PresentedatNitrogen+Syngas2012,2023February2012,Athens,Greece

*Speaker

CO
2
RemovalfromSyngasUsingPiperazineActivated
MDEAandPotassiumDimethylGlycinate

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

ABSTRACT

Althoughmethyldiethanolamine,MDEA,canbeactivatedbyanumberofamines,piperazineis
themostcommonlyusedpromoterinapplicationsinvolvingCO
2
removalfromsyngas,aswellasfrom
naturalgasinLNGproduction.Becauseofitsverylowregenerationenergy,removingCO
2
usingMDEA
alonewouldbepreferred;however,thereactioninsolutionisextremelyslowandtheabsorption
processiscontrolledentirelybyresistancetomasstransferinthesolventphase.Piperazineishighly
reactivewithCO
2
(abouttentimesfasterkineticsthanmonoethanolamine)whichgreatlyenhancesCO
2

absorptionrates.Yetbecauseonlyrelativelysmallconcentrationsofpiperazineareneeded,solvent
regenerationenergyrequirementsarenotmuchhigherthanforMDEAalone.

Aspartofareviewofasolventchangeoutfromaminepromotedhotpotassiumcarbonateto
piperazineactiveMDEA,thispaperaddressestheeffectsofsuchparametersastotalsolventstrength,
piperazinetoMDEAratioandtreatingtemperatureandpressureonthetreatedgasCO
2
contentand
thenecessaryregenerationenergy.ItalsocomparespiperazineactivatedMDEAwithpiperazine
activatedAlkazidDIK(potassiumsaltoftheaminoaciddimethylglycine,KDiMGly)asapotentialsolvent
forCO
2
removalapplications.AlkazidDIKisasolventusedsincethemid1930sforH
2
Sremovalin
refineryandcoalgasapplicationsbutitfelloutoffavourwiththeadventofMDEA.Itiscompletely
nonvolatileandmaybemoreoxidationresistantthantheconventionalamines.

INTRODUCTION
Intheearlydaysofammoniaproduction,monoethanolamine(MEA)wascommonlyusedfor
CO
2
removalfromthesynthesisgasusingtheGirbotolprocess.Somewhatlater,hotpotassium
carbonate(theBenfield,orHotPotprocess)wasused,ofteninasplitflowconfigurationdescribedasa
twostageBenfieldLoHeatprocessforenergyconservation.Inthelast20years,averysubstantial
fractionoftheseplantshavebeenretrofittedusingBASFsaMDEAprocess.
NMethyldiethanolamine(MDEA)isatertiaryaminewhoseaminogroupisincapableofreacting
withCO
2
.However,itisalkalineandsoisanexcellentsinkforprotonsproducebyCO
2
hydrolysis.
Becauseitisnonreactive,aqueousMDEAbyitselfabsorbsCO
2
fartooslowlytobeaneffectivesolvent
fortreatingammoniasynthesisgas.Butwhenspikedwitharelativelysmallconcentrationofpiperazine,
adiaminethatreactsextraordinarilyfastwithCO
2
,theresultingblendisanexcellentsolventfortreating
syngasandremovingCO
2
intheproductionofLNG.
Inthispaper,wefirstpresenttheresultsofaquantitativestudyofthepiperazinepromotionof
MDEA,specificallytheeffectsofpiperazinetoMDEAratio,totalaminestrength,andthetreating
temperatureonperformanceofatypicalammoniasyngasCO
2
removalsystem.Inarecentpatent,
Wagneretal.(2009)proposedusingthealkalimetalsaltsofanumberoftertiaryaminoacids,
appropriatelypromotedwithreactiveaminessuchasMEA.Someofthepotentiallymoreinteresting
resultsofourstudyincludetheutilityofoperatingathighertemperatureswithlowerratherthanhigher
totalamineconcentrations,andtheexistenceofoperatingboundariesthatcanleadtounstable
operationwhenapproachedtooclosely.
Followingadiscussionofaminoacidsandtheirmodeofoperation,wecriticallyanalyzethe
possibilityofusingthepotassiumsaltofthetertiaryaminoaciddimethylglycine,promotedwith
piperazineasasyngastreatingsolvent.Theresultsshowthatitispossibletotreatsyngasquite
effectivelyusingsuchasolventbutwithmuchlowerconcentrationofthepiperazinepromoter.
Furthermore,resultssuggestthatthecrossexchangercommonlyusedasaheatintegrationtoolin
treatingplantscanbecompletelyeliminated.

USINGTERTIARYAMINESFORCO
2
REMOVAL
Beforelookingatspecificchemicalsolvents,itisbeneficialtodescribethefunctionofanamine
thatiscompletelynonreactivetowardsCO
2
,intheCO
2
absorptionprocess,andtogiveaquantitative
pictureofhoweffectivepiperaziner i s, aminesdissociateinwaterand
producehydroxylion:
eallyis.L ke all amine tertiary
RN + E
2
0 - RNE
+
+ 0E
-

Thehydroxylioniswhatgivesaminestheiralkalinity.However,CO
2
doesnotreactwithatertiaryamino
groupbecausethisgrouplacksthemobilehydrogennecessarytoexchangefortheCO
2
andform
carbamate.Instead,theCO
2
merelyabsorbsintowaterandhydrolyzes:

C0
2
+ E
2
0 - E
+
+ EC0
3
-

Theliberatedprotonisneutralizedbytheaminesalkalinityasrepresentedbythehydroxylgroup.Thus,
unlessonecandirectlycatalyzethehydrolysisreactionitself(ascanbedoneusingcarbonicanhydrase,
forexample),CO
2
absorptionratesarenotenhancedatallbyreactionandwillbenofasterthanthey
wouldbeintoessentiallypurewater.Thefunctionofthetertiaryaminethen,isnottoenhance
absorptionratesthroughchemicalreactionbutrathertoincreasedramaticallythecapacityofthe
solvent.ThetroublewithstraightMDEA,however,isthattheCO
2
absorptionrateisalmostalwaystoo
slowforittobeusedalone,exceptforbulkCO
2
removalathighpressure.Itsimplycannotbeused
effectivelyforthedeepCO
2
removalrequiredforsyngasandLNGproduction.TheCO
2
reactionmustbe
promoted,andpiperazineisanexcellentpromoter.
PiperazineisacyclicdiaminewiththestructureshowninFigure1.ItreactswithCO
2
aboutten

Figure1 Piperazine

timesfasterthanMEA.Itssecondorderrateconstantat25C,forexample,isabout59,000Lmol
1
s
1

versusMEAat6,000Lmol
1
s
1
.ThismakespiperazinethemostreactivepromoterofCO
2
kinetics
availablecommercially.Overthelast30years,theaMDEAprocess,firstpatentedbyBASFin1982,has
capturedthelionsshareoftheammoniasyngaspurificationmarket,anditisstillusedinthemajorityof
theworldsammoniaplants.
Insummarythen,althoughMDEAalonecanbeusedforbulkCO
2
removalathighpressure,its
reactionratewithCO
2
ismuchtooslowforittobeusefullyappliedtodeeperCO
2
removalincolumnsof
reasonableheight.Forthat,anactivatorisrequired,andpiperazinehasevolvedastheactivatorof
choice.Today,mostsolventvendorsofferaformofpiperazinepromotedMDEAunderavarietyof
brandandcodenames.

DEEPCO
2
REMOVALUSINGANMDEABASEDSOLVENT
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%H
2
,20.9mol%N
2
,and17.9mol%CO
2
with
thebalancebeingtraceamountsofargon,methane,carbonmonoxide,andwatervapor.Forthisstudy,
theabsorberwaspackedwith15.25m(50ft)of#50IMTPtowerpacking.Theregeneratorwasalso
packed,andcontains10.4m(34ft)of#3CascadeMinirings.Althoughthisabsorberhadalittledeeper
packedbedthanfoundinmanysyngasCO
2
plants,theconclusionsofthepaperareinnowayaffected.
Figure2 OriginalAmineTreatingUnitforAmmoniaSyngas

Figure3 SimplifiedSyngasTreatingPFD

MDEAPiperazineComposition
ThemostcommonlyusedtotalaminestrengthforgenericMDEAandMDEAbasedblendsis50
wt%although,asweshallsee,thisissometimesnotthebestconcentrationtouse.Figure4showshow
therelativeconcentrationsofpiperazineandMDEAina50wt%totalamineblendaffecttheCO
2
leftin
thetreatedgas.Itisapparentfromthefigurethatabout4wt%piperazineisneededtoachieve<1000
ppmvCO
2
andthat5or6wt%piperazineallowsonetoachieveinthevicinityof100ppmvCO
2
.The
treatingperformanceisverysensitivetotheconcentrationthepiperazineadditiveandthisiswhyitisso
importanttomonitorsolutionstrengthforpiperazinecontent.Unfortunately,piperazineissomewhat
volatilesoitsconcentrationtendstofallwithtimemorerapidlythandoesMDEA.Plantperformance
dependscriticallyonmaintainingtherightconcentrationsofthesolventingredients.

Figure4 EffectofPiperazineconcentrationinMDEA(Total
50wt%amine)onCO
2
LevelinTreatedSyngas

SolventTotalAmineStrength
Havingestablishedthatthisplantwilloperatequitecomfortablywith5wt%piperazineand45wt%
MDEA,wethenaskedthequestion,whateffectdoestotalaminestrengthhaveontheCO
2
contentof
thetreatedgas?Figure5summarizesthefindings.ThenumbersnexttopointsontheppmvCO
2
curve
arethecorrespondingCO
2
moleloadings(permoletotalamine)oftherichsolventfromtheabsorber.

Figure5 EffectofTotalAmineStrengthonCO
2
Levelin
TreatedSyngasandonSolventViscosity

Itmightbesurprisingthatthehighertheaminestrengththeworsethetreating.Using50wt%
totalamine(BaseCase),thesimulatedtreatedgashas208ppmvCO
2
andaverysatisfactoryrich
solutionloadingof0.423molesCO
2
permoleoftotalamine.However,45wt%amineallowsa75ppmv
CO
2
gastobeproducedand40wt%aminereducestheCO
2
toabout30ppmv.With30wt%aminethe
residualCO
2
isevenlower.However,onthenegativeside,therichsolutionloadingincreasesto
unacceptablyhighlevelsfromacarbonsteelmetallurgycorrosionstandpoint.Ofcourse,stainless
claddingintherightplaces,andtheuseofstainlessexchangerbundles,wouldovercomethisobjection.
Thereasonforimprovedtreatingwithlowersolventstrengthsisthelowersolventviscositythat
accompaniesreducedamineconcentration.CO
2
absorptionisaprocesswhoserateiscontrolledby
masstransferresistanceintheliquid,orsolvent,phase,andthemoreviscousthatphaseis,thegreater
theresistance.AsFigure5shows,droppingamineconcentrationfrom50wt%to30wt%reduces
solventviscositybyafactorofnearlythree.ThisallowsCO
2
tobeabsorbedfasterandallowsthe15
+

metresofpackingtoextractenoughextraCO
2
toreducethetreatedgasconcentrationfrom208ppmv
tojustalittleover7ppmv.Solventviscosityisanimportantfactorinabsorberperformance,andany
successfulefforttoloweritwillpaydividends.Anotherwaytolowerviscosityistouseahottersolvent.
SolventTemperature
AsFigure6shows,settingthesolventtemperatureat50C,say,ratherthan26Clowerstheviscosityby
afactorofnearlythreeaswell,andtreatingimprovesdramaticallyovertheBaseCase.Thesimulated
resultsshowninthefigurearefora45wt%plus5wt%piperazinesolution.TreatedgasCO
2
content
dropsrapidlywithtemperaturebuteventuallyitlevelsout,thenexperiencesaprecipitousrise.Inthis
case,atemperatureofjustover50Cpresentsanoperationalcliff.Astemperaturerises,ofcourse,the
vaporpressureofCO
2
overthesolventgoesupaswell,andnear50Cthepointisreachedwhere
reducedsolubilitypreventsabsorptionofenoughCO
2
eventocomeclosetomeetinga<1000ppmv
CO
2
specification.TheppmCO
2
levelsuddenlyrisesbecausethesolventscapacityhasbeenreducedto
alevelinsufficienttoabsorbenoughCO
2
.TheexcessCO
2
intheinletsimplypassesrightthroughthe
columnandCO
2
breakthroughisexperienced.Operationally,itwouldbeverydangeroustooperatetoo
closetothistemperaturebecauseitwouldbecomeimpossibletomaintaincontrolofoutletCO
2
levels.

Figure6 EffectofSolventTemperatureonCO
2
Levelin
TreatedSyngasandonSolventViscosity
AMINOACIDSALTBASEDSOLVENTPOTASSIUMDIMETHYLGYCINATE(KDiMGly)
Potassiumdimethylglycinateisthepotassiumsaltofdimethylglycine,andwasknownunderthe
BASFtradenameAlkazidDIK.Thisisatertiaryaminoacidsaltthatsince1935hadbeenusedquite
successfullyandextensively,mainlyinEurope,forselectivelyremovingH
2
Sfromsuchproblematic
streamsasrefineryandcokeovengases.Thesegasestendtobeheavilycontaminatedwithvarious
componentsknowntobehardonconventionalamines.WiththeadventofMDEA,itsusediminished,
andeventuallyitstoppedbeingofferedcommercially.However,KDiMGlyhascertainpropertiessuchas
zerovaporpressureandpossiblyoxidationresistancethataremakingitmoreattractiveinpost
combustionCO
2
capture,andwhichmaymakeitausefulalternativetoMDEAforammoniasyngas.
Asthenameimplies,aminoaci n atoneendofthemoleculeanda
carboxylicacidgroupattheother.In lycineexistsasasocalledzwitterion:
dscontaina aminogroup
aqueous solution,dimethylg
C00 - CE
2
- N(CE
3
)
2
E

+

-

Because the amino group is protonated, it is completely nonreactive towards CO
2
and it is pH neutral
which, from the standpoint of life on earth, is probably a good thing. But as a solvent for CO
2
it is
virtually useless, having neither reactivity nor absorption capacity. However, when the acid group is
titrated(neut d with amino ralize ) KOHthe groupdeprotonates,
K0E + C00 - C
-
E
2
-N(CE
3
)
2
E

+
- K
+
0
-
0C -CE
2
- N(CE
3
)
2

+ E
2
0
andproduceswhatisnowanalkaline,tertiaryamine.AnimportantpropertyisthatKDiMGlyandall
otheraminoacidsaltsexistinwaterasfullydissociatedsalts,makingthemcompletelynonvolatile.
Furthermore,aminoacidsarealreadypartiallyoxidizedwhichmaygivethembetterresistanttofurther
oxidation.
InthecaseofKDiMGly,thetwoadditionalmethylgroupsareattachedtonitrogenattheamino
endofthemolecule,deprivingtheaminogroupoftheprotonnecessaryforreactionwithCO
2
.The
aminogroupistertiary;however,is thesamewasasMDEAand,in
solution,dissociatesaccordingto
itnonethelesshighlyalkalinein
RN + E
2
0 - RNE
+
+ 0E
-

JustasforMDEA,tertiaryaminesdonotreactwithCO
2
(nocarbamateorotherreactionproductswith
theamineareformed)sotheCO
2
absorptionratewillbenearlyidenticalwithwhatitwouldbeinwater,
i.e.,extremelyslow.ButthealkalinitygivesthesolventhighCO
2
holdingcapacity,ifonlytheCO
2
could
getintosolutioninthefirstplace.Thisisdonebypromotingthesolventwithveryfastreacting
piperazine.
ModelStudiesoftheKDiMGlyPiperazineSolvent
Becausechemicalsareboughtandsoldbyweight,weareusedtothinkingaboutsolvent
strengthintermsoftheweightpercentoftheactiveingredients.However,chemistryworksonthe
basisofmoles.TodoasnearlyaonetoonecomparisonwithpiperazinepromotedMDEAaspossibleit
isnecessarytouseequalmolarconcentrationsofthemainconstituent,anditturnsoutthat54.25wt%
KDiMGlyisequivalentto50wt%MDEA.Therefore,thiswasthebaseconcentrationusedintheamino
acidstudy.
KDiMGlyPiperazineComposition
Figure7showsthatevenwithoutthepiperazineadditive,KDiMGlyremovesmoreCO
2
(6.96
mol%CO
2
inthetreatedgas)thantheMDEAmolarequivalent(9.068mol%CO
2
).Thissuggestshigher
drivingforceforabsorption(lowvaporpressureofCO
2
)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
besideeachsimulationdatapointaretherichsolutionCO
2
loadingvalues,whicharehigherthan
correspondingrichloadingsforMDEA.KDiMGlyishardertostripthanMDEAbecauseforthesame
loadingvaluetheCO
2
vaporpressureislower.Inotherwords,becauseofitshigherpH(e.g.,12.05for
54.25wt%KDiMGlyversus11.72for50wt%MDEA,bothat26.5C)KDiMGlyhashigheraffinityforCO
2

thanMDEAdoes.TheleansolutionloadingforpiperazineactivatedMDEAistypically0.003butfor
KDiMGlyundersimilarconditionsitis0.13;thequestioniswhetheradifferenceof0.13loadingunits
makesaKDiMGlysolutionmorecorrosivethanMDEAunderthesameconditions.Becauseitis
bicarbonatethatisresponsibleforcorrosion,theanswerisprobablyyes,andsomestainlessmetallurgy
invulnerablesectionsofprocessequipmentandpipingwouldbeprudent.However,thereisanother
significantbenefittobegainedfromusingpiperazinepromotedKDiMGly.

Basis54.25wt%DiMGly

Basis50wt%MDEA
Figure7 EffectofPiperazineConcentrationonCO
2
LevelinTreatedSyngas

Figure8 EffectofTotalAmineStrengthonCO
2
LevelinTreatedSyngasandonViscosityofKDiMGly
EffectofTreatingTemperatureUsingKDiMGly
AsshowninFigure9,highersolventtemperatures(lowerviscositysolvent)leadtosignificant
improvementstotheresidualCO
2
concentrationinthetreatedgas.UnliketheMDEAbasedsolvent,
thereisnoprecipitouslossofperformancewhenthetemperaturereacheshighvalues.Instead,thereis
abroadminimuminthetreatingperformancecurve.Thisresultsfromthecompetingeffectsof
increasingabsorptionrates(fromdiminishedsolventviscosity),versusincreasingequilibriumCO
2
vapor
pressure(reduceddrivingforceforabsorption)withhighertemperatures.Solventtemperatures
anywherebetween35and85Cpermitverysatisfactorytreating;however,theabilitytouseahigh
temperaturesolventofferspotentialadvantages.

Figure9 EffectofSolventTemperatureonCO
2
LevelinTreatedSyngasandonKDiMGlyViscosity
AdvantagestoTreatingwithHotSolvent
Figure10showshowleanaminetemperatureaffectsthetemperatureoftherichsolvent
leavingtheabsorber.Hereonecanseethatinthepresentcase,foraleanaminetemperatureof85C,
therichaminewillbeatnearly105C.Thismeansthattherichsolventrequiresnopreheatingtoensure
itentersthestripperatareasonabletemperature.Thecrossexchangercanbecompletelyeliminated
fromtheplant,andthiswouldbepossibleevenwithaleansolventtemperatureof60Cwherethebest
CO
2
removalisachieved.TheabilitytorunhothasacertainparallelwiththeHotPotprocessbutdoes

Figure10 EffectofLeanSolventTemperatureonRichAmineTemperature
notneedasemileanprocessflowsheetconfiguration.Instead,theprocessflowsheetisevensimpler
thanforconventionalaminetreating.
PiperazinepromotedKDiMGlyappearstobeaviableoptionforCO
2
removalfromammonia
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.
SolutionviscosityhasaprofoundeffectonCO
2
removalratesandwhatevercanbedoneto
loweritsvalue,consistentwithotheroperatingconstraints,willbebeneficial.
WithKDiMGlythereispotentialto:
Reduceheatexchangersurfaceareas.
Eliminatethecrossexchangeraltogether.
Lowerpotentialaminevaporizationlosses.
Perhapsuseamorerobustamineasthebaseforthesolvent.
Butwhenallissaidanddone,therealkeytounderstandingandimprovingplantperformanceisthe
availabilityanduseofarealmasstransferratebasedsimulator.

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