversionat 14cycleswhere it stabilized. Thesetestswere conductedunder different conditionsthanproposedfor air extraction.Most importantlythe air extractionprocess would hydrateor slakethe resultinglime. Generallylime is regenerated the hydrationprocess, in thuswe do not expecta greatreductionin captureefficiency from onecycle to the next. The process hydrationis of

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CaO(s)+ H2O (I) -+ Ca(OH)2(s)

LiliO = -64.5 kllmot

(13)

The hydrationcauses both expansion the liberationof heatwhich and causes particleto split, exposingfreshsurfaces therebyreducingthe the and effectsof sintering. The inclusionof this reactionin the carbonation processwill likely alterthe perfonnance and durability of the lime cycle, as will the lower temperatures reaction. We believethatthesedifferences of precludethe useof durability datapresented Abanades a deterrent by as from further study. Zsako (1998)statedthat slakedlime undergoes dehydration temperatures at above ~700K underambientconditions. This defmes rangeof possibleoperating the temperatures the hydrationprocess. for Hydrationis highly exothennicandcan provide usefulheatenergyif it is perfonnedefficiently at high temperatures. Thereare othermethodsfor removingCO2from the atmosphere including physicalabsorption refrigerationamongothers. Steinberg and comparedeight differentmethodsof CO2removaland found alkaline wet scrubbingto be the leastenergyintensive(Steinberg and Dang,1977). The estimatedenergyrequiredto strip air of CO2was 0.4 kWh(e/lbmethanolor 4.4 GJ/tonneCO2. The CO2was strippedusing a 0.0I N K2CO3 solutionandwas desorbed hydrogen,from electrolysis, low pressure by and steam. It shouldbe noted thatthis calculation not includelosses did during the conversionof primary fuel to electricity. The feasibilityof air extractionwill dependon the overall cost in comparison alternateremovaltechnologies.The costper unit removalwill to furtherdependonthe energy requirements, durability of the sorbents, the and costsexternalto the process.Theseexternalcostscould includeexcessive water lossesfrom the wet scrubbing. this part of the processwill be in contactwith As the openatmosphere, evaporation be expected.This canbe minimized by can adjustingthe sorbentconcentration which variesthe vaporpressure until it matchesthat of the ambientair. The thennophysical propertiesof sodium hydroxide solutionare known for a wide rangeof concentrations (Olsson, Jernqvist and Aly, 1997). Otherexternalcostswill be delineated during bench and pilot scaledemonstrations. The calcinationreactionis likely the most energy intensivefor the statedprocess.This highlightsthe needfor efficient heat management within the system. Additionally, any significantlime degradation~
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..

6 CONCLUSION Our previous feasibility study mentioned earlier obtained a price range of ~$25- 75 per tonne of CO2extracted (Zeman, 2003). The large range is due to the fluctuations in the price of natural gas and the uncertainty regarding the cost of solid oxide membranes. This range does match up with the quoted cost of MEA capture and does suggest further studies may provide a viable option for extracting CO2 from the atmosphere. Air extraction is not necessarily more expensive than MEA capture in a flue stack. Even though the air contactors must be much larger than the equivalent contact surfaces in the flue stack, their contribution to the total cost may be very small. The recovery MEA sorbents requires similar amounts of energy, and becausethe air is clean and hydroxides are not subject to oxidative losses, the make-up costs are low in a hydroxide system. It is however clear, that the biggest challenge for air extraction will lie in the efficient management of heat and not in the design of the physical reactions. The information highlighted in this paper maps out a large parameter space. We believe that such a broad discussion will prove useful in designing new implementations of processes that have been optimized in the past for entirely different goals. Our objective is quite different from that of the individual studies cited. The overall goal of the process is the maximize CO2 capture while minimizing energy consumption. Variations in the operating conditions of each reaction should be investigated in order to quantify their effect on the entire process. For example, heating the fluid in the causticization reactor representsa compromise between increased energy consumption and longer reaction time. Sophisticated designs may maximize the amount of heat recaptured at elevated temperatures. For example, if the lime is hydrated using steam then the energy output of this reaction increases by the heat of condensation. This would be offset by steam generation elsewhere, but the higher quality heat obtained may be easier to harness. In the end, the minimum theoretical penalty for calcination is 4.1 GJ per tonne of CO2 and the maximum energy recoverable from hydration is 1.5 GJ per tonne of CO2. The resulting minimum net energy penalty is 2.6 GJ per tonne of CO2, which is already lower than the practical energy cost of amine solutions.~
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Theoretical efficiencies may not be achievable in practice but they are an indication of the potential of the method.

REFERENCES
Abanades, J.C.,The maximumcaptureefficiencyof CO2using a carbonation! calcinationcycle ofCaO/CaCO3, ChemicalEngineeringJournal, 90, 303-306 (2002).
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Separationand Purification Technology, 24,403-411 (2001).

Astarita, G., Mass Transfer with Chemical Reaction, pp. 131-152, Elsevier Publishing Company, New York (1967). Boynton, R.S., Chemistry and Technology of Lime and Limestone, Interscience Publishers, New York pp. 3,255,258 (1966).

Dotson,B.E.,A. Krishnagopalan, Causticizing ReactionKinetics, Tappi Proceedings 1990 Pulping Conference, 234-244(1990). Garcia-Labiano, A. Abad, L.F. de Diego, P. Gayan, J. Adanez,Calcinationof F., calciumbasedsorbentsatpressure a broadrangeof CO2concentrations, in ChemicalEngineeringScience, 2381-2393 57, (2002). Herzog,H.J., E.M. Drake,Carbondioxide recoveryand disposalfrom large energysystems, Annu.Rev.Energy Environ.,21, 145-66(1996). Houghton,J.T., Y. Ding, co-chairs,ClimateChange 2001: the ScientificBasis, Intergovernmental Panelon ClimateChange (2001). Imhof, A., Decomposition limestonein a solar reactor,Renewable of Energy,10 No. 2/3, 239-246(1997). Johnston, J.,.l Am. Chem.Soc.,32, p. 938 (1910). Khinast,J., G.F. Krammer, Ch. Brunner, G. Staudinger, Decomposition of limestone:the influenceof CO2andparticlesize on reactionrate, Chemical EngineeringScience, 51(4), 623-634(1996).
Konno, H., N. Yasunori, M. Kitamura, Crystallization of aragonite in the causticizing reaction, Powder Technology, 123, 33-39 (2002).

Lackner,K.S., P. Grimes, H.J. Ziock, Carbondioxide extractionfrom air: Is it an option, Proceedingsofthe 24thAnnual TechnicalConference Coal Utilization on and Fuel Systems (1999). Leci, C.L., S.H. Goldthorpe,Assessment CO2Removalfrom PowerStation of Flue Gas,EnergyConverso Mgmt.,33 (5-8), 477(1997). Lide, D.R., editor in chief, CRCHandbookof Chemistry and Physics81stEd., CRC PressLLC, Boca RatonFlorida (2000).
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