MARINE ADDITIVES SPECIAL

BunkerWorld August/September 2005 page 12

SSpecifications for the various gradesof bunker fuel define the fuel's han-dling characteristics and also help

ensure performance in diesel engines, asmeasured by parameters such as operat-ing efficiency and emissions levels.

Common specifications include physicalproperties such as density, viscosity, flashpoint temperature and pour point temper-ature, plus chemical properties such as sul-fur content, carbon residue, water and sed-iment content, and ash content.

Certain metal species such as sodiumand vanadium are limited because elevatedlevels of these metals can result in severedamage to engines.

There are other oil properties notaddressed in these specifications that alsocan have an impact on overall fuel salability,handling characteristics and performance.

The first is fuel oil asphaltene stability,an important parameter used in blendingdifferent fuel oils to produce a particulargrade. The second is hydrogen sulfide, orH2S content. This is an important issuebecause of the safety implications due tothe potential for human exposure to thisdangerous gas.

Finally, there is a growing awareness offuel odor issues, beyond those related tothe distinct smell of low levels of H2S inthe fuel.

There are also several types of chemicaladditives that can be used to maintain orimprove bunker fuel quality. Below, wedefine some key additive categories, anddiscuss how these additives can impactbunker fuel quality.

Pour Point DepressantsParaffinic crude oils can produce fuel oilblending stocks that contain heavy waxes.These waxes begin to form insoluble pre-cipitates when cooled, which eventually

form large wax crystals. These crystals cancause the oil to stop flowing as the tem-perature of the fuel is reduced. It shouldalso be noted that even if the oil flows, itcan become very viscous at temperaturesabove the pour point.

Pour point depressants work by modi-

fying the wax crystal structure so thatsmaller, irregularly shaped crystals areformed upon cooling. Modifying the waxcrystals prevents the oil from gelling andthus provides better handling propertiesof the fuel at lower temperatures.

Figure 1 shows the typical response ofcrude oil or heavy fuel oil viscosities totreatment with heavy fuel pour pointdepressant chemicals. Bunker fuels usedin cold climates especially can benefitfrom the use of this type of additive.

H2S ScavengersAlthough not a typical quality specifica-tion, the H2S content of bunker fuel is aproperty that most fuel suppliers monitorbecause of safety, corrosion and odorissues. There are a number of terminal,port authority and company H2S specifi-cations used in the industry. If H2S levelsare above specifications, chemical scav-engers can be used to reduce the level tobelow safe limits.

By reducing hydrogen sulfide levels instorage tank vapor space, H2S scavengersalso minimize the rate of bisulfide corro-sion reactions that often reduce the usefullife of carbon steel fuel oil storage tankroofs. Reduced fuel odor can be an addi-tional benefit.

Dewatering AdditivesWater in the fuel oil is an unwanted con-taminant. It has no combustion value andmay also contain dissolved inorganicmaterials that can form deposits in thediesel engine. Dewatering additives canbe used to help remove water from thebunker fuel.

The water will fall to the bottom of thestorage tank where it can be drained out ofthe tank. Leaving the settled water in thetank bottom can result in biological activi-ty that can add unwanted materials to thebunker fuel.

The dewatering procedure can takesome time as the water droplets need tocoalesce and form larger droplets that willeventually drop through the oil phase.Once this has occurred the dry fuel can betransferred on specification.

Asphaltene StabilityImprovers

These large molecules are stabilized in theoil by a complex system of resinmoleculesThe traditional "spot" test isused by blenders to measure heavy fuel oilstability. However, it is not a very repro-ducible method in that the spot test ratingsmay vary depending on subjective inter-pretations of the test results. Newer meth-ods have been developed that give moreobjective results and that give more infor-mation about the asphaltene stability of agiven fuel oil blend.

For example, Figure 2 shows some typ-

ical results from Baker Petrolite's ASITSMAsphaltene Stability Index Test method.This test procedure involves titration ofthe bunker fuel oil sample with asphaltenenon-solvent until the asphaltene floccula-tion point is reached.

The Asphaltene Stability Index, deter-mined by the position of the inflectionpoint in a plot of near-infrared laser trans-mittance vs. volume of solvent added, iscorrelated to fuel oil stability. TheseASITSM plots clearly show the effects ofdifferent blending component ratios onfuel oil stability.

If a fuel oil is unstable as measured byspot or ASIT tests, asphaltene stabilityimprover additives can be used to restorethe desired long term asphaltene stability inthe fuel. The effects of these additives can bemeasured in the fuel oil stability tests.

Metal DeactivatorsVanadium and sodium are two metalsthat can cause significant problems inbunker fuel combustion. High levels ofthese metals in the fuel can result in theformation of adherent slags that can causefouling and corrosion problems in dieselengine cylinders, valves, turbochargersand exhaust gas systems.

In addition, vanadium based slagdeposits can also catalyze formation of sul-fur trioxide (SO3) from sulfur dioxide(SO2) in the exhaust gas. In the presence ofcondensed moisture, SO3 reacts to formsulfuric acid, which can cause corrosion inexhaust gas handling systems.

Additives are available that can mini-mize the harmful effects of vanadium andsodium contaminants in the fuel oil. Theseadditives typically contain magnesiumbased compounds that prevent the forma-tion of adherent, corrosive slags andreduce the catalytic effects of vanadiumcompounds on SO3 formation.

Odor Control AgentsFuel odor is becoming a more prevalentissue in the bunker fuel market. Manycompounds can impact odors to the fuel atvery low levels. Table 1 shows some typ-ical compounds and their threshold limits

for odor detection. Low levels of H2S or mercaptans are typ-

ically the problem. However, as more non-typical blend components are used to makevarious bunker fuel grades, there areincreasing instances of the presence of othercomponents such as amines and olefins thatcan also impart odors to the fuel. Maskingagents have been used, but these requirehigh dosages and merely impart another,more pleasant odor to the fuel.

Newer odor control agents take a differ-ent approach. They act in a number ofways to chemically neutralize the odors. Itis important that these odor control agentsare used only after the levels of any dan-gerous odorous materials, such as H2S, aretested and found to be below levels consid-ered to be harmful.

SummaryMaintaining desired bunker fuel oil qualityis becoming a more challenging task, as theresidual oil blend components change, andas new quality specifications are put inplace. Chemical additives can be animportant and economically attractivemethod for ensuring that specifications aremet by the bunker fuel blender and suppli-er, and that the desired level of fuel per-formance is experienced by the end user.

US-based Baker Petrolite Corp. was among the first companies to realise the benefits of developing additives to ensure that bunker fuel received by the end user can be tailored within within sales specifications,

and have suitable handling and performance characteristics. Mike Nicholson, International Manager for Baker Petrolite’s ‘Prepared to Respond® Services’ highlights the vast potential of these products.

Additives improve fuel oil properties

Pour Point Additive Effect on Viscosity

1 10

100 1000

10000 100000

1000000

15 25 35 45 55 65 75 85 95 105 115 125 135

Temperature (Deg.

Log Viscosity (c

507 cp

Untreated =

150 ppm Dose =

250 ppm Dose = 126 cp

West African Crude

Figure 1: Viscosity vs. Temperature Profileof a Paraffinic Crude Oil Treated with Pour

Point Depressant Chemical

Copyright 2003 Baker Hughes Incorporated

ASITSM Asphaltene Stability Index Test

0

10

20

30

40

50

60

70

0.00 50.00 100.00 150.00 200.00 250.00 300.00

ASIIn

tens

ity

Crude 1Crude 2Crude 3Crude 4Crude 4 + Asphaltene Stabilizer

High FoulingPotential

Medium FoulingPotential

Low Fouling Potential

Additives can greatlyincrease the stability of an oil

Figure 2: Example Output from ASITAsphaltene Stability Index Test

Odor Issues

Odor Agent Threshold Detection Limit H2S 0.0047 ppm Methyl Mercaptan 0.0021 ppm Ethyl Mercaptan 0.001 ppm n - Propyl Mercaptan 0.00075 ppm n - Butyl Mercaptan 0.001 ppm Carbon Disulfide 0.21 ppm Methyl Alcohol 100 ppm Ammonia 46. ppm

Table 1: Potential Odor-CausingCompounds in Bunker Fuel Oils

References(1) Nomura, H.; Nagasawa, T. and Yoshida,E., "Development of Evaluation Methodsfor Stability of Marine Fuels," MarineFuels, ASTM STP 878, C. H. Jones, Ed.,American Society for Testing and Materi-als, Philadelphia, 1985, 215.

Mike Nicholson’s bio

p12-15.qxd 12/08/2005 15:22 Page 1

Bunker World August/September 2005 page 13

VVancouver's Catalyst Energy Inc.has just completed a series of testsof its unique fuel additive,

CombustAll, on the carrier M.V. Skaubrynon a sailing between Vancouver andTokyo with some promising results.

The additives manufacturing companywas delighted with the tests. "From theengine fuel flow meters, the engine wasdefinitely using less fuel," company presi-dent Dana Way told Bunkerworld, puttingthe fuel saving at 3.5%.

"The results were very encouraging -the fuel savings alone will offset the cost of

using CombustAll, added Wade."CombustAll is designed to reduce fuel

consumption and emissions of particulatematter, carbon monoxide (CO), and nitro-gen oxides (NOx), and works by changingthe combustion chemistry of the fuel -whether it be diesel or heavy fuel oil.

In this test, CombustAll was addeddirectly into the fuel supply of theSkaubryn's 15,200 hp main engine burn-ing IFO380 heavy fuel oil and emissionssamples were taken by analytical sam-plers at the main engine exhaust and atthe ship's stack.

The tests were conducted with the sup-port of the Port of Vancouver and localcompany Seaboard International

Shipping, owners of the Skaubryn."Vessel emissions is the focus - reduc-

ing the ship's environmental footprint,"Bruce Webster, Seaboard's Manager forShip Operations, told Bunkerworld.

"We want to be pro-active and get awayfrom the old image of shipowners as pol-luters," he added.

For Seaboard, reducing fuel consump-tion and emissions was a logical step. "It'sabout cleaning up the engines and makingthem more efficient," Webster said, whonoted that Seaboard is currently consider-ing the regular use of CombustAll.

The latest test buildson earlier tests conductedon the Skaubryn inMarch and April, carriedout by two independenttesting companies on theship's three generatorengines, which burn ablend of IFO180 fuel oiland marine diesel oil(MDO).

Results from the testsshowed that CombustAllreduced fuel consump-tion by 2.75%. Just as cru-cially in times ofincreased environemntalscrutiny, emissions ofparticulate matter werereduced by 95%, CO by19%, and NOx by 11.5%.

Total emissionsreductions are achievedby two means: reducedfuel consumption; andthe catalytic effect on thecombustion action. Forexample, the 11.5%reduction in NOx emis-sions from the generatorengine tests was theaggregate of 2.75% lessfuel burnt and 8.75% cat-alytic effect.

Combustall does notdirectly target sulphur oxides (SOx), so inthis case SOx emissions were reduced bythe same amount that fuel consumptionwas reduced.

Based on these results, and the ship'stypical movements over the course of ayear, CombustAll would reduce totalemissions in Canadian waters by 3.5 mt of CO, 2 mt of NOx, and 0.62 mt ofSOx, according to Catalyst Energy's calculations.

The data from the latest test on theSkaubryn's main engine is still beinganalysed to assess the catalytic effect.Based on the just the fuel saving of 3.5%,however, Catalyst Energy estimates thatemissions over the course of the year for

bunkerwwoorrlldd

Canada’s largest and busiest Port is teeming with activity.

Much of that activity is wildlife going about its business.

The Port of Vancouver understands that we need to preserve

our environment. We work to ensure accountability of our Port

partners and tenants to protect the delicate balance of marine

and wildlife that thrive in our busy Port. As we continue

to grow, we are committed to work with the marine industry

to reduce air emissions associated with the movement of cargo

and passengers. We are dedicated to protecting and preserving

the natural environment. Together with our partners,

we are working to keep the Port of Vancouver sustainable.

This is how we maintain our reputation as one of the cleanest

and environmentally innovative Ports in the world. If you want

to learn more about our initiatives call us at 604-665-9177.

Or visit www.portvancouver.com

BUSY CRANES ARE A SIGN OF A HEALTHY PORT.

Vancouver’s Catalyst Energy Inc. has just completedsuccessful tests of its fuel additive, CombustAll, on thecarrier M.V. Skaubryn to the delight of the company’s

President and the Port of Vancouver. Guy Wilson-Roberts,from Bunkerworld’s Vancouver bureau, takes up the story

Canadian additives proveeco-friendly - and cheaper

Catalyst Energy president Dana Way (right) overseesemissions data collection onboard the M.V. Skaubryn

p12-15.qxd 12/08/2005 15:22 Page 2

MARINE ADDITIVES SPECIAL

Bunker World August/September 2005 page 14

SShip management today is faced withthe escalating challenge of risingcosts and increasing regulation -

and much of the focus centers on fuel. The International Maritime

Organization (IMO) MARPOL Annex VIemissions reduction mandate, combinedwith moves by the European Union, theU.S. and other countries are destined tohave a significant impact on the entiremaritime cost structure.

In addition, new engines, pollutioncontrol devices and lower sulfur fuelscould reduce fuel economy and efficiency,thus putting further pressure on Maritimeoperations.

Liquid fuel catalyst One of the key problems facing shipowner/operators will be meeting regula-tory requirements while keeping costsunder control. Recently, a liquid fuel com-bustion catalyst has been introduced thatpromises to solve these problems.

The product, Green Plus, developed byBiofriendly Corporation in the UnitedStates, is a liquid combustion catalyst thatcan be added to all grades of marine dieseland heavy fuel oil to improve fuel econo-my and significantly lower emissions.

Long term ocean-going test results andcertified independent laboratory reportshave verified fuel economy improvementsof 4-7% and emission reductions ofNitrogen Oxides (15-25%), Sulfur Oxides(10-25%), and Particulate Matter (10-20%).

Not a typical additiveThe secret behind these results lies in thefact that Green Plus is a true combustion

catalyst, not a typical additive. Additiveschange the chemical composition of thefuel, whereas a catalyst does not; it simplyenhances the combustion process toachieve more complete combustion.

It does this by working at the molecular

level to "unbundle" the tangle of complexhydrocarbon molecules that make upmarine fuels. This unbundling allowsmore oxygen to reach the fuel and thus itburns more completely.

With more oxygen available to the fuel,more energy is being released more quick-ly at the initiation of the burn when thepiston head is at top center. In addition,the catalytic oxygenation allows the fuel toburn more rapidly and thoroughly to pro-vide greater thrust and hence convertmore energy to work. The more complete,

more linear burn, results in a "dominoeffect" - more horsepower, more torque,less fuel consumed and less emissions outthe stack.

Independent testing has confirmedincreases of 10% in horsepower and

torque as well as 10% lower exhaust tem-peratures, which clearly signal a betterconversion of energy to work. In boiler-based engines, Green Plus allows theair/fuel mixture to be adjusted to decreasethe amount of fuel required to achievesimilar performance levels.

Long Term Tests ConfirmResults

Recently, Biofriendly completed a multi-year test on a 45,000-tonne container ves-sel with a major shipping company com-

Fuel consumption and air emissions currently top the agenda for top shipoperator. Tests that reveal a dramatic fall in both through the application of one

combustion catalyst should raise more than a few eyebrows. US-based Bio-Friendly's product Green Plus is a true combustion catalyst, not a typical additive

- enhancing the combustion process to achieve more complete combustion

A catalyst for a change of mindset

caption

As the implementation date of theworld's first Sulphur Emissions

Control Area (SECA) nears, suppliers andshipowners are increasing their focus onthe practical requirements involved inmeeting the much-publisised regulations.

An array of outstanding technicalquestions remain in terms of how bunkersuppliers and ship operators will manageto meet the IMO legislation MARPOLAnnex VI's measures for Sulphur Oxide(SOx) capping at 1.5%.

However, a solution to one increasing-ly complex and potentially costly dilem-ma facing ship operators - that of alter-nating marine lubricants when switchingfuel tanks upon entering and departingSECAs - may be at hand, according to oneUK additive manufacturer.

Technical experts have raised aware-ness about the effects of using LSFO on anengine's lubrication system, but compara-

tively little attention has been given to theissue of lubrication when using LSFO.

Most solutions to the problem havecentred around the development ofmarine lubricants specifically designedfor use with LSFO, but Infineum MarineAdditive Technology Group (Infineum)says there is an alternative.

One of the main performance featuresof marine diesel cylinder lubricants(MDCLs) is to provide protection againstcylinder liner corrosive wear from sul-phur acids produced when fuel oil iscombusted in a marine cross-head engine.

Most 70 base number (BN) MCDLproducts currently on the market havebeen developed on the basis of fuel oilwith a sulphur content in excess of 3%and an MCDL feed rate of 0.7-1.5 g/kWh.

The implementation of a 1.5% cap onsulphur content means that changes toMDCL quality and/or feed rates are nec-

essary to avoid over-lubrication and theformation of calcium carbonate depositson the piston that may lead to pistoncrown burning, bore polish and/orscuffing.

Meanwhile, marine lubricant manufac-turers have been developing new lubri-cants specifically designed for use inengines burning LSFO.

One operator, Wallenius Wilhelmsenhas adopted a policy of burning LSFO asstandard. As such, its lubrication man-agement is quite straight-forward.Others, however, have installed dual fueland lubricant storage systems to copewith the changes between high and lowsulphur fuel oil when moving to andfrom SECAs.

Infineum claims that it is possible toswitch between high and low sulphurfuel oils without the need for complicateddual lubricant control systems.

By using a fuel additive in the fuel oil,the company claims it is possible to opti-mise the MDCL feed rate to accommodatechanges in fuel sulphur level withoutexposing the engine to the risk ofincreased cylinder liner corrosive wear ordeposit build-up on the piston.

Infineum presented a paper at theCIMAC Congress in Kyoto, Japan whichshowed additive delivered via the fuelallowed a 30% decrease below the normalMDCL feed rate without scuffing (in aBolnes 1 DNL 190 cross-head engine).

Because the additive is introduced intothe combustion zone via the fuel, the effi-ciency of acid neutralisation is enhanced,and thus a single MDCL grade can bespecified for both high and low sulphurfuels without the need for duel lubricantcontrol systems, according to Infineum.

www.infineum.com

Additives promoted as solution to SECA dual tank lube dilemma

the ship would be reduced by 2.7 mt ofCO, 11mt of NOx, and 5 mt of SOx.

The Port of Vancouver has been partic-ularly pleased with the test results.

"We're hoping to encourage others tofollow suit," Alicia Blancarte, Port ofVancouver Director of EnvironmentalPrograms, told Bunkerworld.

"Many technologies have an addedcost, but CombustAll enables both emis-sions and fuel consumption to bereduced," Blancarte said.

As part of initiatives to reduce shore-based emissions in the port, CombustAlltests were carried out last year on diesel-powered cargo handling equipment attwo of the port's container terminals.

Based on the results, terminal operatorTSI Terminal Systems Inc. will now beusing CombustAll in its cargo handlingequipment at the Vanterm terminal whilethe Port of Vancouver is using the addi-tive for its shore-based maintenanceequipment.

The Port of Vancouver is part of theWest Coast Diesel Emissions ReductionCollaborative (WCDERC), along withports on the US West Coast and withCanadian and US regulatory agencies,with the aim of reducing air emissionsfrom port operations.

"Ships are sticking out like a sorethumb," Blancarte told Bunkerworld."Shipowners should expect tougher emis-sions controls."

As port operations like Vancouver'sexpand, local communities are expectingaction from shipowners on ship emissions.

"They don't have twenty years torespond," Blancarte said, and noted thatVancouver is one of several West Coastports investigating lower emissions lev-els in the region through SulphurEmission Control Areas (SECAs) andother restrictions.

While low-sulphur fuels are part of thesolution, other ship emissions - such asNOx and particulate matter - will also betargeted, Blancarte said.

Additives like CombustAll, whichreduce a range of different ship emissions,are therefore likely to have an importantfuture role to play.

p12-15.qxd 12/08/2005 15:22 Page 3

Bunker World August/September 2005 page 15

prising over 30 voyages over more than125,000 miles at sea.

The results showed a fuel economyimprovement of more than 7%, even afterfactoring in variables such as containerloads, slip, speed, etc. Other long-termtests on vessels ranging up to 155,000tons show fuel economy improvementsfrom 4-7%.

Emissions reductions dueto Green Plus have shownthe following results: NOxreductions of 15-25%, SOxreductions of 10-25% andParticulate Matter reductionsof 10-20%. These levels couldhelpoperators achieve IMO standards.

To go along with its impres-sive results in the maritimeworld, Green Plus wasrecently approved by theState of Texas as a viableemissions reduction solutionto meet the State's new strin-gent Texas Low EmissionDiesel (TxLED) law.

After passing a series ofcomplex Federal heavy-dutydiesel engine emissions tests,the Texas Commission onEnvironmental Quality(TCEQ) approved GreenPlus as the first additive-based alternative diesel for-mulation solution for bothon and off road (includingmarine and locomotive)diesel fuels.

The TxLED law, whichgoes into effect October 1,2005, requires Texas dieselproducers and importers tosupply a diesel fuel formu-lation that meets the TexasLow Emission Dieselrequirements in the 110counties in Texas designat-ed as U.S. EPA non-attain-ment areas (areas whichhave consistently surpassedthe ozone and other air pol-lution levels). Producersand importers may now use Green Plus as their solu-tion to meet the require-ments of Texas LowEmission Diesel in the 110affected counties.

As a result, the use ofGreen Plus as part of TxLEDfuel will reduce all of theharmful gaseous and pollu-tant emissions from currentdiesel fuel. Most important-ly, Green Plus could poten-tially help Texas reducesmog-causing NitrogenOxides (NOx) by over 13,000tonnes per year.

The notification ofapproval can be found on theState of Texas web site ath t t p : / / w w w . t n r c c .state.tx.us/oprd/sips/cle-andiesel.html#Formulations

Cost-effectiveness -operational ease

A liquid fuel combustion catalyst like Green Plus could be considered the most cost-effective solution on the market, because it literally pays the customer a dividend in fuel savings while at the same time reducingcertain key emissions to meet IMO and

other standards. As a nanotechnology, very small

amounts of the catalyst are necessary totreat large amounts of fuel. A few barrelsof Green Plus will treat many thousandsof tonnes of fuel. It can be injected intofuel lines or even added to bunkersthrough sounding tubes depending onthe application.

bunkerwwoorrlldd

PDVSADELTAVEN

The key to our success...At Deltaven we pride ourselves on our dedication and commitment to providing the bestservice to our clients.You will always come first when you buy bunkers at any one of our 30 PDV supplypoints on the Venezuelan coast or the Caribbean.We can supply all ranges of gas-oil, diesel oil, intermediate and heavy fuels as well as marinelubricants for every vessel. All of our products meet with international specification ISO-8217, so that when you use PDV products, you’ll know you’re using the best.Think quality - ThinkDeltaven.

Avenida Francisco de MirandaTore Peqiven, #17-44ChacaoCaracasVenezuela

Think Quality - Think DeltavenTel: +58 212 201 4212After Hours: +58 416 620 9826Email: bunkers@pdvsa.comFax: +58 212 201 4242Web: www.pdvsa-deltaven.com

A fuel catalyst could be the break-through the industry has been seeking.More information can be obtained atwww.biofriendly.com or www.greenplus.co.uk

Green Plus -Government

Approved

p12-15.qxd 12/08/2005 15:22 Page 4