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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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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).
(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)
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)
(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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1(;0
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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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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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);
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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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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(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.
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M~l~d, G., T.A. Boden,andR.J.Andres,Global,Regional,and NationalCO2 Emissions.In Trends:A Compendium Data on Global Change, of CarbonDioxide InformationAnalysis Center, Oak RidgeNational Laboratory,U.S. Department of Energy,Oak Ridge,Tenn.,U.S.A. (2003). Mimura, T., H. Simayoshi, T. Suda, M. Iijima, S. Mituoka, Development of energysavingtechnologyfor flue gas carbondioxide recoveryin powerplant by chemicalabsorption methodandsteamsystem, EnergyConverso Mgmt.,38, S5762 (1997). Miner, R., B. Upton, Methodsfor estimatinggreenhouse emissionsfrom lime gas kilns at kraft pulp mills, Energy,27, 729-738(2002). Oates,J.A.H., Lime andLimestone: chemistryand technology, production and uses, 213, Weinheim:Wiley-VCH, New York (1998). p. Olsson,J., A. Jemqvist, G. Aly, Thermophysical propertiesof aqueous NaOHH2Osolutionsat high concentrations, InternationalJournal of Thermo physics, 18(3),779-793(1997). Snoeyink,V.L., D. Jenkins,WaterChemistry, 295, JohnWiley and Sons,New p. York (1980). Spector,N.A., B.F. Dodge,Removalof carbondioxide from atmospheric air, Trans.Am. Inst. Chem.Engrs.,42,827-48 (1946). Steinberg, M., V-D. Dang, Productionof syntheticmethanolfrom air and water using controlledthermonuclear reactorpower-I. Technology and energy requirement,EnergyConverso Mgmt.,17,97-112(1977). Tepe,J.B., B.F. Dodge,Absorptionof CarbonDioxide by SodiumHydroxide Solutionsin a PackedColumn, Trans.Am. Inst. Chem.Engrs.,39,255 (1943). Theliander,H., C. Hanson,Steamdrying andfluidized bed calcinationof lime mud, Tappi Journal,76(11),181-188(1993). Thompson,W.J., Y. Wang,The effectsof steamand carbondioxide on calcite decomposition usingdynamicx-ray diffraction, ChemicalEngineeringScience, 50(9), 1373-1382 (1995). White, C.M., B.R. Strazisar,E.J. Granite, J.S.Hoffman, H.W. Pennline, Separation Captureof CO2from Large StationarySources Sequestration and and in GeologicFormations -Coalbeds and DeepSalineAquifers,.J: oftheAir & Waste Management Association, 645-715(2003). 53, Zappelli, P., E. Gambarotta,V. Meda, A. Tortorella,CO2separation from flue gas: Evaluationof a solid sorbent based process, Proceedingsofthe 2nd Annual Conference Carbon Sequestration, on Exchange Monitor (2003). Zeman,F.S., An investigation into the feasibility of capturingcarbondioxide directly from the atmosphere, Proceedingsof the 2ndAnnual Conference on Carbon Sequestration, ExchangeMonitor (2003). Zsako,J., M. Hints, Use of thermalanalysisin the studyof sodiumcarbonate
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causticization by means of dolomitic lime, Journal of Thermal Analysis, 53, 323331 (1998).
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