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DieselFuelAdditives

DieselNetTechnologyGuideWhatisDieselFuel
DieselNet.com.CopyrightEcopointInc.Revision2016.01a

DieselFuelAdditives
HannuJskelinenandPaulRichards

Abstract:Thecharacteristicsofdieselfuelcanbeimprovedthroughtheuseofadditives,whichareadded
attherefinery,atthedistributionterminal,orbytheenduser.Themanydifferentadditivescanbe
categorizedindifferentwaysbasedonthechemistry,purpose,etc.Oneconvenientwayofcategorizing
themistogroupthemasadditivesusedtoAidHandlingandDistribution,toImproveFuelStability,to
ProtectEnginesandFuelSystemsandadditivestoInfluencetheCombustionProcess.Someadditives
mayinfluencemorethanonecategoryandofcourseadditivescanbecombinedtoproducemultifunctional
additivepackages.
Introduction
AdditivestoAidHandlingandDistribution
AdditivestoImproveFuelStability
AdditivestoProtecttheEngineSystems
AdditivestoInfluencetheCombustionProcess

1.Introduction
Untilthelatterpartofthetwentiethcenturytherewaslittleornouseofdieselfueladditives.Duethe
versatilityandrobustnessofthedieselengine,suitabledieselfuelcouldbeproducedfromablendof
straightrunatmosphericdistillationcomponents.Wherearefinerhadanecessitytobiasproduction
towardsgasolinethenthedieselpoolcouldoftenbesupplementedwithcrackedgasoilsfromthe
gasolinerefiningprocess.Asfuelsulfurlevelsweregraduallyreducedthenadditionalprocessingcould
berequireddependingonthecrudeoilsource.Withtheincreasingfueldemand,changingdemandmix
andtighteningspecificationstherefiningprocesseshavechangedandwithittheuseofdieselfuel
additives.Althoughthereisnorigorousdefinitionofwhatconstitutesanadditive,asopposedtoa
blendingcomponent,itisgenerallyacceptedthatanadditiveissomethingaddedatlessthan1%w/w
(i.e.10,000mg/kgor10,000ppm).Becauseofthislowtreatrateofadditivesthephysicalpropertiesof
thefuel,suchasdensity,viscosity,andvolatilityarenotchangedsignificantly.
Toincreasetheyieldofdieselfueltherefinermustcutdeeperintothecrudefeedstocknecessitating
theuseofflowimproverstorestorethelowtemperatureperformanceofthefuel.Withincreasing
demandforimprovedignitionqualityandincreasingcetanenumberspecificationstheuseofignition
improveradditiveshasalsorisen.Aslegislationspecifyingultralowerfuelsulfurlevelshasspread,the
abilityofthedieselfueltolubricatethefuelinjectionequipmenthasdiminishedthishasnecessitated
theuseoflubricityadditives.Theadditivesdiscussedinthispapercanbecategorizedasfollows:
Fuelhandlinganddistributionadditives
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Lowtemperatureoperabilityadditives
Flowimprovers
Waxantisettlingadditives
Cloudpointdepressants
Deicingadditives
Otherfuelhandlingadditives
Antifoamadditives
Dragreducingadditives
Staticdissipateradditives
Biocides
Demulsifiers
Dehazers
Corrosioninhibitorsforfueldistributiuonsystem
Markerdyes
Deodorantsandreodorants
Fuelstabilityadditives
Antioxidants
Stabilizers
Metaldeactivators
Dispersants
Engineprotectionadditives
Corrosioninhibitorsforvehiclefuelsystem
Injectorcleanlinessadditives
Lubricityadditives
Combustionadditives
Ignitionimprovers
Smokesuppressants
Combustioncatalysts
Themorewidespreadinclusionofbiodieselaspartofthedieselfuelblendwillalsonecessitatetheuse
offueladditives.However,theseadditiveswillusuallybeincludedinthebiodieselitselfinorderto
ensurethatthebiodieselmeetstherelevantspecification.Thisisdiscussedingreaterdetailunder
BiodieselMonoAlkylEsters.Therefore,blendingdieselfuelwithonspecificationbiodieselshould
notrequireadditionaladditization.
Additivesmaybeaddedtodieselfuelatthreedifferentstages:(1)attherefinery,(2)inthefuel
distributionsystem,and(3)afterthefuelhasleftthecontroloftheproducer.Additivesofthelatter
group,whenaddedbytheenduserorareseller,arecalledaftermarketadditives.Onenotableexception
tothislatterpointistheuseofFuelBorneCatalysts(FBC)thatareaddedtothefuelonthevehicleand

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formpartofthevehiclemanufacturersemissionscontrolstrategy.Theseadditivesarediscussedin
FiltersUsingFuelBorneCatalysts.
RefineryAdditization.Fuelrefinersmustensurethattheirproductsmeettherelevantspecifications
forthelocationandtimeofyear,andaresuitablefortheintendeduse.Thiscanbeachievedthrough
suchmeansasthechoiceofcrudeoil,refineryprocessing,blending,ortheuseofadditives.Thefinal
choiceofmethodsisdrivenbyeconomics.Theextenttowhichaparticularrefinerywillrelyon
additivesisthereforedependantonmanyfactorsandtheexactextentofadditiveusageremainsunclear.
DistributionSystemAdditization.Pipelineoperatorssometimesinjectdragreducingadditives(to
increasethepipelinecapacity)and/orcorrosioninhibitors.Tohelpcontrolcostsitiscommonpractice
inmanycountriesforoilrefinerstoproduceafuelmeetingthebasiclegislatedspecificationandtosell
orexchangethisfueltootherfuelmarketingcompanies.However,thereisagrowingawarenessofthe
needformarketplaceproductdifferentiationthisappliestofuelasmuchasanyotherproduct.Itisthus
becomingcommoninmanycountriesforadditivepackagestobeincludedattherefineriesdistribution
terminaltosupportthemarketingcompanysqualityclaimsorstandardsforexampletoproduce
regularorpremiumgradedieselfuelsorsimplytotryanddifferentiateonecompanyfromanother.
ThispracticehasbeenwidelyadoptedinEuropeandotherpartsoftheworld.Additivescanalsobe
addedattheretailpumpallowingfuelretailerstomarketmorethanonegradeofdieselfuelataretail
sitewithouttheneedforseparatestoragetanks.
AftermarketAdditives.Someuserswilltreattheirfuelwithadditivestomeettheirparticularneeds,
forinstancecoldclimateoperation,orbecausetheybelievetheyneedahigherqualityfuel.Awide
rangeofaftermarketadditivesareavailablefromanumberofsuppliers.Someoftheseadditivesmay
havelegitimateuses.Forinstance,theuseofdeicersmaybewarrantedundercoldweatherconditions
and/orwhenproblemswithfuelsystemicingareencountered.Inmanycases,however,aftermarket
additivespackagesconsistofcompoundssuchasdetergents,lubricityimproversandcetaneenhancers
thatwouldnormallybeaddedattherefineryorfuelterminalbythefuelmarketer.
Usersshouldbecautiouswhenconsideringtheuseofanyaftermarketadditives.Someaftermarket
additivesareaggressivelymarketed,withperformanceclaimsthatareoftentoogoodtobetrue.Yet,in
mostcases,theyarenotneededandshouldbeavoidedthisisespeciallytrueofmodernhigh
technologydieselengines.Goodqualitycommercialfuelsfromreputablemarketerscontainallthe
additivesthatafuelneedsandhavebeenextensivelytestedtominimizethepossibilityofadverse
interactionsbetweendifferentadditiveand/orfuelcomponents.
Iftheuserstillfeelsthatadditivesareneeded,theyshouldbechosenbasedoncarefulresearch,and
usedinaccordancewiththerecommendationsoftheadditivesupplierandtheenginemanufacturer.
Inappropriateuseofadditivesmayhaveadverseeffectsontheengine,andmayaffectenginewarranties
(forexample,someenginemakersrequirethatalcoholbaseddeicersnotbeused).

2.AdditivestoAidHandlingandDistribution
2.1LowTemperatureOperabilityAdditives
2.1.1Overview
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Theseadditiveswhichcanlowerthepourpoint,cloudpoint,orimprovethelowtemperature
propertiesareusuallypolymersthatinteractwiththewaxcrystalsformedindieselfuelwhichis
cooledtoasufficientlylowtemperature.Usuallythisoccursatorbelowthemeasuredcloudpoint.The
polymersmodifythesize,shape,and/ordegreeofagglomerationofthewaxcrystals.Theadditives
mustbeblendedintothefuelbeforeanywaxhasformed,whenthefueliswellaboveitscloudpoint.
Differentadditivesareeffectivefordifferentfuels,andtheireffectivenessmustbedetermined
experimentally.Thebenefitsfromdifferenttypesoflowtemperatureoperabilityadditivesarelistedin
Table1[Chevron1998].
Table1
Lowtemperatureoperabilityadditivebenefits
AdditiveType

TypicalTreatRate
ppm

TypicalBenefit
C

Cloudpoint

2002000

34

57

LTFT

502000

812

1525

CFPP

1002000

1520

2535

Pourpoint

100300

3040

5070

TheimportanceoflowtemperatureoperabilityadditivescanbeillustratedwithFigure1(datafrom
Faure[Faure2000])whichshowsthedifferencebetweencloudpointandCFPPandcloudpointandpour
pointforuntreatedfuelsandfuelstreatedwithadditives(thecloudpointofthesefuelswasshownin
thedieselfuelpaper).

Figure1.DifferencebetweencloudpointandCFPPandpourpointforuntreatedandtreated
fuels
Fueltreatment:250mg/kgofanEVAbasedflowimprover

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Formanyoftheuntreatedfuels,thedifferencebetweencloudpointandCFPPwasnegligible
meaningthatvehicleoperabilityproblemscouldoccuratorjustbelowthecloudpoint.Useofan
additive,however,isshowntoprovidesignificantbenefitsformostofthefuels,thereforeextendingthe
lowtemperaturerangeoverwhichtheycanbeusedwithoutoperabilityproblems.Itisalsoworth
notingthatwithouttheuseofadditives,thefuelsofthisexamplecouldgelabout27Cbelowthecloud
pointasevidencedbythedifferencebetweencloudpointandpourpoint.Gelledfuelwouldnotflow
easily.Additivesextendthisrangeto10Cormorebelowthecloudpoint.
Twoimportantgeneralclassesofadditivesusedtoimprovelowtemperaturevehicleoperabilityare
flowimproversandwaxantisettlingadditives(WASA).Furthertypesoflowtemperatureoperability
additivesincludecloudpointdepressantsanddeicingadditives.

2.1.2Flowimprovers
Flowimprovers,alsoknownasCFPPadditivesandmiddledistillateflowimprovers(MDFI),donot
preventwaxcrystalsfromforminginthefuel.Rather,theirmechanismofactionreliesonkeepingwax
crystalssmallenoughsotheydonotblockfuelfiltersaseasily.Althoughtherearestandardtestsfor
testingthesepropertiesthedesignofthevehiclefuelsystem[Mikkonen2012]andthefuelfilteritself
[Arnault2014]canplayanimportantroleinthecoldweatherperformance.
Flowimproveradditives,usuallypolymericinstructure,includesuchcopolymersaspolyacrylates,
polymethacrylates,fumarates,polyolefinsandpoly(ethylenecovinylacetate)(EVA).These
copolymersarecomposedofahydrocarbonchainthatprovidestheinteractionbetweenadditivesand
theparaffininthefuelandapolarsegmentthatisresponsibleforthewaxcrystalmorphology
modificationnecessarytoinhibittheaggregationofcrystals.
EVAcopolymersareverycommonandhavebeenstudiedextensively[Marie2005][Zhang2009].The
actionofEVAflowimproversdependsnotonlyonthestructureoftheEVAmoleculesbutthewax
distributioninthefuelandthefuelcompositionitself.Theiractionisbelievedtoinvolvetwo
mechanisms.First,theadditiveactsasanucleatorandformsmorecrystallizationnucleithanwould
occurinthefuelwithoutadditive.Fuelwaxthencrystallizesontothesenucleiandbecauseoftheirhigh
number,thewaxcrystalsremainsmaller.Second,theadditiveactsasagrowtharrestorbyreducingthe
tendencyofcrystalstoagglomerateandgrowbytheadsorptionoftheadditiveonthegrowingcrystal
surface.Thefunctionalgroupsontheflowimprovermoleculespreventtheadherenceofnewwax
crystalsontoagrowinglattice.
Nalkanesinfuelnottreatedwithaflowimproveradditiveoftenformlargeplatelikecrystals,Figure
2a.Bycontrast,fuelstreatedwithanEVAflowimproveroftenformsmallneedlelikecrystals,Figure
2b,whichhavelesstendencytoblockfuelfilters.Someofthecrystalsmaypassthroughfilterswith
sufficientlylargeporesize,whilethosetrappedonthefilterproduceamorepenetrablelayerand
dissolvemorerapidlyasthefueliswarmed.

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Figure2.Effectoflowtemperatureoperabilityadditivesondieselfuelwaxformation
(a)untreatedbasefuel(b)flowimprover(c)flowimproverpluswaxantisettlingadditive
(Source:Infineum)

Anumberoffactorsmustbeconsideredtomaximizetheperformanceofflowimproveradditives
includingtheirsolubilityinthefuelandthequantityandsizedistributionofthewaxinthefuel.
Otherwise,themechanismofactionandtheefficacyoftheadditivemaysuffer[Marie2005].
Somecharacteristicsoffuelsthatareeitherunresponsivetoflowimprovingadditivesorrequire
increasedlevelsofadditivetoeffectimprovementinlowtemperatureoperabilityinclude:
adifferenceoflessthanabout100Cbetweenthe20%and90%distillationtemperatures,
adifferenceoflessthanabout25Cbetweenthe90%distillationtemperatureandthefinal
boilingpoint,
afinalboilingpointaboveorbelowthetemperaturerange340Cto380C.
acloudpointbelowabout20C.
thesolvencyofthefuelitself[Goberdhan2015].
Thesefuelsmayhaveawaxdistributionthatmakesthemrespondpoorlytoflowimproveradditives.
Flowimproveradditivesforsuchfuelsmayrequireadditionalcomponentstoensuregoodresponse.
Combpolymersareoneoptionthathasbeensuggested[Botros2001][Tack1989][Brown1998].Additives
forthesefuelsmayalsoincorporatewaxestomakethefuelmoreresponsivetotheflowimprover
additive[Jackson2001][Jackson2002].Theinclusionofbiodieselinthemoderndieselfuelscanalsohave
verysignificanteffectofcoldflowperformance[Poirier2008][Yamane2013]thisisdiscussedfurtherin
thepaperonbiodiesel.

2.1.3WaxAntiSettlingAdditives
Whileflowimproversgreatlyreducethesizeofwaxcrystalsthatformbelowthefuelscloudpoint
temperature,thecrystalscanstillsettletothebottomofthefueltankleavingaclearupperphaseanda
bottomphaseveryrichinwaxcrystals.Thisbottomlayercanstillcausefilterpluggingproblemsas
fuelisnormallydrawnfromthebottomofthevehiclestank.Waxantisettlingadditives(WASA),
alwaysusedinconjunctionwithflowimprovers,furtherslowdowncrystalgrowthandkeepcrystals
smallenoughsothattheysettleatamuchslowerrateandremaindispersedinthefuelforamuch
longerperiodoftime(Figure2c).Reliablevehicleoperationtoabout15Cbelowthecloudpointofthe
fuelcanbeobtainedwiththecombineduseofWASAandflowimprovers[Gairing1995].
TwodifferentmechanismsofactionoftheWASAarethoughttobeimportant:
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1.WASA,whenusedwithEVAflowimprovers,reducestheparaffincrystalsizecomparedtoEVA
flowimproversalone.Thisreducesthesettlingrate,accordingtotheStokeslaw:

v=(2r2/9)(dpdm)g

(1)

where:
vsettlingrate,m/s
rparticleradius,m
matrixdynamicviscosity,kg/ms
dpparticledensity,kg/m3

dmmatrixdensity,kg/m3,

ggravitationalacceleration,9.81m/s2.

Crystalsizeswhichareinthemmrangeinuntreatedfuelcanbereducedtoabout1020m
byEVAcopolymerflowimprovers.WASAfurtherreducescrystalsizestoabout5m.
2.Sizereductionofcrystals,however,isnotenoughtoexplainthefullvariationsofsettlingrate
typicallyobserved.Themainmechanismwhichlowerssettlingrateisthroughthestabilizationof
thecolloidalsuspensionofparaffincrystalsandtheresultingreductionincrystalaggregationand
amuchslowersettlingrate[Marie2004][Yuhui2006].Thesesuspensionscanhoweverbeunstable
givensufficienttime,significantsettlingcanoccurinarapidmanner[Faure2000].
TheefficiencywithwhichWASAlowerthesettlingratecanbesignificant.Figure3showsthe
efficiencywithwhichWASAloweredsettlingrateinanumberoffuelswithdifferentwax
concentrationstreatedwithflowimproverandflowimprover+WASA.Themaximumefficiency
shownis85%[Faure2000].

Figure3.EfficiencyofWASAforfuelstreatedwithflowimproveronlyandflowimprover+
WASA
FI=250mg/kgWASA=375mg/kgefficiency=100[1(WaxsettledwithFI)/(Waxsettledwith
FI+WASA)]fuelheldfor5hat15C.

WASAcanconsistofcompoundssuchasacidamidesandpolymersmodifiedwithaminogroups.EVA
copolymersmodifiedtocontainhighlypolarfunctionalgroupsareoftenused.Theyaresmaller
moleculesthanflowimproversandgenerallyresemblesurfactantswhichgivethemtheirdispersing
potential.Otherchemistriesthathavebeenconsideredincludequaternarysalts,ionicliquidsand
Geminisurfactants[Maithufi2010].

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Dependingontheirstructureandthetypeofflowimprovertheyareusedwith,WASAadditivesmayor
maynothaveanimpactCFPPtestsresults[Yuhui2006][Faure2000].Vehicletestshowever,haveshown
thatimprovementsinlowtemperaturevehicleoperabilityof2.5to4.5CcanbeachievedwithWASA
usedinconjunctionwithflowimproversevenwhenthereisnomeasurableimpactonCFPP[Rickeard
1989].

2.1.4CloudPointDepressants
Flowimprovers,whileprovidingsignificantlowtemperatureoperabilitybenefits,havelittleimpacton
cloudpoint.Cloudpointdepressant(CPD)additivesarecommonlyusedbyrefinersinplaceof
keroseneadditiontomeetpipelinecloudpointspecifications(waxbuilduponpetroleumproduct
pipelinewallscantrapcontaminantsandrestrictpipelineflowarea)ratherthanimprovevehicle
operability.Theyshiftthethermodynamicequilibriumbyirreversiblydecreasingthecrystallization
temperaturebyfixinglongernalkanesinsidecomplexpolymerstructures.Thishastheeffectof
increasingthesolubilityofhighermolecularmassnalkanes.AsshowninTable1,cloudpoint
depressantsprovideonlyasmallbenefitatnormaltreatrates.Ithasbeensuggestedthat500ppmof
CPDwillsolubilize0.4%massofnalkanesinafuel[Claudy1992].
WhenCPDsareusedinconjunctionwithaflowimprover,anantagonisticbehaviorissometimes
observedinfuelswithlowconcentrationsoflightnalkanes.TheCPDcanseriouslyimpairthe
performanceoftheflowimprover.Toavoidthisproblem,acarefulselectionofcloudpointdepressant
chemistryoroptimizationoftheconcentrationofCPDandflowimproveradditiveisrequired.Ineither
case,theefficiencyoftheCPDdecreases[Letoffe1995].Examplesofchemistriesusedascloudpoint
depressantsareethylenevinylacetatecopolymers,vinylacetateolefincopolymers,alkylestersof
styrenemaleicanhydridecopolymers,polyalkylacrylates,polyalkylmethacrylates,alkylestersof
unsaturatedcarboxylicacids,polyalkylfumarates,andolefincopolymers[Ziegler2000].

2.1.5DeIcingAdditives
Freewaterindieselfuelisamajorsourceoflowtemperatureoperabilityproblems.Dieselfuelisnot
entirelyhydrophobicandcandissolvesmallamountsofwatertypicallylessthan100ppm.Asthe
temperatureofthefueldrops,thewatersolubilityinthefueldecreasesanddissolvedwaterwillbegin
tocondenseout,appearingastinydroplets.Overtime,thesedropletscancoagulateandsettletothe
bottomofthetankwherealayerofwatercanbuildup.Thus,evenifproperhandlingproceduresand
precautionshavebeentakentokeepwateroutofallpointsofthefuelhandlingchain,watercanappear
inthefuelwhenthetemperaturedrops.Thiswatercanfreezeatlowtemperatures,pluggingfuellines
orfiltersandblockingtheflowoffuel.
Twodifferenttypesofadditivesareusedtopreventicingproblems:(1)surfactantsand(2)freezing
pointdepressants(antifreezes).Surfactantssuchasamines,diamines,amides,orglycolestersoffatty
acidshelpkeepthewaterdropletsdispersedbylimitingcoagulation.Whiletheymaynotpreventthe
waterdropletsfromfreezing,theicecrystalsformedarekeptsmallenoughtopassthroughthefuel
filter.Surfactantdeicersareeffectiveatconcentrationsfrom1060ppm.Othersurfaceactive
substancesaddedtofuelsmayalsohaveantiicingproperties.Freezepointdepressantsinclude
alcohols,glycols,dimethylformamide,andotherwatersolublepolarsubstances.Dependingonthe
type,theyareusedinconcentrationsrangingfrom0.022vol%.Isopropanolisacommonalcoholthat
isfoundinmanydeicingadditives.Methanolandethanolshouldnotbeusedbecauseofpotential
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damagetosealsandfuelsystemcomponents.Allalcoholshavearelativelylowflashpoint(1117C)
andevenrelativelysmallamountsaddedtodieselfuelcansignificantlylowertheflashpointofthe
fuel.

2.2OtherFuelHandlingAdditives
2.2.1AntifoamAdditives
Foamingofdieselfuelcaninterferewithfillingthefueltankfoamcanreachthetankfillerneckand
causethefillingoperationtobestoppedbeforethetankisfullorthefoamcanoverflowthefillerneck
whiletryingtofillthetankwithliquid.Thiscanbeaparticularnuisancetocustomersasdieselengines
becomemorecommoninpassengercars.Theinclusionofanantifoamalsoreducesspillageandthus
helpstokeepthefuelstationforecourtcleanandreducetheriskofcontamination.
Antifoamadditivesaretypicallyorganosiliconecompounds,thechoiceofsiliconecompoundandany
cosolventarechosentosuittheparticularcharacteristicsofthefuelbeingtreated.Thechoiceof
antifoampackageisusuallydeterminedbythespeedwithwhichafoamlayercollapsesafterbeing
vigorousshakentosimulatetheeffectofairentrainmentduringtankfilling.Theuseofantifoam
additivesiskepttoaminimumduetoconcernsoversiliconcompoundscontributingtosediment
formation,resultinginsludge,cloggedfilters,andinjectordeposits.Thusantifoamadditivesareusually
usedatconcentrationsof10ppmorless.

2.2.2DragReducingAdditives
Pipelineoperatorssometimesusedragreducingadditivestoincreasethepipelinecapacity.These
additivesarehighmolecularweightoilsolublepolymersthatshearveryrapidlywhentheadditized
productpassesthroughapump,thus,ithasnoeffectonfuelperformanceinengines.Adragreducing
additivecanincreasethemaximumpipeflowrateby2040%.Dragreducingadditivesaretypically
usedatdoseratesbelow15ppmbutcouldbeusedatlevelsupto50ppm.

2.2.3StaticDissipaterAdditives
Sometimesreferredtoasantistaticadditivesareaddedtodieselfueltoavoidtheriskofanexplosion
duetoachargeofstaticelectricitybuildingupduringfastratesofpumping.Thereuseindieselfuelis
becomingmorecommonbecausetherefineryprocessesusedtoproduceultralowsulfurdieselfuel,
willalsoremovemanyoftheotherpolarcompoundsfromthefuelthusreducingthenaturalstatic
dissipationpropertiesofthefuel.
Theadditivesworkbyincreasingtheconductivityofthefueltherebyhelpingtodissipateany
electrostaticchargegeneratedduringpumping.Themostcommonlyusedtypeofstaticdissipatersare
polysulfonecopolymers,butotherchemistriessuchasolefinacrylonitrilecopolymers,aliphatic
aminesfluorinatedpolyolefinsandchromiumsaltsmayalsobeused.Additivetreatratesarekeptvery
low,typicallyonlyafewppm.

2.2.4Biocides
Thegrowthofmicroorganismsusuallyoccursinfueltankwaterbottomsaerobicoranaerobic
organismsliveinthewaterandfeedatthefuel/waterinterface.Thisbiomasscanthenblockfiltersif
drawnoutwiththefuel.Thefuelistreatedwithbiocidestopreventthisgrowth.Theadditiveshouldbe
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solubleinboththefuelandthewater,soitcanattackthemicrobesinbothphases.Awiderangeof
chemicaltypescanbeusedthisincludesboroncompounds,amines,andimines.However,thebacteria
candevelopresistance,sotheadditivetypemustbechangedfromtimetotime.Sincebiocidesare
toxic,thebiomassandwaterthatcontainbiocidesmustbedisposedofappropriately.
Biocidesareassessedbyincubationoftreatedanduntreatednutrientmediathathavebeeninoculated
withtherelevantstrainofbacteria.Atreatrateashighas600ppmcanbeusedfordirectadditiontothe
waterbottoms.Amuchsmallerdoseratecanbeusedforadditiontothefuelasitgoesintostorage.

2.2.5Demulsifiers
Thesearehighlysurfaceactivecompoundsthatarechosenfortheirlimitedsolubilityinoilandwater.
Examplescanbepreparedbyreactingahydrophobicmoleculesuchasalongchainalkylphenolwith
ethyleneorpropyleneoxide.Demulsifiersandtheirtreatratemustbecarefullychosenbecauseasthey
arethemselvessurfactantstheycanaddtotheactivitythatiscausingtheemulsion,ortheycaninterfere
withtheeffectivenessofothersurfactantsthatmaybepresenttoproduceabeneficialeffect.They
typicallyareusedintheconcentrationrangeof530ppm.

2.2.6Dehazers
Hazyfuelisduetothepresenceoffinelydisperseddropletsofwater,i.e.aformofemulsion.Dehazer
additivesarethereforeoftengroupedtogetherwithdemulsifieradditives.Hazyfueltendstooccuras
isolatedincidents,itisthusoftenthemostpracticalsolutiontotestalternativeadditivesonsite,in
samplesdrawndirectlyfromtheaffectedtank,beingcarefultomaintainthesampletemperature.
Warmingthesamplebymovingittothelaboratorymayinitselfcausethehazetoclear.
Effectivedehazeradditivesincludequaternaryammoniumsalts,typicallyusedinaconcentrationrange
similartodemulsifieradditives.

2.2.7CorrosionInhibitors
Thesecompoundsaresurfactantmaterialsthathaveapolargroupatoneendandan
oleophilic/hydrophobicgroupattheother.Thepolargroupattachestometalsurfacesandformsa
barrierthatpreventsattackbycorrosiveagentstheothergrouprepelswaterandprovidesanoilylayer
topreventrustformation.ThisisillustratedinFigure4.Theyareaddedprimarilytopreventthe
corrosionofpetroleumtanksandpipesbywater.

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Fuel
Water
Fuel soluble
group
Polar head
group

Metal surface
Figure4.Schematicillustrationofsurfaceactivemoleculesprotectingametalsurface

Chemicalcompoundsusedasanticorrosionadditivesincludeestersoraminesaltsofalkenylsuccinic
acids,alkylorthophosphoricacids,alkylphosphoricacidsandarylsulfonicacids.Corrosioninhibitors
typicallyareusedintheconcentrationrangeof515ppm,however,asthesecompoundsattach
themselvestometalsurfacestheremaybeonlyabout1ppmleftinthefuelattheendofthepipeline.
Acidbasedcorrosioninhibitorswillreadilyreactwithcausticsodawhichisoftenusedinrefinery
processesandwithpoorhousekeepingcanenterthefuelsupplychain.Thiswillobviouslyreducethe
effectivenessoftheacidcorrosioninhibitorandhasbeenblamedfordepositformationinengines
[Schwab2010].Ithasfurtherbeenshownthatthepresenceofanyacidicspeciesinfuelcombinedwith

intimatecontactwithasourceofsodiumbaseincreasestheriskofinternalinjectordeposit[Reid2014].
Ithasbeenpostulatedthatthisoccursduethehighdipolemomentofthemetalcarboxylatesaltsformed
bythereactionofacidandalkaliattractingittowardsclustersofwatermoleculesforminganinverse
micelle.Theformationoftheinversemicelleallowswater,metalcarboxylatesandotherhighlyionic
speciestoremainsolubleinthefueluntilitreachesanenvironmentthatchallengesitsstabilitysuchas
increasesintemperature,pressureandsheerforcesthatarefoundinhighpressurefuelinjection
systems[Trobaugh2013].

2.2.8Markers
Dyesaremainlyusedtomarkfuelforlegalreasonssuchasproofoftaxevasion,fueladulterationor
possiblytheft.Forexample,dieselfuelforoffroadusemaybesubjecttoreducedtaxationandcanbe
dyedtoenabledetectionofitsillegaluseinonroadvehicles.Dyescanalsobeusedtodifferentiate
brandedproducts.Azodyestendtobeusedforredsandorangeswhileanthroquinonedyestendtobe
usedforgreensandblues.Treatratesareusuallylessthan10ppm.
Insomecases,suchaswiththereddiazodyes,thedyecanberenderedcolorlesswithanacidoralkali
oritcanberemovedaltogetherusingactivatedcarbon.Alternativelychemicalmarkers,suchas((3
(secbutyl)4(decyloxy)phenyl)methanetriyl)tribenzenedevelopedbyDow,canbeusedinsteadofa
dye.Onceaddedtothefuel,thesemarkersaremoredifficulttoremoveandcanbedetectedusing
portablegaschromatographymassspectrometryinstruments.

2.2.9DeodorantsandReOdorants
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Deodorantsorodormasksmaybeemployedtotryandmaskthenaturalsmellofdieselfuelwhichis
oftenconsideredunpleasant.Againthisisbecomingmoreimportantasdieselpassengercarbecome
morecommon.Asanalternative,additivesareavailabletogivethedieselfuelanalternativemore
pleasantfragrance.Treatratesof10to20ppmareused.

3.AdditivestoImproveFuelStability
3.1Antioxidants
Antioxidantsblockcertainoxidationprocessesinthefuel,terminatingfreeradicalchainreactionsthat
leadtofuelinstability.Themostcommonlyusedantioxidantsarehinderedphenols.Theytypicallyare
usedintheconcentrationrangeof1080ppm.Withlegislatedreductionsinfuelsulfuradditional
hydrotreatingofdieselfuelhasbecomenecessary.Thiscanimprovefuelstabilitybyremoving
nitrogenandoxygencontainingcompoundsandsaturatingthemorereactiveolefiniccompounds,thus
reducingtheneedforantioxidants.However,ultralowsulfurfuelshaveshownatendencytoform
peroxides,thusconsiderationmuststillbegiventothecorrectchoiceofantioxidanttreatment.

3.2Stabilizers
Additivesofthisclassblockacidbasereactionsanothertypeofprocessesthatcancausefuel
instability.Thestabilizerstypicallyarestronglybasicamines,whichreactwithweaklyacidic
compoundstoformproductsthatremaindissolvedinthefuel,butdonotreactfurther.Examplesare
longchainparaffinicamines,cyclicaminesorothernitrogencontainingcompounds.Stabilizersare
usedintheconcentrationrangeof50150ppm.

3.3MetalDeactivators
Metaldeactivatorschelateheavymetalionspresentinfuel(copper,iron)thatcancatalyzereactions
involvedinfuelinstability.Examplesofmetaldeactivatorsares2(2hydroxyphenyl)benzoxazole,n,n'
disalicylidene1,2propanediamine,tetra(acetylacetone)pentraerythrityltetramineandhydroxyl
oximes.Theytypicallyareusedintheconcentrationrangeof115ppm.

3.4Dispersants
Dispersantsaresurfaceactivematerials,theydonotpreventthefuelinstabilityreactions,buttheyhelp
todisperseanyinsolubleproductsthatareformed,thuspreventingthemfromclusteringintoaggregates
thatcouldharmenginecomponents.Additivesarerarelyusedsimplytoactasdispersants,other
compounds,particularlydepositcontroladditives,thatarealsosurfaceactivewillusuallyprovide
enoughdispersantaction.

4.AdditivestoProtecttheEngineSystems
4.1CorrosionInhibitors
Corrosioninhibitorsareaddedprimarilytopreventcorrosioninthefueldistributionsystemas
discussedintheprevioussection.Protectingthevehiclefuelsystemisalsocriticallyimportant,
especiallyforthelatesttechnologyprecisionfuelinjectionsystems.Acorrosioninhibitoristhusoften
includedinmultifunctionaldieseladditivepackagestoensureprotectionofthevehiclefuelsystem.
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Selectionofadditivetypeandtreatrateisusuallydeterminedbyusingastandardrustpreventiontest
suchasASTMD665.Forthistestapolishedsteelspindleisimmersedinamixtureoffuelandwater
followingthetesttheappearanceofthespindlevisuallyassessed.

4.2InjectorCleanlinessAdditives
Depositformationondieselfuelinjectorshasbeenanissueforagreatmanyyears[Barker2011],
interestingly,attemptstousevegetableoilcausedsignificantdepositformation[Barsic1981].Particulate
matterfromthecombustionprocess,alongwithdegradationproductsoffuelandlubricant,can
agglomerateandadheretotheexposedsurfaceofthefuelinjector.Thiscanevenincludetheinjector
nozzlehole.Excessivedepositsmaycausedeformationintheinjectorspraypattern,orevencompletely
clogsomeofthenozzleholes.Theimpairedairfuelmixtureformationmayleadtoincreasedemissions
anddecreasedfueleconomy.Morerecentlydepositformationontheinternalcomponentsofthefuel
injectorshasbecomeaproblem.Theseissuescanbeaddressedbytheuseofinjectorcleanliness
additives,oftenreferredtoasdepositcontroladditives(DCA).Thesearesurfaceactivemoleculesthat
actasadispersantandalsotopreventdepositsadheringtotheinjectorsurfaces.Figure5provides
schematicillustrationofhowsurfaceactivemoleculescanformamonomolecularfilmarounddeposit
precursorparticlesformingamicellekeepingtheparticlesdispersedwithinthefuel.Metalsurfacesare
protectedbytheoleophilicgroupwhichrepelsthedepositparticleorthemicelleinthesamewayit
wouldrepelawaterdropletasillustratedinFigure5.

Fuel
Surfactant
molecule

Deposit
precursor

Metal surface
Figure5.SchematicrepresentationofDCAactingtodispersedepositsandprotectsurfaces

SomechemistriesusedasDCAsincludepolyamines,polyetheramides,succinimides,Mannichreaction
productsandquaternizednitrogencompounds.Afullerdiscussionofinjectordepositsandtheircontrol
canbefoundunderInjectorDeposits.

4.3LubricityAdditives
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Lubricityadditivesareneededtocompensateforthepoornaturallubricityofultralowsulfurfuels,
whichlosetheirnaturallubricatingpropertiesduringhydrotreatment.Lubricityadditivesarealso
surfaceactivecompoundscontainingapolargroupwhichisattractedtometalsurfacesandalong
oleophilictailthatensuressolubilityinthefuel.Theadditiveformsathinprotectivesurfacefilmon
metalasillustratedinFigure4.Thisfilmactsasaboundarylubricantwhentwometalsurfacescome
intocontactandassuchrequiresdifferentpropertiestothesurfaceactivecompoundsusedascorrosion
inhibitorsorDCAs.Butitshouldbenotedthatanumberoftheseothersurfaceactiveadditivescanalso
providesomelubricityenhancementifpresentinsufficientquantities[Fox2007].Biodieselfuelscanbe
themselvesveryeffectivelubricantsduetothepropertiesoffattyacidmethylesters(FAME)and/or
theeffectofcertaincommonbiodieselcontaminants[Knothe2005].
Anumberofvegetablesourcedaswellassyntheticcompoundsarecommonlyusedaslubricity
additives:
Monocarboxylicfattyacids(sometimesreferredtoasmonoacids).
AmidesReactionproductsofmonocarboxylicfattyacidswithanamine,suchasmono,dior
triethanolamine.
NonsyntheticestersEstersmadefromunsaturatedhigherorder(~C36)cyclicdicarboxylic
acidsknowncommerciallyasdimeracids.
SyntheticestersCompoundscontaininganestermoietyattachedtoapolyolefin.
Dimeracidsontheirowndidseesomelimitedapplicationaslubricityadditivesbuttheywere
associatedwithfuelinjectionpumpstickingandfiltercloggingproblems.
Monocarboxylicanddimeracidsusedintheabovechemistriesareoftenproducedfromtalloil,aby
productofpulpandpapermanufacturing.Talloilfattyacid(TOFA)ispreferredoverothervegetable
oilfattyacidsinpartbecauseofitsbetterlowtemperatureproperties.However,ithasbeenobserved
thatacidtypelubricityadditiveswillinteractwithbasiccompoundsuchassodiumhydroxideusedin
thefuelrefiningindustryandthismayreducethelubricityperformanceoffuelsreachingthecustomer
[Cook2012].

Additivechemistriescanbeusedindividuallyorincombination.Themonoacidtypeisparticularly
effectiveandistypicallyusedintheconcentrationrangeof1050ppminlowsulfur(<500ppmS)
dieselfuels.Esters,beinglesspolar,requireahigherconcentrationrangeof50250ppm.
ConcentrationsinULSD(<15ppmS)fuelsmaybehigher.
Theeffectoflubricityadditiveconcentrationcanshowastronglynonlinearbehaviorwhenmeasured
withsomebenchtestssuchastheHighFrequencyReciprocatingRig(HFRR).Thelubricityresponseis
oftenthoughnotnecessarilyalwayssimilartothatshowninFigure6.Eitherlittle(additiveC)oran
approximatelylinear(additivesAandB)improvementinlubricityisshownatlowtreatrates.Thisis
followedbyarapidimprovementinlubricityastreatratefurtherincreases.Additionalincreasesintreat
rateagainshoweitheralinearorlittleimprovement.

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HFRR WSD, m

600

500

400

B
C
A

300
0

50

100

150

200

250

300

Treat Rate, mg/L

Figure6.EffectoftreatmentrateonHFRRlubricity

Amodelforthisbehaviorhasbeenproposed[Fox2007]thatconsidersadditiveswithantiwear
propertiestobeinequilibriumwithanyadditivesadsorbedasafilmonthemetalwearsurfaces.Atlow
concentrationsoflubricityenhancingadditives(othersurfaceactiveadditivescanalsoprovidea
lubricityenhancement),thecoverageofwearsurfacesisincompleteandantiwearactioncanbepoor.
Astheconcentrationlevelreachesthepointwerefullcoverageofthewearsurfacebytheadditiveis
possible,thesurfaceweardropsquickly.Additionalincreasesinadditiveconcentrationhavelittleorno
effect.
Thismodelalsoseemstoaccountforapparentdifferencesinthetreatmentrateexpressedasmassof
additiveperunitvolumeoffuel,mg/dm3forexamplethedifferencebetweenadditivesBandCin
Figure6isanexample.Astreatrateincreases,theconcentrationofpolargroupsthatareabletoattach
themselvestowearsurfacesandallowadditivemoleculestoperformtheirantiwearfunctionalso
increases.Heavieradditivemoleculeswithfeweractivepolargroupspermassofadditivethusneed
highertreatrateswhenexpressedinunitssuchasmg/dm3.Whenadditivetreatratesarerather
expressedintermsofmolarconcentration(mole/dm3),theresponsebehaviorofadditiveswithvery
differentmolecularweightsandtotalnumberofpolargroupspermoleculeseemstobeverysimilar.
Theonsetoftherapidincreaseinlubricitystartsatabout0.0020.004mole/dm3andiscompleteat
about0.0040.006mole/dm3.Bycomparison,whenexpressedasmg/dm3,theresponsedepends
stronglyontheadditive.Theonsetoftherapidincreaseinlubricitycanstartbetween100700mg/dm3
andbecompleteat3001300mg/dm3[Fox2007].
Itwasnotedthatthenumberofpolargroupspermoleculefortheadditivesthatweretestedhadlittle
impactonthemolarconcentrationatwhichlubricitystartedtorapidlyincrease[Fox2007].The
additivesusedinthisworkcontainedfrom2toasmanyas20polargroupspermolecule.Thissuggests
thatonlyasmallnumberofpolarsitesavailableoneachmoleculebindtothesurface.Therestofthe
polargroupsformpartofthetail.Itisnotclearhowgeneralthisconclusionisasthenumberof
additivestestedwaslimited.
Someproblemsassociatedwithlubricityadditiveshavebeenreported:
Problemswithinlineinjectionpumpswasexperiencedinthe1980sinEurope[Mikkonen1987]
[Caprotti1998].Depositsformedontheplungers,barrelsanddeliveryvalvesofsomeinline
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injectionpumpsafter5,00020,000kmofdriving,causingstickingofplungerswhenfuel
containinglubricityadditivewasused.Smallamountsofengineoilmixedwithdieselfuelinthe
inlineinjectionpumpandachemicalreactionbetweenthefuellubricityadditiveandtheengine
oilwasidentifiedasthecauseofthedeposits.Asimilarproblemoccurringin1996was
demonstratedtobearesultofaninteractionbetweendimeracidlubricityadditivesandthe
lubricatingoil[Mozdzen1998].
Fuelfilterpluggingaftertheintroductionoflowsulfurdieselfuelswasanotherproblemthatwas
linkedtosometypesoflubricityadditives[Caprotti1998].Ithasbeensuggestedthatareaction
betweendimeracidsandoverbaseddetergentsfoundinlubricatingoilthatentersthefuelsystem
throughtheoillubricatedfuelinjectionpumpresultedintheformationofthefilterclogging
deposits[Wooten2003][Fang2003].
Fuelinjectordepositformationhasalsobeenlinkedtoacidbasedlubricityimproveradditives
whenusedincombinationwithcertainotherfueladditives[Ullmann2008].Inthepresenceof
alkalimetalcontaminationofthedieselfuelthenacid/basereactionscanoccurasdiscussed
previouslyforcorrosioninhibitors.
Toavoidsuchproblems,additivesuppliersandfuelproducersuseaseriesofteststodemonstratethat
additivesdonotcauseunexpectedvehicleproblemswhenmakingdecisionsaboutlubricityadditive
chemistryandtreatrates[Batt1996][Mozdzen1998].Thesetestsincludeinjectorpumprigtestsand
lubricatingoilcompatibilityteststodemonstratenoharmperformanceonthevehicle.Compatibility
withotherfueladditivesandtheeffectonstoragestabilityofthefuelisalsochecked.
Concernsandproblemsrelatedtofuelhandlingissueslongbeforethefuelreachesthevehiclesfuel
tankcanalsohaveimpactsonthefinaldecisionofwhattypesofadditivestouse.In2004,justbefore
thestartofCaliforniasdieselfuellubricityrequirementandtheinclusionofa520mHFRRwearscar
diameterinASTMD975,therewasconcernthattheincreaseduseofsometypesoflubricityadditives
thatwouldbeusedtomeetthisrequirementcouldleadtocontaminationofjetfuelwiththelubricity
additiveifjetfuelimmediatelyfollowdieselfuelthroughadistributionpipeline[CARB2004][CARB
2005].TwoknowncasesofthisoccurredinCaliforniainthedecadebefore2004wherethejetfuelhad

tobedivertedtootheruses[CARB2004a].Thelubricityadditivesthatwereusedfordieselfuelwerenot
approvedforjetfuelandtherewasconcernthatthiswouldleadtounexpectedproblemsassociatedwith
jetfuel(jetfuellubricitycanbeimprovedwithorganicacidbasedcorrosioninhibitors[Peyton2002]).
Thecontaminationwouldoccurthroughwhatisreferredtoastrailback.Whendieselfuelis
transportedthroughthepipelinesystem,becauseitisasurfaceactivecompound,someofthelubricity
additivewouldadsorbontothepipelinewalls.Ifjetfuelwasthentransportedthroughthesamepipe
immediatelyafterwards,theadsorbedlubricityadditivewouldslowlybereleasedintothejetfuel.Asa
resultsomepipelinesissuedeitheranoutrightbanontheshipmentofdieselfuelcontaininglubricity
additivesorrequiredthatthelevelandtypeofadditivebethesameasthatshippedinthepast.Forfuel
producersaffectedbythispipelinedecision,theadditionoflubricityadditivetothefuelnowneededto
becarriedoutatfuelterminalsinsteadoftherefinerywhereithadbeendoneinthepast.Thispractice
hasnowbecomecommonintheUSA.
Addinglubricityadditiveatfuelterminalscanimpactthechoiceofadditivecomposition.Terminal
additizationisusuallydonebyinjectingtheadditiveintothefuelasitenterstheterminalorattherack
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asthefuelisbeingloadedontotrucks.Fueltemperatureatthesepointstendstobemuchlowerthan
thatatarefineryandensuringthattheadditiveisproperlyblendedintothefuelandthatthissolutionis
stablebecomesaconcernespeciallywhenambienttemperaturesarelow.Thismayrequiresuch
additionalmeasuressuchasreformulationoflubricityadditiveconcentrates(additiveplusasolvent)to
ensureastablesolutionforsufficientlylongperiodsoftimeatlowambienttemperaturestoallowgood
mixingintodieselfuel[Dietz2007][Schwab2006][Breakspear2007].However,ifthelubricityadditiveis
formulatedaspartofamultifunctionalpackagethenthiswillbeconsideredaspartofthepackage
formulation.

5.AdditivestoInfluencetheCombustionProcess
5.1IgnitionImprovers
Ignitionimproveradditivesareusedtoimprovetheignitionquality,orreducetheignitiondelayi.e.the
timebetweenwhenfuelisinjectedintothecombustionchamberandwhenignitionoccurs.TheCetane
Number(CN)isthemostwidelyacceptedmeasureofignitionqualityandbecauseignitionimprovers
areusuallycharacterizedbythefactthattheyincreaseCNtheyareoftenreferredtoasCetaneNumber
Improvers(CNI).Raisingthecetanenumberofthefuelcanfacilitatequietercombustionandlower
emissions.Anadditivethatwilldecomposereadily,atelevatedtemperatures,toformfreeradicalsthat
willacceleratetheoxidationofthefuelislikelytobeaneffectiveignitionimprover.Overhalfa
centuryago,manychemicalcompoundsincludingalkylnitrates,ethernitrates,nitrosocompoundsand
peroxidesweretestedfortheireffectivenessasignitionimprovers[Robbins1951].
2Ethylhexylnitrate(2EHNorisooctylnitrate)hasbecomethemostcommonignitionimproverdue
toitslowproductioncostsandgoodresponseinawiderangeoffuels.
2EHNisusedatdoselevelstypicallyvaryingfrom0.05%to0.4%(m/m),toyieldabout3to8cetane
numberimprovement.Theincreaseincetanenumberisgreaterforafuelwhosenaturalcetanenumber
isalreadyhigh.Theincrementalincreasebecomessmallerasmore2EHNisadded.Thisisillustratedin
Figure7whichshowsresponsecurvesforseveralfuelsconsistingprimarilyofalkanesandaromatics
[Gairing1995].Thefuelswiththehighestnaturalcetanenumber(highalkanes,lowaromatics)showthe
bestresponseto2EHN.Correlationstocalculatethecetanenumberincreaseasafunctionof2EHN
concentrationcanbefoundintheliterature[Sobotowski1995][Thompson1997].

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Figure7.EffectofEHNadditiononcetanenumberincreaseforfuelswithdifferent
aromatic/alkaneproportions

Anothercategoryofcetanenumberimproversareperoxidebasedcompounds,forexampleditertiary
butylperoxide(DTBP).Theireffectisalsostronglydependentonfuelcomposition[Clothier1993]
[Clothier2000].Thesehavebeenshowntobelesseffectivethan2EHN[Aradi1995][Goodrich1998]
[Schwab1999]andaregenerallymoreexpensive.Peroxidebasedcetanenumberimproversareusedin

CaliforniabecauseCARBdieselfuelhasamaximumnitrogencontentspecificationwhichlimitsthe
amountof2EHNthatcouldbeaddedtothefuel.
Nitratebasedcetaneimproveradditivessuchas2EHNcanhaveadetrimentaleffectonthethermal
stabilityofdieselfuel[Bacha1998].Theautodecompositiontemperatureof2EHNisabout155C,just
abovethe150CatwhichthermalstabilityismeasuredwithASTMD6468.2EHNdecomposition
productsandtheirinteractionwithinsolubleprecursorscanpromotefuelinstability.Thisisan
especiallyimportantconsiderationforfuelsthathaveathermalstabilityrequirement,suchastheNIST
definedpremiumdieselintheUSA.Carefullyselectedfuelstabilizeradditivesmayneedtobeusedin
conjunctionwithnitratebasedcetanenumberimproveradditivestoavoidfilterpluggingproblems.
Peroxidebasedcetaneimprovers,suchasDTBP,havemuchlessofaneffectonthermalstability
[O'Rear2004].

Ithasbeenshownthatcetanenumberimproveradditivescanhaveadetrimentaleffectonfuellubricity
measuredwiththeHFRRtestmethod[Selvidge2006].Basedonthisobservation,increasedamountsof
lubricityadditivemayberequiredwhen2EHNisusedwhenlubricityismeasuredonlybytheHFRR
test.ThiseffectmayonlybeanartefactoftheHFRRtestas2EHNhasnotbeenshowntodegrade
lubricitywithinjectionpumprigtests.

5.2SmokeSuppressants
Blacksmokeemissionscanbereducedthroughtheadditionofcertainorganometalliccompoundsthat
actascatalysts[Saito1973][Howard1980].Bariumorganometallicshavecommonlybeeninvestigated
[Norman1966][Golothan1967]andwereusedoccasionallyassmokesuppressantsintheUSAduringthe

1960s.TheywerelaterbannedbytheEPA,becauseofthepotentialhealthhazardofbariumemissions.
Othermetalscanbealsousedassmokesuppressants,includingcalcium,iron,cerium,orplatinum.
Whiletheycanbeeffectiveatreducingsootemissions,theseadditivescanleadtosignificantdeposits
inthecombustionchamberandhavelongtermimpactsonengineperformance[Brandes1970].Their
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abilitytoreducesootemissionsisatleastpartiallyoffsetbythefactthat8595%oftheadditiveis
exhaustedfromtheengineandthereforecontributestototalPM(massandnumber).Astighter
emissionslegislationhasnecessitatedalowermassofsootemissionsthecontributionofashfroma
smokesuppressanthasbecomemoresignificant.Itisthusmoredifficulttoshowabenefitfromsome
suppressantadditivescomparedtothedetrimentaleffectsofincreasedmetalashemissions.Concern
overtheemissionsofmetalparticleshasresultedinthebanningofmetallicadditivesfromdieselfuelin
manyregionsincludingtheUSA,EuropeandJapan.

5.3CombustionCatalysts
Combustioncatalystsarepromotedasawaytoreducefuelconsumptionandemissionsthroughan
improvementincombustionefficiency.Theseadditivesfallintotwogroups:organometalliccompounds
andveryfinedispersionsofinorganicmaterialwhichisoftenreferredtoasnanoparticlesornano
additives.Theorganometalliccompoundsarenotstrictlycatalystswithinthemselves,buttheyoxidise
duringthecombustionprocesstoproducethecatalysts.Theinorganicproductsofcombustionareagain
initiallyverysmallparticlestheseparticlesmayagglomeratetoformlargerparticlesormaybe
containedwithinsootparticles.Variousmetalshaveattractedtheattentionofresearchers:aluminium,
iron,boron[Mehta2014],manganese,magnesium[Keskin2011],cerium[Wakefield2008],bimetallic
platinumandcerium[Valentine2000].
Onebenefitthatiscommonlyclaimedfortheseadditivesisthattheyimprovecombustionefficiency.
However,itmustberealizedthatthecombustionefficiencyinmoderndieselenginesistypicallybetter
than99%,thusleavingverylittlepotentialforfurtherimprovement.Severalstudieshaveshownthatin
somecases,thesematerialscanprovideabouta57%improvementinfueleconomy[Haring1993][Kelso
1990][Valentine2000].Someauthorsfoundbetterresponseinolderenginesandinvehiclesoperatingin

busycitycenterswithlowdailymileage[Hayat2000].However,otherstudiesutilizingveryold
technologyenginesreportedthattheuseofvariouscombustioncatalystsmadealmostnochangeinfuel
economyorexhaustsootlevels[Moulton1984].
Anotherpotential,andperhapsmorelikely,mechanismbywhichtheseadditivesoperateisthrough
reductionorcleanupofdepositsinthecombustionchamber,turbochargerandheatexchangersin
contactwithexhaustgas.Theseadditiveswouldsurvivethecombustionprocessandcouldprovidea
cleaningbenefittohightemperatureenginecomponentsanalogoustothatofdetergentadditivesusedto
cleanfuelinjectors.Whileresearchonthisaspectofcombustioncatalystsisscant,thereisevidence
thatthismayinfactbethemostsignificantbenefit.Inonetrialonamarinevesselwithalowspeed
twostokedieseloperatedonbunkerfuel,thevesselwasabletooperateforaperiodof3months
withouttheneedforcleaningtheturbocharger[Cliber2008].Withoutthefueladditive,theturbocharger
wouldhaveneededtobesoftblasteddailyandwaterwashedmonthly.Additionally,heatexchangers,
pistonringsandvalveswerereportedtoshownodeposits.Fuelconsumptionbenefitsof5%were
claimed.
Combustioncatalyststypicallyrequireseveralhundredhoursofengineoperationwiththefueladditive
beforesignificantbenefitsareobserved.Thislongtimedelaymayberequiredtocleanawayexisting
depositsortocoattheinsideofthecombustionchamberwiththecatalyst.Inonestudy,thenetresult
wasareductioninignitiondelayandthebenefitswerelargelyexplainedthroughthelattermechanism
[Caton1991].Therewasnosignificantimpactonheatreleaserateafterignition.
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Somehaveevenclassifiedorganometalliccombustioncatalystssimplyascetaneimprovers[Suppes
1996],assuggestedbythefactthattheyreduceignitiondelay.Thefuelconsumptionbenefitsand

emissionreductionbenefitsarealsoverysimilartothosesometimesreportedforcetaneimprover
additives.Themaindrawbackoverconventionalcetaneimproversisthatseveralhundredhoursof
operationarerequiredbeforetheimpactofcombustioncatalystsisobserved.
Stillanothermechanismsuggestedbyacombustioncatalystsupplieristofacilitatechemicalreactions
thatdepositpolymercomplexesofphosphorusandnitrogenonthesurfaceofferrousandnonferrous
metals(inadditiontocatalyzingthecombustionprocess).Thesecomplexesareclaimedtosmoothand
passivatethemetalsurface,increasereflectivityandreduceoxygenreactivity.Whiletheactual
mechanismoftheadditivehasnotbeenclarified,testsonanEMDlocomotiveengineshowedfuel
consumptionimprovementsof815%,someNOxreductionsatnotches2,3and4butalsosignificant
PMincreasesatallnotchsettingsrangingfrom40170%[EPA2005].ThePMincreaseddespite
significantdecreasesinexhaustopacity.DutycycleweightedPMresultsdidhoweverremainbelowthe
Tier0locomotiveemissionstandarddespitethelargeincrease.
OneinterestingobservationfromthisstudywasthatSO2emissionsincreasedby50%aftertheengine
wasrunwiththeadditive.Sincethefuelsulfurleveldidnotchange,thiswouldsuggestthateither
engineoilconsumptionincreasedbymorethan50%(thisistheonlyothersourceofsulfur)orthatthe
lubricatingoilwaschangedtoonewithahighersulfurlevelinthetimebetweentests.ThefactthatPM
emissionsincreasedsubstantiallywhileopacitydecreasedwouldbeconsistentwithanincreaseinoil
consumption.Opacityismainlyaffectedbycombustiongeneratedsoot,whilePMwouldrepresent
combustiongeneratedsootandorganiccarbon(thelatterbeingknowntooriginatelargelyfromthe
lubricatingoil).
Theformationofphosphatedepositsinthecombustionchamberresultingfromanyadditiveswouldbe
asignificantconcernoverthelongterm.Depositformationintheupperlandandringgrooveareaof
thepistoncaninterferewiththeringactionandeventuallyleadtoringsticking.Phosphatesfromthe
engineoilareknowntocontributetodepositsintheupperlandandtopringgrooveareaofthepiston
[Smith2002].Thesedepositscanresultinincreasedoilconsumption[Burnett1992][McGeehan1983]
[Schetelich1986]andeventuallyinreducedenginedurabilityandperformance.Thepresenceof

phosphorousaknowncatalystpoisoninadditiveswouldalsobeofconcernforenginesusing
catalyticaftertreatmentdevices.
Itshouldalsobenotedthatinmanyjurisdictionstheadditionofmetalstodieselfuelisnowprohibited
duetotheadversehealtheffectsofparticulateemissions.

References
Aradi,A.,Ryan,T.,1995.CetaneEffectonDieselIgnitionDelayTimesMeasuredinaConstantVolumeCombustionApparatus,SAE
TechnicalPaper952352,doi:10.4271/952352
Arnault,N.,Ryan,T.,2014.CetaneEffectonDieselIgnitionDelayTimesMeasuredinaConstantVolumeCombustionApparatus,SAE
TechnicalPaper952352,doi:10.4271/952352
Bacha,J.D.,D.G.Lesnini,1998.DieselFuelThermalStabilityat300F,Proceedingsofthe6thInternationalConferenceonStability,
HandlingandUseofLiquidFuels(H.N.Giles,Ed.),U.S.Dept.ofEnergy,Washington,DC,USA,Vol.2,671684,
http://www.fischertropsch.org/DOE/_conf_proc/MISC/Conf971014Vol%202/971014Vol
2,%20Part%203,%20Pages%20671%20%20773.pdf

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