Glycol Dehydrators

Thestillcolumnventonglycoldehydratorscanbeanotablesourceoforganicemissions atsomesites;however,overall,itismoresignificantasapotentialsourceofodoriferous emissionsandtoxicorganicairpollutants. Thespecificcontroltechnologiesthatmaybeusedtoreduceoreliminateemissionsfrom thestillcolumnventinclude, Optimizationofkeyprocessvariables. Disposaloftheventedvapoursbythermaloxidation. Recoveryofthevapoursusingacondenserunit. Specificationofenhanced,lowemissionglycoldehydrationtechnology(i.e.,the DRIZOprocess). Specification of an alternate, more environmentally friendly dehydration technology(i.e.,membranedehydrationprocess).

Processoptimizationoffersthemostimmediateandcosteffectivemeansofreducingthe amountofemissions.Disposalofthevapoursbythermaloxidationisasimple,effective meansofcontrollingtheemissionsatamoderatecost.However,ithasthedisadvantage ofcreatingcombustionemissions. Recoveryofthevapours usingacondenserisan interestingsolutionthatmayactuallyhaveapositiveeconomicbenefittoit.Useofthe DRIZO process or possibly membrane dehydration technology may be worth consideringforuseatnewfacilities. AnadditionaladvantageofthevapourcondenserandDRIZOprocessesisthattheymay allowdehydrationofsomesourgasstreams. Source Characterization Glycoldehydrationisthemostcommonprocessforremovingwatervapourfrom naturalgas.Itisfrequentlyusedinthefieldtopreventhydratesingasgathering systems,andatgasprocessingplantstosatisfysalesspecifications. Process Description Glycoldehydrationisacontinuousliquiddesiccantprocessinwhichwaterorwater vapourisremovedfromhydrocarbonstreamsbyselectiveabsorptionandtheglycolis regeneratedorreconcentratedbythermaldesorption.Themostcommonapplicationof thisprocessisthedehydrationofnaturalgasstreams;however,variationsoftheprocess

are also used to dehydrate natural gas condensates at gas processing plants. The discussionsthatfollowaredirectedtowardsnaturalgasapplications.Nonetheless,the basicglycolregenerationprocessisthesameregardlessoftheapplicationsomanyofthe available emission reduction methods and technologies will apply to both types of applications. Theuseoftriethyleneglycol(TEG)isstandardfordehydrationofnaturalgas. Theabsorptionoccursinatrayedvesselcalledthecontactororabsorbercolumn.The leandryglycolliquorentersthetopofthecolumnandthewetgasentersthebottomof thecolumn.Astheleanglycolflowsdownthroughthetrays,itcontactstheupflowof thewetgas.Theleanglycolabsorbsthewaterfromthewetgasandexitsthroughthe bottom of the column as rich glycol. The gas exits the top of the column as a dry productwithanacceptableresidualmoisturecontentrangeof0.03to0.06g/m3 (2to 4lb/mmscf)ofgas. Alowpressure flashseparatorissometimesinstalledbetweenthecontactorandthe regeneratortoreleaseanysolutiongasthatmaybeentrainedintherich(wet)glycol, especiallyifaglycolenergyexchangepumpisusedinthesystem.Thistypeofpump usespressureenergyintherichglycoltopumpdryglycolintothecontactor.Thegas separatedintheflashseparatormaybeusedtosupplementthefuelandstrippinggas requiredforthereboiler. Anyexcessventgasisdischargedthroughabackpressure valvetoatmosphere. Fromtheflashseparator,therichglycolispassedthroughaheatexchangecoilinthe surgetanktopreheattherichglycol.Therichglycolthenflowstoapackedstripping stillattachedtothetopofareboiler.Inthestillcolumn,thewetglycolflowsdownto thereboilerwhilecontactinghotgases(mostlywatervapourandglycol)risingupfrom thereboiler. Themixingofthesetwostreamshelpstofurtherpreheatthewetglycol andtocondenseandrecoveranyglycolvapoursbeforethegasesareventedfromthe topofthestill. Inthereboilertheglycolisheatedtoapproximately175o to205oCtoremoveenough watervapourtoreconcentrateitto99.5percentormore.Sometimesasmallamountof naturalgasisinjectedintothebottomofthereboilertostripwatervapourfromthe glycol. Thewatervapourrisesthroughthestrippingstillandtheleanglycolflowsto thesurge tankwhereitiscooleddown bypreheatingtherichglycolfromtheflash separator.

Finally, the glycol is pumped back to the top of the absorber column to repeat this circuit.Therequiredcirculationrateisdeterminedbytheactualpurityoftheglycolat theinlettothecontactor,thenumberoftraysorpackingheightinthecontactor,andthe desireddewpointdepression(API,1990).Typicalvaluesforplantapplicationsare17to 50LTEG/kgH2Oremoved,andforfieldapplicationsare20to35LTEG/kgH2O.

Atmospheric Emissions Thetypeandamountofemissionsfromthestillcolumnventdependsontheactual process design, operating conditions, and the composition and flow rate of the raw naturalgas.Foratypicalunitequippedwithaflashseparator,thecompositionofthe vented vapours may be expected to vary (on a relative mass basis) as follows (Schievelbein,1992):50to90percentwater,5to50percentcondensablehydrocarbons, and small amounts of noncondensable hydrocarbons. The concentration of non condensable gas increases dramatically if a flash separator is not used. Toluene is usuallythemostconcentratedcondensablehydrocarboncomponent,butrarelydoesit exceed10percentbyweight.Dehydratorsinfieldapplicationsmightbevaporizing0.08 to0.8m3/d(0.5to5bbls/d)ofhydrocarbons. Theprimarycausesofhydrocarbonemissionsaresecondaryabsorption/desorptionby the TEG, entrainment of some gas from the contactor in the rich TEG, and use of strippinggasinthereboiler.However,secondaryabsorption/desorptionbytheglycol isperhapsthemostimportantsinglecause. The key secondary compounds that may be removed by the TEG are aromatic hydrocarbons (e.g., benzene, toluene, ethylbenzene, and xylenes [BTEX]), which are notabletoxicsubstances. TEGalsohasastrongaffinityforreducedsulphurspecies (e.g.,hydrogensulphide,mercaptansandcarbondisulphide),whicharealsotoxicand highlymalodorous. However,forthepurposesofthisdocument,attentionisfocused ontheBTEXandotherhydrocarbonemissions. Throughtheconcentratingeffectoftheabsorptionprocess,thepresenceofevensmall amountsofBTEXinthenaturalgascanresultinveryhighconcentrationsinthevented effluent.ThemolarconcentrationofBTEXattheoutletoftheventcaneasilybeseveral hundredtimeshigherthanintherawgas. TheamountofBTEXemitteddependslargelyonitsconcentrationintherawnaturalgas andontheglycolcirculationrate.BTEXdoesnotoccurinallrawnaturalgasstreams, butwhereitdoesoccur,itsconcentrationisusuallylessthanonepercentbyvolume (Thompsonetal.,1992).Theglycolcirculationrateisdeterminedbythegasflowrate

and the amount of water to be removed. At 6900 kPa, glycol can absorb up to7.5 standard litres of gas foreverylitre of glycol circulated(Sams, 1992). A gasdriven glycol pump adds additional gas during its pumping operation. Approximately 0.5 actuallitresofgas(i.e.,atprocessconditionsinthecontactor)isrequiredtopumpone litreofglycol.Strippinggasflowsarenormally7.5standardlitresperlitreofglycol. SincetheboilingpointsofBTEXrangefrom80oCto140oC,verylittleofthismaterialis releasedintheflashtank(Thompsonetal.,1992).MostoftheBTEXisseparatedfrom theglycolinthestill. Althoughmanyofthelighterhydrocarbons(e.g.,entrainedgas fromthecontactor)mayberemovedfromtheglycolintheflashtank,someremainin theglycolandareseparatedinthestill. The amount of BTEX emitted bya glycol dehydrator in a given application may be estimatedusingseveraldifferentcommerciallyavailableprocesssimulationpackages which have been specifically tuned for this type of problem (e.g., HYSIMTM by Hyprotech, PRO/IITM by Simulation Sciences, and PROSIMTM by Bryan Research & Engineering, Inc.). However, a somewhat less accurate, although much less costly, packagenamedGRIDEHYhasbeendevelopedforthissamepurposeandisavailable fromGasResearchInstitute(Thompsonetal.,1992).Ifthecompositionandflowrateof theinletgasandthedesignandoperatingconditionsofthedehydratorareknown,GRI DEHIisreportedlyabletocalculatebenzeneemissionstowithin20percentofactual values,andtoluene,ethylbenzene,andxylenesemissionstowithin20to50percent. Avarietyoftestmethodsarealsoavailableforestablishingaromaticemissionsfrom glycol dehydrators (Schievelbein, 1992; Grizzle, 1992; Rueter and Evans, 1992). The simplest and most cost effective approach of reasonable accuracy is perhaps the rich/leanglycolmassbalancemethod.Thismethodconsistsofanalyzingsamplesofthe richandleanglycolandthenperformingamassbalancebasedontheglycolcirculation rate.Theresultsareestimatedtobelowbyasmuchas20percentforBTEXandasmuch as40percentforVOCvalues(Schievelbein,1992).Themostaccuratemethodsaretotal capture condensation and partial stack condensation/flow measurement; however, these methods are also much more costly to perform. The limited data available (Grizzle,1992)indicatethatdirectsamplingandanalysisoftheventstreammayprovide goodVOCvaluesbutpoorBTEXresults. EmissionReductionMethodsandTechnologies Theamountofemissionsandtheconcentrationoftoxicandodoriferouscompoundsin thevapoursaremajorfactorsinchoosingthebestoptionforreducingventingemissions

fromthestillcolumnonglycoldehydrators. Maintenanceneedsinfieldapplications canalsobeimportant,particularlyforremotelocations. Some simple process modifications and optimization work may be done to help minimizetheamountofemissionsandlowerthecostofanyaddonoptions.Ifresulting totalhydrocarbonemissionsarelow,thenthesimplestandmostcosteffectivesolution maybetodisposeof the emissionsbythermal oxidation. Thismaybea minimum requirementifmalodourproblemsariseorifthereisarisktohumanhealthduetotoxic emissions. However,theuseofcondenserstorecoverthecondensablehydrocarbons may offer a very attractive payback in some cases. Moreover, the noncondensable hydrocarbonscanbeusedasfueltoimprovetheenergyefficiencyofthedehydration process. TheDRIZOprocessmaybeconsideredfornewapplicationsormaypossiblyberetrofit toexistingunits.Ithasthebenefitsofreducedemissionsandincreasedwaterremoval. Process Optimization Thereareseveralprocessoptionsthatmaybeimplementedandprocessvariablesthat may be optimized to help minimize the amount of venting emissions from the still column. These are itemized below and generally pertain to directly or indirectly minimizingtheglycolcirculationrateandtheheatingloadonthereboiler.Forremote fielddehydrators, itmaybeworthwhiletoinstall aSCADA systemtoallowcentral monitoringofsomeofthekeyvariables.

FlashTank:Ifappreciablequantitiesofnaturalgasareabsorbedorentrainedin theglycol,atwophaseflashseparatorshouldbeinstalleddownstreamofthe glycolglycol heat exchanger and glycol pump (especially if a glycol energy exchangepumpisused).Theseparatedgascanbeusedasfuelforthereboiler orasstrippinggas,orsenttoflarefordisposal. Ifsignificantamountsofhydrocarbonliquidsareencounteredatthispoint,the flash tank should be designed for threephase separation. Otherwise, the hydrocarbon liquids could cause problems in the reboiler (i.e., gradual coke accumulationonthefire tube[PearceandSivalls,1984])andleadtoreduced boilerefficiencyandincreasedcombustionemissions.

GlycolCirculationRate:Theamountofmoisturecontrolprovidedbyaglycol dehydrator is, for the most part, determined by the glycol circulation rate. However,sincethisratealsodeterminestheamountofventingemissions,itis importantthatthecirculationratenotbesetanyhigherthanisneeded.

Notwithstandingthis,usualpracticeistosetthecirculationrateforpeakflows plus a comfortable safety factor (e.g., 10 percent [Pearce, 1982]). Thereafter, adjustments to the circulation rate with changes in throughput are made infrequently, if at all. Consequently, there is considerable potential for optimizationoftheglycolcirculationrate. Thiswillnotonlyreduceventing emissions,butwillremoveunnecessaryloadfromthereboilerandtherebylower combustionemissionsandconservefuel. Oneoptionistoconductperiodicperformancetests(e.g.,sampletherichand lean glycol) on each unit and manually adjust the glycol circulation rate. Sometimesitmayevenbenecessarytoreplacetheexistingpumpwithasmaller pump(i.e.,itisnotuncommonfortheglycolpumpandothercomponentsofthe dehydratortobeoversizedbecauseofproductiondeclinesorlowgasdemand). AccordingtoBallard(1986),theleanglycolweightpercentshouldbeabout98to 99.5+. The rich glycol will vary from about 93 to 97 percent. If the spread between the lean and the rich glycol content is too narrow (about 0.5 to 1.5 percent),itusuallymeanstheglycolcirculationrateistoohighandshouldbe decreased. Ifthespreadistoowide(over4to5percent)itusuallymeansthe glycolcirculationrateistoolowandshouldbeincreased. Another option is to implement a continuous feedback control loop using a dependablemoistureanalyzer.Theanalyzerisinstalledonthesalesgaslineand theoutputsignalisusedtoregulateavariablespeedglycolrecirculationpump tomaintainthemoisturesetpointwithinspecifiedlimits. Theselimitsmaybe establishedbasedonvariousfactorsdirectlyrelatedtoweatherconditionsand contractrequirements. Lastly,whenglycoldehydratorsarebought,considerusingmoretrays,usually about 10, to lower the required glycol circulation rate (Ballard, 1986). The requiredcirculationraterapidlydecreasesasthenumberoftraysareincreased from6traysupto10trays.

InletGasTemperatureandPressure:Theamountofemissionsthatmayoccur forawellposeddehydrationapplicationinvolvingproperlytrainedoperatorsis ultimatelydeterminedbytheamountofwaterintheinletgas. Thisinturnis determinedbytheinlettemperatureandpressureofthegas.Thewatercontent ofthegaswilldecreasethrough condensation astemperatureisloweredand pressure is increased. So, also, will the concentration of higherboilingpoint aromatics and their corresponding emissions. Accordingly, the operating

temperatureshouldbeminimizedandtheoperatingpressuremaximizedtothe fullestextentpossible.However,inmostcasestemperaturewillbetheeasiestto adjustandwilllikelyofferthegreatestgains. Sometimesifthepressuresarerelativelylow,itmaybefeasibletoinstallaninlet aircoolerwhentheinletgastemperatureistoohigh. Itshouldbenoted,however,thatTEGbecomessufficientlyviscoustoimpair efficientcontactattemperaturesbelowabout15oC(API,1990).

LeanGlycolTemperature:Itisimportantthattheglycolenteringthecontactor be cooled to 5o to 15o C above the temperature of the gas stream to prevent hydrocarbon condensation in the absorber and subsequent foaming (Ballard, 1986;API,1990).Athighertemperatures,morewatervapourwillremaininthe gasstreamresultingintheneedforhigherglycolcirculationratesandincreased loadingofthereboiler.Highertemperatureswillalsocontributetohigherglycol lossesthroughvaporizationintothesalesgasstream. StrippingGas: Strippinggasmaybeusedtoobtainhigherglycolpuritiesto helplowerglycolcirculationrates.ThiswilltendtolowerBTEXemissionsbut increasemethaneemissions.Thebenefitsofusingstrippinggasdiminishrapidly beyond rates of about 15 to 20 L/L of TEG solution circulated (Hernandez Valencia,1992). ReboilerTemperature:Theoperatingtemperatureofthereboilershouldbeas highaspossiblewithoutexceeding205oCtoensuremaximumreconcentrationof the TEG and thereby suppress the necessary glycol circulation rate. Higher temperatureswillleadtoexcessiveglycollossesintothestillcolumnventgas andpossiblythermaldecompositionoftheglycol. On a standard unit (i.e. one with a gas fired reboiler) this temperature is thermostatically controlled and fully automatic. Nonetheless, the reboiler temperature shouldbe occasionallyverifiedwitha testthermometertomake suretruereadingsarebeingrecorded(Ballard,1986).Thereboileroperatesbest whenitisabletoachieveauniformtemperature.Ifthetemperaturefluctuates excessively when operating below the design capacity, the fuel gas pressure shouldbereduced.Conversely,ifthereboilertemperaturecannotberaisedas desired,itmaybenecessarytoincreasethefuelgaspressureuptoabout200kPa andreadjustthedampersontheairintake.

StillColumnTemperature: Itisalsoimportant thattheoverheadcondenser temperatureinthetopofthestrippercolumnbeoptimized.Ifthetemperatureis toolow,excessivereflux,andconsequentlyunnecessaryloadingofthereboiler willoccurresultinginincreasedcombustionemissions.Ifthetemperatureistoo high, excessive TEG losses to the atmosphere will occur. At atmospheric pressure, the boiling point of water is 100oC and of TEG is 288oC (The Dow ChemicalCompany,1981). AccordingtoBallard(1986),thetemperatureinthetopofthestillcolumnshould be about 96oC. Below 93oC there is a possibility that the water will start condensing and washing back into the still column. When this temperature reaches121oCandabove,theglycolvaporizationlosseswillsharplyincrease.

Energy Efficient Variable Speed Pumping Systems: The use of an energy efficient glycol pump is important to help reduce energy costs and related combustionorventingemissions. Inastandardapplication,theglycolenergy exchange pump is perhaps the simplest most energy efficient means of circulatingtheglycol,providedthattheflashgasisutilizedasfuelorstripping gas.However,thespeedofthispumpmustbeadjustedmanually;thereforeitis notsuitableforusewhereacontinuousmoisturecontrolsystemisproposed.An energyefficientalternativeinthiscaseistouseagasoperatedpump,wherefuel gasisusedasthesupplymediumandtheventedgasisstoredinanaccumulator atapressuresuitableforuseasfueltothereboiler.However,thiswillrequire that richglycolliquidlevelcontrolbeinstalledonthecontactor. Nonetheless, thisapproachhastheaddedbenefitofnotrequiringanyelectricitywhichmay oftenbeunavailableinfieldapplications.

Thelimiteddataandexperiencesthathavebeenpresentedintheliterature (Ballard, 1986;RichardsonandWhiteStevens,1986)indicatethatthereispotentialforsubstantial reductions in BTEX emissions and fuel consumption by glycol dehydrators through regularoptimizationoftheseunits. Key issues and constraints include the following: Not all glycol dehydrators necessarily need to be optimized beyond what is alreadybeingdone. The potential for substantial improvements may be greatly limited by the possibleovercapacityoftheunitforexistingproductionrates. Itmaybemore sensible in some cases to simply replace the dehydrator with a more appropriatelysizedunitoranalternatedehydrationtechnology.

A potential operating problem experienced by some moisture analyzers in naturalgasapplicationsisinterferenceduetocoatingofresidualglycolonthe detector.Thiscanapparentlybeovercomebyinstallingandmaintainingagood filteringsystemonthesamplelinetothedetector.

Oxidation Units Thevapoursfromthestillcolumnventmaybedisposedofbyroutingthemtoasuitable continuousoxidationunit.Alowpressureflaresystemorthermalincineratorunitmay beconsidered.(Athermalincineratormaybedistinguishedfromaflarebyitsuseofa refractory lined chamber to contain the flame heat and promote some post flame combustion). Bothdeviceshavebeenusedsuccessfullyinthisapplicationandcanbedesignedwith automatic ignition systems to ensure a continuous flame. If electric power is not availableonsite,asolarpanelandbatterysystemmaybeusedtooperatetheigniterora "piezometric"devicemaybeemployed. However,thefollowingfactorsgenerallymaketheincineratorthepreferredchoicefora thermaloxidationunit:

Thelowdischargepressureofthedehydratorstillcolumnprovideslittleenergy todrivetheventgastoaflare.Aneductormaybeusedtomovethegasbutthis mayresultinhighoperatingcosts(Rutbergetal.,1985).Ifanincineratorisused there is generally enough natural draft for the vapours to flow to the unit unassisted. Thehighwatercontentofthegasmayleadtofreezeoffoftheflarelineduring winter operation unless the system is heat traced or designed for dedicated dehydratorservice(i.e.,theflarelineisslopedandinsulatedsoanywaterthat condenseswilldrainbackintothedehydrator).Adedicatedincineratorcanbe safelyplacedmuchclosertothedehydratortohelpreducethecostofdoingthis. Fuelgasmustbeaddedtotheventgastoincreaseitsheatingvaluetoapoint where good combustion may be assured. The use of supplementary fuel is usuallynotrequiredwithanincineratorduetoitsbetterretentionoftheflame heat. Moreover,incineratorsareabletoprovidebetterdestructionefficiencies thanflaresystemsandaremoreaestheticallyappealingsincethereisnovisible flame.

Aproperlydesignedandoperatedflarewithastable,smokelessflamemayprovide destructionefficienciesabove98percent(McCrills,1988).Anincineratormayprovide efficienciesabove99percent. Apowersourceisneededforignitionofthewastegasandsupplementalfuelmaybe requiredtomaintainastableflameifthecalorificvalueofthegasesislow. Vapour Recovery Condensers Anumberofdifferentvapourrecoverycondenser(VRC)systemshaverecentlybeen developedintheUnitedStatestocontrolBTEXemissionsfromthestillcolumnventon glycoldehydrators.Mostofthesesystemshavebeeninhousedevelopmentsbysomeof themajoroperatingcompanies.Patentapplicationhavebeenfiledforatleastfourofthe VRC designs, namely the Texaco (Schievelbein, 1992), Conoco (Choi, 1992), RBTEX (Lowell and Sivalls, 1992; Gamez et al. 1993) and Armellini Engineering (Armellini, 1992)processes.Fieldevaluationsofthefirsttwocontrolsystemshavebeenconducted, anddemonstrationoftheRBTEXsystemiscurrentlyinprogress. ThebasicVRCprocessconsistsofcoolingtheventedgasfromthestillcolumnto50 oCor less.Astandardofftheshelfaircoolerorothertypeofcoolerisusuallyemployedfor thispurpose.Thecoolingcausesthewatervapourandmostofthearomaticsandother heavyhydrocarbonstocondense. Thenoncondensablevapourisessentiallymethane andmaybeusedforfuel,incineratedorcompressedintothenaturalgasstreamtobe dehydrated. The condensate is separated into water and hydrocarbon liquid and transferredintoappropriatestoragetanksforsubsequentdisposition.Thewatermust bedisposedofinanenvironmentallyacceptablemannerandthehydrocarbonliquid maybeusedforfuelorsold. The hydrocarbon liquid is mostly BTEX (about 60 percent [Choi, 1992]) and the remainingconstituentsarenhexaneandotherparaffinichydrocarbons. There is some scatter in the measured efficiencies of VRCs with respect to BTEX emissions(Schievelbein,1992;Grizzle,1992).However,thevaluesaregenerallygreater than90percentifaflashtankisemployedupstreamofthereboiler.Ifaflashtankisnot usedefficienciesgenerallydroptomuchlessthan50percent.