PresentedatNitrogen+Syngas2012,2023February2012,Athens,Greece
*Speaker
CO
2
RemovalfromSyngasUsingPiperazineActivated
MDEAandPotassiumDimethylGlycinate
[Link]*,[Link]&[Link]
OptimizedGasTreating,Inc.
12337JonesRd.,Suite432
Houston,TX77070
ABSTRACT
Althoughmethyldiethanolamine,MDEA,canbeactivatedbyanumberofamines,piperazineis
themostcommonlyusedpromoterinapplicationsinvolvingCO
2
removalfromsyngas,aswellasfrom
[Link],removingCO
2
usingMDEA
alonewouldbepreferred;however,thereactioninsolutionisextremelyslowandtheabsorption
[Link]
reactivewithCO
2
(abouttentimesfasterkineticsthanmonoethanolamine)whichgreatlyenhancesCO
2
[Link],solvent
regenerationenergyrequirementsarenotmuchhigherthanforMDEAalone.
Aspartofareviewofasolventchangeoutfromaminepromotedhotpotassiumcarbonateto
piperazineactiveMDEA,thispaperaddressestheeffectsofsuchparametersastotalsolventstrength,
piperazinetoMDEAratioandtreatingtemperatureandpressureonthetreatedgasCO
2
contentand
[Link]
activatedAlkazidDIK(potassiumsaltoftheaminoaciddimethylglycine,KDiMGly)asapotentialsolvent
forCO
2
removalapplications.AlkazidDIKisasolventusedsincethemid1930sforH
2
Sremovalin
[Link]
nonvolatileandmaybemoreoxidationresistantthantheconventionalamines.
INTRODUCTION
Intheearlydaysofammoniaproduction,monoethanolamine(MEA)wascommonlyusedfor
CO
2
[Link],hotpotassium
carbonate(theBenfield,orHotPotprocess)wasused,ofteninasplitflowconfigurationdescribedasa
twostageBenfieldLoHeatprocessforenergyconservation.Inthelast20years,averysubstantial
fractionoftheseplantshavebeenretrofittedusingBASFsaMDEAprocess.
NMethyldiethanolamine(MDEA)isatertiaryaminewhoseaminogroupisincapableofreacting
withCO
2
.However,itisalkalineandsoisanexcellentsinkforprotonsproducebyCO
2
hydrolysis.
Becauseitisnonreactive,aqueousMDEAbyitselfabsorbsCO
2
fartooslowlytobeaneffectivesolvent
[Link],
adiaminethatreactsextraordinarilyfastwithCO
2
,theresultingblendisanexcellentsolventfortreating
syngasandremovingCO
2
intheproductionofLNG.
Inthispaper,wefirstpresenttheresultsofaquantitativestudyofthepiperazinepromotionof
MDEA,specificallytheeffectsofpiperazinetoMDEAratio,totalaminestrength,andthetreating
temperatureonperformanceofatypicalammoniasyngasCO
2
[Link],
Wagneretal.(2009)proposedusingthealkalimetalsaltsofanumberoftertiaryaminoacids,
[Link]
resultsofourstudyincludetheutilityofoperatingathighertemperatureswithlowerratherthanhigher
totalamineconcentrations,andtheexistenceofoperatingboundariesthatcanleadtounstable
operationwhenapproachedtooclosely.
Followingadiscussionofaminoacidsandtheirmodeofoperation,wecriticallyanalyzethe
possibilityofusingthepotassiumsaltofthetertiaryaminoaciddimethylglycine,promotedwith
[Link]
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
-
[Link],CO
2
doesnotreactwithatertiaryamino
groupbecausethisgrouplacksthemobilehydrogennecessarytoexchangefortheCO
2
andform
[Link],theCO
2
merelyabsorbsintowaterandhydrolyzes:
C0
2
+ E
2
0 - E
+
+ EC0
3
-
[Link],
unlessonecandirectlycatalyzethehydrolysisreactionitself(ascanbedoneusingcarbonicanhydrase,
forexample),CO
2
absorptionratesarenotenhancedatallbyreactionandwillbenofasterthanthey
[Link],isnottoenhance
absorptionratesthroughchemicalreactionbutrathertoincreasedramaticallythecapacityofthe
[Link],however,isthattheCO
2
absorptionrateisalmostalwaystoo
slowforittobeusedalone,exceptforbulkCO
2
[Link]
effectivelyforthedeepCO
2
[Link]
2
reactionmustbe
promoted,andpiperazineisanexcellentpromoter.
[Link]
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
[Link],anactivatorisrequired,andpiperazinehasevolvedastheactivatorof
[Link],mostsolventvendorsofferaformofpiperazinepromotedMDEAunderavarietyof
brandandcodenames.
DEEPCO
2
REMOVALUSINGANMDEABASEDSOLVENT
Usinganamineprocesssimulatorthatisfoundeduponreal,massandheattransferratesallows
[Link],theProTreatsimulatorwas
[Link]
[Link]
[Link]
plantsperformancecharacteristicsandquantitativelyunderstandhownumerousplantoperating
[Link],wehaveusedProTreattoanswersuchquestions
as,Whatisthebestsolventconcentrationandformulationtouse?andHowdoesthetreating
temperatureaffectperformance?.Althoughnopublicdomainplantdataexist,orareavailabletous
ontheuseofDiMGlyasasolventforsyngaspurification,aratherlimitedamountoffundamentaldata
onvaporliquidequilibriumandphysicalpropertiesissufficienttodetermineagreatdealabouthowthis
[Link].
[Link]
[Link]
complexschemeforreturningpartofthecondensatefromtheregeneratoroverheadcondenserstoa
[Link]
complexthanneededtoillustratethemainpointsofthepapersoithasbeengreatlysimplifiedtothe
[Link],andwehaveeliminatedany
considerationofanaminerecoverysectionatoptheabsorber.Theplantwasdesignedtotreat208000
NCMHrawgasat26.4baraand37Ccontaining60.2mol%H
2
,20.9mol%N
2
,and17.9mol%CO
2
with
thebalancebeingtraceamountsofargon,methane,carbonmonoxide,[Link],
theabsorberwaspackedwith15.25m(50ft)of#[Link]
packed,andcontains10.4m(34ft)of#[Link]
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
[Link],piperazineissomewhat
[Link]
dependscriticallyonmaintainingtherightconcentrationsofthesolventingredients.
Figure4 EffectofPiperazineconcentrationinMDEA(Total
50wt%amine)onCO
2
LevelinTreatedSyngas
SolventTotalAmineStrength
Havingestablishedthatthisplantwilloperatequitecomfortablywith5wt%piperazineand45wt%
MDEA,wethenaskedthequestion,whateffectdoestotalaminestrengthhaveontheCO
2
contentof
thetreatedgas?[Link]
2
curve
arethecorrespondingCO
2
moleloadings(permoletotalamine)oftherichsolventfromtheabsorber.
Figure5 EffectofTotalAmineStrengthonCO
2
Levelin
TreatedSyngasandonSolventViscosity
Itmightbesurprisingthatthehighertheaminestrengththeworsethetreating.Using50wt%
totalamine(BaseCase),thesimulatedtreatedgashas208ppmvCO
2
andaverysatisfactoryrich
solutionloadingof0.423molesCO
2
[Link],45wt%amineallowsa75ppmv
CO
2
gastobeproducedand40wt%aminereducestheCO
2
toabout30ppmv.With30wt%aminethe
residualCO
2
[Link],onthenegativeside,therichsolutionloadingincreasesto
[Link],stainless
claddingintherightplaces,andtheuseofstainlessexchangerbundles,wouldovercomethisobjection.
Thereasonforimprovedtreatingwithlowersolventstrengthsisthelowersolventviscositythat
[Link]
2
absorptionisaprocesswhoserateiscontrolledby
masstransferresistanceintheliquid,orsolvent,phase,andthemoreviscousthatphaseis,thegreater
theresistance.AsFigure5shows,droppingamineconcentrationfrom50wt%to30wt%reduces
[Link]
2
tobeabsorbedfasterandallowsthe15
+
metresofpackingtoextractenoughextraCO
2
toreducethetreatedgasconcentrationfrom208ppmv
[Link],andany
[Link].
SolventTemperature
AsFigure6shows,settingthesolventtemperatureat50C,say,ratherthan26Clowerstheviscosityby
afactorofnearlythreeaswell,[Link]
resultsshowninthefigurearefora45wt%plus5wt%[Link]
2
content
dropsrapidlywithtemperaturebuteventuallyitlevelsout,[Link]
case,[Link],ofcourse,the
vaporpressureofCO
2
overthesolventgoesupaswell,andnear50Cthepointisreachedwhere
reducedsolubilitypreventsabsorptionofenoughCO
2
eventocomeclosetomeetinga<1000ppmv
CO
2
[Link]
2
levelsuddenlyrisesbecausethesolventscapacityhasbeenreducedto
alevelinsufficienttoabsorbenoughCO
2
.TheexcessCO
2
intheinletsimplypassesrightthroughthe
columnandCO
2
[Link],itwouldbeverydangeroustooperatetoo
closetothistemperaturebecauseitwouldbecomeimpossibletomaintaincontrolofoutletCO
2
levels.
Figure6 EffectofSolventTemperatureonCO
2
Levelin
TreatedSyngasandonSolventViscosity
AMINOACIDSALTBASEDSOLVENTPOTASSIUMDIMETHYLGYCINATE(KDiMGly)
Potassiumdimethylglycinateisthepotassiumsaltofdimethylglycine,andwasknownunderthe
BASFtradenameAlkazidDIK.Thisisatertiaryaminoacidsaltthatsince1935hadbeenusedquite
successfullyandextensively,mainlyinEurope,forselectivelyremovingH
2
Sfromsuchproblematic
[Link]
[Link],itsusediminished,
[Link],KDiMGlyhascertainpropertiessuchas
zerovaporpressureandpossiblyoxidationresistancethataremakingitmoreattractiveinpost
combustionCO
2
capture,andwhichmaymakeitausefulalternativetoMDEAforammoniasyngas.
Asthenameimplies,aminoaci n atoneendofthemoleculeanda
[Link] 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,[Link]
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.,[Link]
2
holdingcapacity,ifonlytheCO
2
could
[Link]
piperazine.
ModelStudiesoftheKDiMGlyPiperazineSolvent
Becausechemicalsareboughtandsoldbyweight,weareusedtothinkingaboutsolvent
[Link],chemistryworksonthe
[Link]
isnecessarytouseequalmolarconcentrationsofthemainconstituent,anditturnsoutthat54.25wt%
KDiMGlyisequivalentto50wt%[Link],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
[Link]
vaporizationlossesand,ofcourse,thecompletelynonvolatilenatureofKDiMGlyeliminatesthis
inventorylossmechanism.
EffectofTotalAmineStrength
LowertotalamineconcentrationissimulatedtohaveaneffectsimilartoMDEA,althoughtheviscosity
reductionisnotasgreat(afactoroftwoversusafactorofthreeforMDEA)andthereforetheimpactof
[Link]
besideeachsimulationdatapointaretherichsolutionCO
2
loadingvalues,whicharehigherthan
[Link]
loadingvaluetheCO
2
[Link],becauseofitshigherpH(e.g.,12.05for
54.25wt%KDiMGlyversus11.72for50wt%MDEA,bothat26.5C)KDiMGlyhashigheraffinityforCO
2
thanMDEAdoes.TheleansolutionloadingforpiperazineactivatedMDEAistypically0.003butfor
KDiMGlyundersimilarconditionsitis0.13;thequestioniswhetheradifferenceof0.13loadingunits
[Link]
bicarbonatethatisresponsibleforcorrosion,theanswerisprobablyyes,andsomestainlessmetallurgy
[Link],thereisanother
significantbenefittobegainedfromusingpiperazinepromotedKDiMGly.
Basis54.25wt%DiMGly
Basis50wt%MDEA
Figure7 EffectofPiperazineConcentrationonCO
2
LevelinTreatedSyngas
Figure8 EffectofTotalAmineStrengthonCO
2
LevelinTreatedSyngasandonViscosityofKDiMGly
EffectofTreatingTemperatureUsingKDiMGly
AsshowninFigure9,highersolventtemperatures(lowerviscositysolvent)leadtosignificant
improvementstotheresidualCO
2
[Link],
[Link],thereis
[Link]
increasingabsorptionrates(fromdiminishedsolventviscosity),versusincreasingequilibriumCO
2
vapor
pressure(reduceddrivingforceforabsorption)[Link]
anywherebetween35and85Cpermitverysatisfactorytreating;however,theabilitytouseahigh
temperaturesolventofferspotentialadvantages.
Figure9 EffectofSolventTemperatureonCO
2
LevelinTreatedSyngasandonKDiMGlyViscosity
AdvantagestoTreatingwithHotSolvent
Figure10showshowleanaminetemperatureaffectsthetemperatureoftherichsolvent
[Link],foraleanaminetemperatureof85C,
[Link]
[Link]
fromtheplant,andthiswouldbepossibleevenwithaleansolventtemperatureof60Cwherethebest
CO
2
[Link]
Figure10 EffectofLeanSolventTemperatureonRichAmineTemperature
[Link],theprocessflowsheetisevensimpler
thanforconventionalaminetreating.
PiperazinepromotedKDiMGlyappearstobeaviableoptionforCO
2
removalfromammonia
[Link](whichmayalreadyexistinapiperazine
promotedMDEAplant)exceedsthebenefitsofloweraminelosses,smallerheatexchangers,andthe
eliminationoftheusuallyquitelargecrossexchanger.
SUMMARY
Usingminimalnewdata(somevaporliquidequilibriumandpHdatafordeterminingamine
dissociationconstantstogetherwithestimatedsolutionproperties),arealmassandheattransferrate
[Link]
extraordinaryversatileandcapableofaccuratelypredictingtheperformanceofproposedunits,without
pilotplantingorthegatheringoffielddata,i.e.,[Link]
[Link]
rapidlymovingawayfromthetriedandtrue,butantiquated,equilibriumstageapproach,withitsneed
forengineerguessedefficienciesandtransferunitheights.
ThiscontributionhasshowthatwithpiperazineactivatedMDEA:
Onemustbecarefultomonitorsolutioncompositionandcontrolthepiperazinelevel
becauseperformanceisquitesensitivetothisparameter,
Themaximofalwaysusing50wt%totalaminesolventisfalse,andsignificant
[Link]
50wt%ruleshouldbeexaminedineachandeverycase,
Whentreatinggoalsarenotbeingmet,usingacolderaminemaybeastepinthewrong
direction.
SolutionviscosityhasaprofoundeffectonCO
2
removalratesandwhatevercanbedoneto
loweritsvalue,consistentwithotheroperatingconstraints,willbebeneficial.
WithKDiMGlythereispotentialto:
Reduceheatexchangersurfaceareas.
Eliminatethecrossexchangeraltogether.
Lowerpotentialaminevaporizationlosses.
Perhapsuseamorerobustamineasthebaseforthesolvent.
Butwhenallissaidanddone,therealkeytounderstandingandimprovingplantperformanceisthe
availabilityanduseofarealmasstransferratebasedsimulator.
REFERENCES
Wagner,R.,[Link],RemovalofCarbonDioxidefromCombustionExhaustGases,
PatentApplicationUS2009/0320682A1,31December2009.
