CO2RemovalfromSyngasUsingPiperazineActivated

MDEAandPotassiumDimethylGlycinate


R.ScottAlvis*,NathanA.Hatcher&RalphH.Weiland
OptimizedGasTreating,Inc.
12337JonesRd.,Suite432
Houston,TX77070

ABSTRACT

Althoughmethyldiethanolamine,MDEA,canbeactivatedbyanumberofamines,piperazineis
themostcommonlyusedpromoterinapplicationsinvolvingCO2removalfromsyngas,aswellasfrom
naturalgasinLNGproduction.Becauseofitsverylowregenerationenergy,removingCO2usingMDEA
alonewouldbepreferred;however,thereactioninsolutionisextremelyslowandtheabsorption
processiscontrolledentirelybyresistancetomasstransferinthesolventphase.Piperazineishighly
reactivewithCO2(abouttentimesfasterkineticsthanmonoethanolamine)whichgreatlyenhancesCO2
absorptionrates.Yetbecauseonlyrelativelysmallconcentrationsofpiperazineareneeded,solvent
regenerationenergyrequirementsarenotmuchhigherthanforMDEAalone.

Aspartofareviewofasolventchangeoutfromaminepromotedhotpotassiumcarbonateto
piperazineactiveMDEA,thispaperaddressestheeffectsofsuchparametersastotalsolventstrength,
piperazinetoMDEAratioandtreatingtemperatureandpressureonthetreatedgasCO2contentand
thenecessaryregenerationenergy.ItalsocomparespiperazineactivatedMDEAwithpiperazine
activatedAlkazidDIK(potassiumsaltoftheaminoaciddimethylglycine,KDiMGly)asapotentialsolvent
forCO2removalapplications.AlkazidDIKisasolventusedsincethemid1930sforH2Sremovalin
refineryandcoalgasapplicationsbutitfelloutoffavourwiththeadventofMDEA.Itiscompletely
nonvolatileandmaybemoreoxidationresistantthantheconventionalamines.

PresentedatNitrogen+Syngas2012,2023February2012,Athens,Greece
*Speaker

INTRODUCTION
Intheearlydaysofammoniaproduction,monoethanolamine(MEA)wascommonlyusedfor
CO2removalfromthesynthesisgasusingtheGirbotolprocess.Somewhatlater,hotpotassium
carbonate(theBenfield,orHotPotprocess)wasused,ofteninasplitflowconfigurationdescribedasa
twostageBenfieldLoHeatprocessforenergyconservation.Inthelast20years,averysubstantial
fractionoftheseplantshavebeenretrofittedusingBASFsaMDEAprocess.
NMethyldiethanolamine(MDEA)isatertiaryaminewhoseaminogroupisincapableofreacting
withCO2.However,itisalkalineandsoisanexcellentsinkforprotonsproducebyCO2hydrolysis.
Becauseitisnonreactive,aqueousMDEAbyitselfabsorbsCO2fartooslowlytobeaneffectivesolvent
fortreatingammoniasynthesisgas.Butwhenspikedwitharelativelysmallconcentrationofpiperazine,
adiaminethatreactsextraordinarilyfastwithCO2,theresultingblendisanexcellentsolventfortreating
syngasandremovingCO2intheproductionofLNG.
Inthispaper,wefirstpresenttheresultsofaquantitativestudyofthepiperazinepromotionof
MDEA,specificallytheeffectsofpiperazinetoMDEAratio,totalaminestrength,andthetreating
temperatureonperformanceofatypicalammoniasyngasCO2removalsystem.Inarecentpatent,
Wagneretal.(2009)proposedusingthealkalimetalsaltsofanumberoftertiaryaminoacids,
appropriatelypromotedwithreactiveaminessuchasMEA.Someofthepotentiallymoreinteresting
resultsofourstudyincludetheutilityofoperatingathighertemperatureswithlowerratherthanhigher
totalamineconcentrations,andtheexistenceofoperatingboundariesthatcanleadtounstable
operationwhenapproachedtooclosely.
Followingadiscussionofaminoacidsandtheirmodeofoperation,wecriticallyanalyzethe
possibilityofusingthepotassiumsaltofthetertiaryaminoaciddimethylglycine,promotedwith
piperazineasasyngastreatingsolvent.Theresultsshowthatitispossibletotreatsyngasquite
effectivelyusingsuchasolventbutwithmuchlowerconcentrationofthepiperazinepromoter.
Furthermore,resultssuggestthatthecrossexchangercommonlyusedasaheatintegrationtoolin
treatingplantscanbecompletelyeliminated.

USINGTERTIARYAMINESFORCO2REMOVAL
Beforelookingatspecificchemicalsolvents,itisbeneficialtodescribethefunctionofanamine
thatiscompletelynonreactivetowardsCO2,intheCO2absorptionprocess,andtogiveaquantitative
pictureofhoweffectivepiperazinereallyis.Likeallamines,tertiaryaminesdissociateinwaterand
producehydroxylion:

Thehydroxylioniswhatgivesaminestheiralkalinity.However,CO2doesnotreactwithatertiaryamino
groupbecausethisgrouplacksthemobilehydrogennecessarytoexchangefortheCO2andform
carbamate.Instead,theCO2merelyabsorbsintowaterandhydrolyzes:

Theliberatedprotonisneutralizedbytheaminesalkalinityasrepresentedbythehydroxylgroup.Thus,
unlessonecandirectlycatalyzethehydrolysisreactionitself(ascanbedoneusingcarbonicanhydrase,
forexample),CO2absorptionratesarenotenhancedatallbyreactionandwillbenofasterthanthey
wouldbeintoessentiallypurewater.Thefunctionofthetertiaryaminethen,isnottoenhance
absorptionratesthroughchemicalreactionbutrathertoincreasedramaticallythecapacityofthe
solvent.ThetroublewithstraightMDEA,however,isthattheCO2absorptionrateisalmostalwaystoo
slowforittobeusedalone,exceptforbulkCO2removalathighpressure.Itsimplycannotbeused
effectivelyforthedeepCO2removalrequiredforsyngasandLNGproduction.TheCO2reactionmustbe
promoted,andpiperazineisanexcellentpromoter.
PiperazineisacyclicdiaminewiththestructureshowninFigure1.ItreactswithCO2aboutten

Figure1 Piperazine

timesfasterthanMEA.Itssecondorderrateconstantat25C,forexample,isabout59,000Lmol1s1
versusMEAat6,000Lmol1s1.ThismakespiperazinethemostreactivepromoterofCO2kinetics
availablecommercially.Overthelast30years,theaMDEAprocess,firstpatentedbyBASFin1982,has
capturedthelionsshareoftheammoniasyngaspurificationmarket,anditisstillusedinthemajorityof
theworldsammoniaplants.
Insummarythen,althoughMDEAalonecanbeusedforbulkCO2removalathighpressure,its
reactionratewithCO2ismuchtooslowforittobeusefullyappliedtodeeperCO2removalincolumnsof
reasonableheight.Forthat,anactivatorisrequired,andpiperazinehasevolvedastheactivatorof
choice.Today,mostsolventvendorsofferaformofpiperazinepromotedMDEAunderavarietyof
brandandcodenames.

DEEPCO2REMOVALUSINGANMDEABASEDSOLVENT
Usinganamineprocesssimulatorthatisfoundeduponreal,massandheattransferratesallows
avirtualplanttobeconstructedonacomputer.Inthepresentwork,theProTreatsimulatorwas
used.ProTreatistheworldsonlytruemasstransferratebasedcommercialsimulatordedicatedtogas
treating.AvirtualplantbuiltusingProTreatallowsonetoexperimentwithawidevarietyofdifferent
processconfigurationsandwhatifscenarios.Itisrelativelyeasytolearnagreatdealaboutaparticular
plantsperformancecharacteristicsandquantitativelyunderstandhownumerousplantoperating
parametersaffectthatperformance.Inwhatfollows,wehaveusedProTreattoanswersuchquestions
as,Whatisthebestsolventconcentrationandformulationtouse?andHowdoesthetreating
temperatureaffectperformance?.Althoughnopublicdomainplantdataexist,orareavailabletous
ontheuseofDiMGlyasasolventforsyngaspurification,aratherlimitedamountoffundamentaldata
onvaporliquidequilibriumandphysicalpropertiesissufficienttodetermineagreatdealabouthowthis
chemicalwillperforminasyngastreatingsituation.Butthatisforthenextsectionofthepaper.
AProTreatPFDoftheaminesectionofatypicalammoniasyngasplantisshowninFigure2.It
hasasingleabsorberbutthereareidenticaltwinregeneratorsinparallel.Thereisalsoarather
complexschemeforreturningpartofthecondensatefromtheregeneratoroverheadcondenserstoa
shortwashsectionintheabsorberforrecoveringaminevapors.Theflowsheetisquiteabitmore
complexthanneededtoillustratethemainpointsofthepapersoithasbeengreatlysimplifiedtothe
PFDshowninFigure3.Thesimplifiedflowsheethasasingleregenerator,andwehaveeliminatedany
considerationofanaminerecoverysectionatoptheabsorber.Theplantwasdesignedtotreat208000
NCMHrawgasat26.4baraand37Ccontaining60.2mol%H2,20.9mol%N2,and17.9mol%CO2with
thebalancebeingtraceamountsofargon,methane,carbonmonoxide,andwatervapor.Forthisstudy,
theabsorberwaspackedwith15.25m(50ft)of#50IMTPtowerpacking.Theregeneratorwasalso
packed,andcontains10.4m(34ft)of#3CascadeMinirings.Althoughthisabsorberhadalittledeeper
packedbedthanfoundinmanysyngasCO2plants,theconclusionsofthepaperareinnowayaffected.

Figure2 OriginalAmineTreatingUnitforAmmoniaSyngas

Figure3 SimplifiedSyngasTreatingPFD

MDEAPiperazineComposition
ThemostcommonlyusedtotalaminestrengthforgenericMDEAandMDEAbasedblendsis50
wt%although,asweshallsee,thisissometimesnotthebestconcentrationtouse.Figure4showshow
therelativeconcentrationsofpiperazineandMDEAina50wt%totalamineblendaffecttheCO2leftin
thetreatedgas.Itisapparentfromthefigurethatabout4wt%piperazineisneededtoachieve<1000
ppmvCO2andthat5or6wt%piperazineallowsonetoachieveinthevicinityof100ppmvCO2.The
treatingperformanceisverysensitivetotheconcentrationthepiperazineadditiveandthisiswhyitisso
importanttomonitorsolutionstrengthforpiperazinecontent.Unfortunately,piperazineissomewhat
volatilesoitsconcentrationtendstofallwithtimemorerapidlythandoesMDEA.Plantperformance
dependscriticallyonmaintainingtherightconcentrationsofthesolventingredients.

Figure4 EffectofPiperazineconcentrationinMDEA(Total
50wt%amine)onCO2LevelinTreatedSyngas

SolventTotalAmineStrength
Havingestablishedthatthisplantwilloperatequitecomfortablywith5wt%piperazineand45wt%
MDEA,wethenaskedthequestion,whateffectdoestotalaminestrengthhaveontheCO2contentof
thetreatedgas?Figure5summarizesthefindings.ThenumbersnexttopointsontheppmvCO2curve
arethecorrespondingCO2moleloadings(permoletotalamine)oftherichsolventfromtheabsorber.

Figure5 EffectofTotalAmineStrengthonCO2Levelin
TreatedSyngasandonSolventViscosity

Itmightbesurprisingthatthehighertheaminestrengththeworsethetreating.Using50wt%
totalamine(BaseCase),thesimulatedtreatedgashas208ppmvCO2andaverysatisfactoryrich
solutionloadingof0.423molesCO2permoleoftotalamine.However,45wt%amineallowsa75ppmv
CO2gastobeproducedand40wt%aminereducestheCO2toabout30ppmv.With30wt%aminethe
residualCO2isevenlower.However,onthenegativeside,therichsolutionloadingincreasesto
unacceptablyhighlevelsfromacarbonsteelmetallurgycorrosionstandpoint.Ofcourse,stainless
claddingintherightplaces,andtheuseofstainlessexchangerbundles,wouldovercomethisobjection.
Thereasonforimprovedtreatingwithlowersolventstrengthsisthelowersolventviscositythat
accompaniesreducedamineconcentration.CO2absorptionisaprocesswhoserateiscontrolledby
masstransferresistanceintheliquid,orsolvent,phase,andthemoreviscousthatphaseis,thegreater
theresistance.AsFigure5shows,droppingamineconcentrationfrom50wt%to30wt%reduces
solventviscositybyafactorofnearlythree.ThisallowsCO2tobeabsorbedfasterandallowsthe15+
metresofpackingtoextractenoughextraCO2toreducethetreatedgasconcentrationfrom208ppmv
tojustalittleover7ppmv.Solventviscosityisanimportantfactorinabsorberperformance,andany
successfulefforttoloweritwillpaydividends.Anotherwaytolowerviscosityistouseahottersolvent.

SolventTemperature
AsFigure6shows,settingthesolventtemperatureat50C,say,ratherthan26Clowerstheviscosityby
afactorofnearlythreeaswell,andtreatingimprovesdramaticallyovertheBaseCase.Thesimulated
resultsshowninthefigurearefora45wt%plus5wt%piperazinesolution.TreatedgasCO2content
dropsrapidlywithtemperaturebuteventuallyitlevelsout,thenexperiencesaprecipitousrise.Inthis
case,atemperatureofjustover50Cpresentsanoperationalcliff.Astemperaturerises,ofcourse,the
vaporpressureofCO2overthesolventgoesupaswell,andnear50Cthepointisreachedwhere
reducedsolubilitypreventsabsorptionofenoughCO2eventocomeclosetomeetinga<1000ppmv
CO2specification.TheppmCO2levelsuddenlyrisesbecausethesolventscapacityhasbeenreducedto
alevelinsufficienttoabsorbenoughCO2.TheexcessCO2intheinletsimplypassesrightthroughthe
columnandCO2breakthroughisexperienced.Operationally,itwouldbeverydangeroustooperatetoo
closetothistemperaturebecauseitwouldbecomeimpossibletomaintaincontrolofoutletCO2levels.

Figure6 EffectofSolventTemperatureonCO2Levelin
TreatedSyngasandonSolventViscosity
AMINOACIDSALTBASEDSOLVENTPOTASSIUMDIMETHYLGYCINATE(KDiMGly)
Potassiumdimethylglycinateisthepotassiumsaltofdimethylglycine,andwasknownunderthe
BASFtradenameAlkazidDIK.Thisisatertiaryaminoacidsaltthatsince1935hadbeenusedquite
successfullyandextensively,mainlyinEurope,forselectivelyremovingH2Sfromsuchproblematic
streamsasrefineryandcokeovengases.Thesegasestendtobeheavilycontaminatedwithvarious
componentsknowntobehardonconventionalamines.WiththeadventofMDEA,itsusediminished,
andeventuallyitstoppedbeingofferedcommercially.However,KDiMGlyhascertainpropertiessuchas
zerovaporpressureandpossiblyoxidationresistancethataremakingitmoreattractiveinpost
combustionCO2capture,andwhichmaymakeitausefulalternativetoMDEAforammoniasyngas.
Asthenameimplies,aminoacidscontainanaminogroupatoneendofthemoleculeanda
carboxylicacidgroupattheother.Inaqueoussolution,dimethylglycineexistsasasocalledzwitterion:

Becausethe aminogroupisprotonated,itiscompletely nonreactivetowardsCO2anditispHneutral
which, from the standpoint of life on earth, is probably a good thing. But as a solvent for CO2 it is
virtually useless, having neither reactivity nor absorption capacity. However, when the acid group is
titrated(neutralized)withKOHtheaminogroupdeprotonates,

andproduceswhatisnowanalkaline,tertiaryamine.AnimportantpropertyisthatKDiMGlyandall
otheraminoacidsaltsexistinwaterasfullydissociatedsalts,makingthemcompletelynonvolatile.
Furthermore,aminoacidsarealreadypartiallyoxidizedwhichmaygivethembetterresistanttofurther
oxidation.
InthecaseofKDiMGly,thetwoadditionalmethylgroupsareattachedtonitrogenattheamino
endofthemolecule,deprivingtheaminogroupoftheprotonnecessaryforreactionwithCO2.The
aminogroupistertiary;however,isitnonethelesshighlyalkalineinthesamewasasMDEAand,in
solution,dissociatesaccordingto

JustasforMDEA,tertiaryaminesdonotreactwithCO2(nocarbamateorotherreactionproductswith
theamineareformed)sotheCO2absorptionratewillbenearlyidenticalwithwhatitwouldbeinwater,
i.e.,extremelyslow.ButthealkalinitygivesthesolventhighCO2holdingcapacity,ifonlytheCO2could
getintosolutioninthefirstplace.Thisisdonebypromotingthesolventwithveryfastreacting
piperazine.
ModelStudiesoftheKDiMGlyPiperazineSolvent
Becausechemicalsareboughtandsoldbyweight,weareusedtothinkingaboutsolvent
strengthintermsoftheweightpercentoftheactiveingredients.However,chemistryworksonthe
basisofmoles.TodoasnearlyaonetoonecomparisonwithpiperazinepromotedMDEAaspossibleit
isnecessarytouseequalmolarconcentrationsofthemainconstituent,anditturnsoutthat54.25wt%
KDiMGlyisequivalentto50wt%MDEA.Therefore,thiswasthebaseconcentrationusedintheamino
acidstudy.
KDiMGlyPiperazineComposition
Figure7showsthatevenwithoutthepiperazineadditive,KDiMGlyremovesmoreCO2(6.96
mol%CO2inthetreatedgas)thantheMDEAmolarequivalent(9.068mol%CO2).Thissuggestshigher
drivingforceforabsorption(lowvaporpressureofCO2)whenKDiMGlyisusedinaplantoperating
underotherwiseidenticalconditionsofsolventrate,reboilerduty,equipmentdetails,andsoon.
Considerablylesspiperazine(2wt%versus4wt%)isneededtoachieve1000ppmvtreatedgas,andthe
responsetopiperazineadditionishigher.Lowerpiperazineconcentrationsmeanreducedpotential
vaporizationlossesand,ofcourse,thecompletelynonvolatilenatureofKDiMGlyeliminatesthis
inventorylossmechanism.

EffectofTotalAmineStrength
LowertotalamineconcentrationissimulatedtohaveaneffectsimilartoMDEA,althoughtheviscosity
reductionisnotasgreat(afactoroftwoversusafactorofthreeforMDEA)andthereforetheimpactof
lowertotalamineconcentrationisnotasgreat.Figure8showsthesimulationresults.Thenumbers
besideeachsimulationdatapointaretherichsolutionCO2loadingvalues,whicharehigherthan
correspondingrichloadingsforMDEA.KDiMGlyishardertostripthanMDEAbecauseforthesame
loadingvaluetheCO2vaporpressureislower.Inotherwords,becauseofitshigherpH(e.g.,12.05for
54.25wt%KDiMGlyversus11.72for50wt%MDEA,bothat26.5C)KDiMGlyhashigheraffinityforCO2
thanMDEAdoes.TheleansolutionloadingforpiperazineactivatedMDEAistypically0.003butfor
KDiMGlyundersimilarconditionsitis0.13;thequestioniswhetheradifferenceof0.13loadingunits
makesaKDiMGlysolutionmorecorrosivethanMDEAunderthesameconditions.Becauseitis
bicarbonatethatisresponsibleforcorrosion,theanswerisprobablyyes,andsomestainlessmetallurgy
invulnerablesectionsofprocessequipmentandpipingwouldbeprudent.However,thereisanother
significantbenefittobegainedfromusingpiperazinepromotedKDiMGly.

Basis54.25wt%DiMGly Basis50wt%MDEA

Figure7 EffectofPiperazineConcentrationonCO2LevelinTreatedSyngas

Figure8 EffectofTotalAmineStrengthonCO2LevelinTreatedSyngasandonViscosityofKDiMGly
EffectofTreatingTemperatureUsingKDiMGly
AsshowninFigure9,highersolventtemperatures(lowerviscositysolvent)leadtosignificant
improvementstotheresidualCO2concentrationinthetreatedgas.UnliketheMDEAbasedsolvent,
thereisnoprecipitouslossofperformancewhenthetemperaturereacheshighvalues.Instead,thereis
abroadminimuminthetreatingperformancecurve.Thisresultsfromthecompetingeffectsof
increasingabsorptionrates(fromdiminishedsolventviscosity),versusincreasingequilibriumCO2vapor
pressure(reduceddrivingforceforabsorption)withhighertemperatures.Solventtemperatures
anywherebetween35and85Cpermitverysatisfactorytreating;however,theabilitytouseahigh
temperaturesolventofferspotentialadvantages.

Figure9 EffectofSolventTemperatureonCO2LevelinTreatedSyngasandonKDiMGlyViscosity

AdvantagestoTreatingwithHotSolvent
Figure10showshowleanaminetemperatureaffectsthetemperatureoftherichsolvent
leavingtheabsorber.Hereonecanseethatinthepresentcase,foraleanaminetemperatureof85C,
therichaminewillbeatnearly105C.Thismeansthattherichsolventrequiresnopreheatingtoensure
itentersthestripperatareasonabletemperature.Thecrossexchangercanbecompletelyeliminated
fromtheplant,andthiswouldbepossibleevenwithaleansolventtemperatureof60Cwherethebest
CO2removalisachieved.TheabilitytorunhothasacertainparallelwiththeHotPotprocessbutdoes

Figure10 EffectofLeanSolventTemperatureonRichAmineTemperature
notneedasemileanprocessflowsheetconfiguration.Instead,theprocessflowsheetisevensimpler
thanforconventionalaminetreating.
PiperazinepromotedKDiMGlyappearstobeaviableoptionforCO2removalfromammonia
syngas.Itsaquestionofwhetherthecostofbettermetallurgy(whichmayalreadyexistinapiperazine
promotedMDEAplant)exceedsthebenefitsofloweraminelosses,smallerheatexchangers,andthe
eliminationoftheusuallyquitelargecrossexchanger.

SUMMARY
Usingminimalnewdata(somevaporliquidequilibriumandpHdatafordeterminingamine
dissociationconstantstogetherwithestimatedsolutionproperties),arealmassandheattransferrate
basedaminesimulatorallowstheconstructionofavirtualplantinsoftware.Thevirtualplantis
extraordinaryversatileandcapableofaccuratelypredictingtheperformanceofproposedunits,without
pilotplantingorthegatheringoffielddata,i.e.,veryinexpensively.Masstransferratebasedmodeling
hasbeenaroundsincethemid80sandisafairlymaturetechnology.Thegastreatingindustryisnow
rapidlymovingawayfromthetriedandtrue,butantiquated,equilibriumstageapproach,withitsneed
forengineerguessedefficienciesandtransferunitheights.
ThiscontributionhasshowthatwithpiperazineactivatedMDEA:
Onemustbecarefultomonitorsolutioncompositionandcontrolthepiperazinelevel
becauseperformanceisquitesensitivetothisparameter,
Themaximofalwaysusing50wt%totalaminesolventisfalse,andsignificant
improvementstotreatinglevelscanberealizedbyoperatingatlowerconcentrations.The
50wt%ruleshouldbeexaminedineachandeverycase,
Whentreatinggoalsarenotbeingmet,usingacolderaminemaybeastepinthewrong
direction.
SolutionviscosityhasaprofoundeffectonCO2removalratesandwhatevercanbedoneto
loweritsvalue,consistentwithotheroperatingconstraints,willbebeneficial.
WithKDiMGlythereispotentialto:
Reduceheatexchangersurfaceareas.
Eliminatethecrossexchangeraltogether.
Lowerpotentialaminevaporizationlosses.
Perhapsuseamorerobustamineasthebaseforthesolvent.
Butwhenallissaidanddone,therealkeytounderstandingandimprovingplantperformanceisthe
availabilityanduseofarealmasstransferratebasedsimulator.

REFERENCES
Wagner,R.,U.LichtfersandV.Schuda,RemovalofCarbonDioxidefromCombustionExhaustGases,
PatentApplicationUS2009/0320682A1,31December2009.