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MARINE ADDITIVES SPECIAL

Additives improve fuel oil properties

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 Petrolites Prepared to Respond Services highlights the vast potential of these products.
pecifications for the various grades of bunker fuel define the fuel's handling characteristics and also help ensure performance in diesel engines, as measured by parameters such as operating efficiency and emissions levels. Common specifications include physical properties such as density, viscosity, flash point temperature and pour point temperature, plus chemical properties such as sulfur content, carbon residue, water and sediment content, and ash content. Certain metal species such as sodium and vanadium are limited because elevated levels of these metals can result in severe damage to engines. There are other oil properties not addressed in these specifications that also can have an impact on overall fuel salability, handling characteristics and performance. The first is fuel oil asphaltene stability, an important parameter used in blending different fuel oils to produce a particular grade. The second is hydrogen sulfide, or H2S content. This is an important issue because of the safety implications due to the potential for human exposure to this dangerous gas. Finally, there is a growing awareness of fuel odor issues, beyond those related to the distinct smell of low levels of H2S in the fuel. There are also several types of chemical additives that can be used to maintain or improve bunker fuel quality. Below, we define some key additive categories, and discuss how these additives can impact bunker fuel quality.

Intensity

fying the wax crystal structure so that smaller, irregularly shaped crystals are formed upon cooling. Modifying the wax crystals prevents the oil from gelling and thus provides better handling properties of the fuel at lower temperatures. Figure 1 shows the typical response of crude oil or heavy fuel oil viscosities to treatment with heavy fuel pour point depressant chemicals. Bunker fuels used in cold climates especially can benefit from the use of this type of additive.

ical results from Baker Petrolite's ASITSM Asphaltene Stability Index Test method. This test procedure involves titration of the bunker fuel oil sample with asphaltene non-solvent until the asphaltene flocculation point is reached.
ASITSM Asphaltene Stability Index Test
70 60 50 40 30 20 10 0
0.00

Crude 1 Crude 2

for odor detection. Low levels of H2S or mercaptans are typically the problem. However, as more nontypical blend components are used to make various bunker fuel grades, there are increasing instances of the presence of other components such as amines and olefins that can also impart odors to the fuel. Masking agents have been used, but these require high dosages and merely impart another, more pleasant odor to the fuel.
Odor Issues
Odor Agent H2S Methyl Mercaptan Ethyl Mercaptan n-Propyl Mercaptan n-Butyl Mercaptan Carbon Disulfide Methyl Alcohol Ammonia Threshold Detection Limit 0.0047 ppm 0.0021 ppm 0.001 ppm 0.00075 ppm 0.001 ppm 0.21 ppm 100 ppm 46. ppm

Although not a typical quality specification, the H2S content of bunker fuel is a property that most fuel suppliers monitor because of safety, corrosion and odor issues. There are a number of terminal, port authority and company H2S specifications used in the industry. If H2S levels are above specifications, chemical scavengers can be used to reduce the level to below safe limits. By reducing hydrogen sulfide levels in storage tank vapor space, H2S scavengers also minimize the rate of bisulfide corrosion reactions that often reduce the useful life of carbon steel fuel oil storage tank roofs. Reduced fuel odor can be an additional benefit.

H2S Scavengers

Additives can greatly increase the stability of an oil

Crude 3 Crude 4 Crude 4 + Asphaltene Stabilizer

High Fouling Potential

50.00 100.00

Medium Fouling Potential

150.00 200.00

Low Fouling Potential

250.00 300.00

ASI

Copyright 2003 Baker Hughes Incorporated

Figure 2: Example Output from ASIT Asphaltene Stability Index Test The Asphaltene Stability Index, determined by the position of the inflection point in a plot of near-infrared laser transmittance vs. volume of solvent added, is correlated to fuel oil stability. These ASITSM plots clearly show the effects of different blending component ratios on fuel oil stability. If a fuel oil is unstable as measured by spot or ASIT tests, asphaltene stability improver additives can be used to restore the desired long term asphaltene stability in the fuel. The effects of these additives can be measured in the fuel oil stability tests.

Table 1: Potential Odor-Causing Compounds in Bunker Fuel Oils Newer odor control agents take a different approach. They act in a number of ways to chemically neutralize the odors. It is important that these odor control agents are used only after the levels of any dangerous odorous materials, such as H2S, are tested and found to be below levels considered to be harmful.

Paraffinic crude oils can produce fuel oil blending stocks that contain heavy waxes. These waxes begin to form insoluble precipitates when cooled, which eventually

Pour Point Depressants

Pour Point Additive Effect on Viscosity

1000000 Lo 100000 g 10000 Vi sc 1000 osi 100 ty 10 (c

Untreated =

150 ppm Dose =

507 cp

Water in the fuel oil is an unwanted contaminant. It has no combustion value and may also contain dissolved inorganic materials that can form deposits in the diesel engine. Dewatering additives can be used to help remove water from the bunker fuel. The water will fall to the bottom of the storage tank where it can be drained out of the tank. Leaving the settled water in the tank bottom can result in biological activity that can add unwanted materials to the bunker fuel. The dewatering procedure can take some time as the water droplets need to coalesce and form larger droplets that will eventually drop through the oil phase. Once this has occurred the dry fuel can be transferred on specification.

Dewatering Additives

250 ppm Dose = 126 cp

1 15 25 35 45 55 65 75 85 95 105 115 125 135

West African Crude

Temperature (Deg.

Figure 1: Viscosity vs. Temperature Profile of a Paraffinic Crude Oil Treated with Pour Point Depressant Chemical form large wax crystals. These crystals can cause the oil to stop flowing as the temperature of the fuel is reduced. It should also be noted that even if the oil flows, it can become very viscous at temperatures above the pour point. Pour point depressants work by modi-

These large molecules are stabilized in the oil by a complex system of resin moleculesThe traditional "spot" test is used by blenders to measure heavy fuel oil stability. However, it is not a very reproducible method in that the spot test ratings may vary depending on subjective interpretations of the test results. Newer methods have been developed that give more objective results and that give more information about the asphaltene stability of a given fuel oil blend. For example, Figure 2 shows some typ-

Asphaltene Stability Improvers

Vanadium and sodium are two metals that can cause significant problems in bunker fuel combustion. High levels of these metals in the fuel can result in the formation of adherent slags that can cause fouling and corrosion problems in diesel engine cylinders, valves, turbochargers and exhaust gas systems. In addition, vanadium based slag deposits can also catalyze formation of sulfur trioxide (SO3) from sulfur dioxide (SO2) in the exhaust gas. In the presence of condensed moisture, SO3 reacts to form sulfuric acid, which can cause corrosion in exhaust gas handling systems. Additives are available that can minimize the harmful effects of vanadium and sodium contaminants in the fuel oil. These additives typically contain magnesium based compounds that prevent the formation of adherent, corrosive slags and reduce the catalytic effects of vanadium compounds on SO3 formation. Fuel odor is becoming a more prevalent issue in the bunker fuel market. Many compounds can impact odors to the fuel at very low levels. Table 1 shows some typical compounds and their threshold limits

Metal Deactivators

Maintaining desired bunker fuel oil quality is becoming a more challenging task, as the residual oil blend components change, and as new quality specifications are put in place. Chemical additives can be an important and economically attractive method for ensuring that specifications are met by the bunker fuel blender and supplier, and that the desired level of fuel performance is experienced by the end user.

Summary

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

Mike Nicholsons bio

Odor Control Agents

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bunkerworld w Canadian additives prove eco-friendly - and cheaper

Vancouvers Catalyst Energy Inc. has just completed successful tests of its fuel additive, CombustAll, on the carrier M.V. Skaubryn to the delight of the companys President and the Port of Vancouver. Guy Wilson-Roberts, from Bunkerworlds Vancouver bureau, takes up the story

ancouver's Catalyst Energy Inc. has just completed a series of tests of its unique fuel additive, CombustAll, on the carrier M.V. Skaubryn on a sailing between Vancouver and Tokyo with some promising results. The additives manufacturing company was delighted with the tests. "From the engine fuel flow meters, the engine was definitely using less fuel," company president Dana Way told Bunkerworld, putting the fuel saving at 3.5%. "The results were very encouraging the fuel savings alone will offset the cost of

Shipping, owners of the Skaubryn. "Vessel emissions is the focus - reducing the ship's environmental footprint," Bruce Webster, Seaboard's Manager for Ship Operations, told Bunkerworld. "We want to be pro-active and get away from the old image of shipowners as polluters," he added. For Seaboard, reducing fuel consumption and emissions was a logical step. "It's about cleaning up the engines and making them more efficient," Webster said, who noted that Seaboard is currently considering the regular use of CombustAll. The latest test builds on earlier tests conducted on the Skaubryn in March and April, carried out by two independent testing companies on the ship's three generator engines, which burn a blend of IFO180 fuel oil and marine diesel oil (MDO). Results from the tests showed that CombustAll reduced fuel consumption by 2.75%. Just as crucially in times of increased environemntal scrutiny, emissions of particulate matter were reduced by 95%, CO by 19%, and NOx by 11.5%. Total emissions reductions are achieved by two means: reduced fuel consumption; and the catalytic effect on the combustion action. For example, the 11.5% reduction in NOx emissions from the generator engine tests was the aggregate of 2.75% less Catalyst Energy president Dana Way (right) oversees fuel burnt and 8.75% catemissions data collection onboard the M.V. Skaubryn alytic effect. Combustall does not directly target sulphur oxides (SOx), so in using CombustAll, added Wade." this case SOx emissions were reduced by CombustAll is designed to reduce fuel the same amount that fuel consumption consumption and emissions of particulate was reduced. matter, carbon monoxide (CO), and nitroBased on these results, and the ship's gen oxides (NOx), and works by changing typical movements over the course of a the combustion chemistry of the fuel year, CombustAll would reduce total whether it be diesel or heavy fuel oil. emissions in Canadian waters by 3.5 In this test, CombustAll was added mt of CO, 2 mt of NOx, and 0.62 mt of directly into the fuel supply of the SOx, according to Catalyst Energy's Skaubryn's 15,200 hp main engine burncalculations. ing IFO380 heavy fuel oil and emissions The data from the latest test on the samples were taken by analytical samSkaubryn's main engine is still being plers at the main engine exhaust and at analysed to assess the catalytic effect. the ship's stack. Based on the just the fuel saving of 3.5%, The tests were conducted with the suphowever, Catalyst Energy estimates that port of the Port of Vancouver and local emissions over the course of the year for company Seaboard International

BUSY CRANES ARE A SIGN OF A HEALTHY PORT.

Canadas 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

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MARINE ADDITIVES SPECIAL

the ship would be reduced by 2.7 mt of CO, 11mt of NOx, and 5 mt of SOx. The Port of Vancouver has been particularly pleased with the test results. "We're hoping to encourage others to follow suit," Alicia Blancarte, Port of Vancouver Director of Environmental Programs, told Bunkerworld. "Many technologies have an added cost, but CombustAll enables both emissions and fuel consumption to be reduced," Blancarte said. As part of initiatives to reduce shorebased emissions in the port, CombustAll tests were carried out last year on dieselpowered cargo handling equipment at two of the port's container terminals. Based on the results, terminal operator TSI Terminal Systems Inc. will now be using CombustAll in its cargo handling equipment at the Vanterm terminal while the Port of Vancouver is using the additive for its shore-based maintenance equipment. The Port of Vancouver is part of the West Coast Diesel Emissions Reduction Collaborative (WCDERC), along with ports on the US West Coast and with Canadian and US regulatory agencies, with the aim of reducing air emissions from port operations. "Ships are sticking out like a sore thumb," Blancarte told Bunkerworld. "Shipowners should expect tougher emissions controls." As port operations like Vancouver's expand, local communities are expecting action from shipowners on ship emissions. "They don't have twenty years to respond," Blancarte said, and noted that Vancouver is one of several West Coast ports investigating lower emissions levels in the region through Sulphur Emission Control Areas (SECAs) and other restrictions. While low-sulphur fuels are part of the solution, other ship emissions - such as NOx and particulate matter - will also be targeted, Blancarte said. Additives like CombustAll, which reduce a range of different ship emissions, are therefore likely to have an important future role to play.

A catalyst for a change of mindset

Fuel consumption and air emissions currently top the agenda for top ship operator. Tests that reveal a dramatic fall in both through the application of one combustion catalyst should raise more than a few eyebrows. US-based BioFriendly's product Green Plus is a true combustion catalyst, not a typical additive - enhancing the combustion process to achieve more complete combustion
hip management today is faced with the escalating challenge of rising costs and increasing regulation and much of the focus centers on fuel. The International Maritime Organization (IMO) MARPOL Annex VI emissions reduction mandate, combined with moves by the European Union, the U.S. and other countries are destined to have a significant impact on the entire maritime cost structure. In addition, new engines, pollution control devices and lower sulfur fuels could reduce fuel economy and efficiency, thus putting further pressure on Maritime operations.

catalyst, not a typical additive. Additives change the chemical composition of the fuel, whereas a catalyst does not; it simply enhances the combustion process to achieve more complete combustion. It does this by working at the molecular

more linear burn, results in a "domino effect" - more horsepower, more torque, less fuel consumed and less emissions out the stack. Independent testing has confirmed increases of 10% in horsepower and

One of the key problems facing ship owner/operators will be meeting regulatory requirements while keeping costs under control. Recently, a liquid fuel combustion catalyst has been introduced that promises to solve these problems. The product, Green Plus, developed by Biofriendly Corporation in the United States, is a liquid combustion catalyst that can be added to all grades of marine diesel and heavy fuel oil to improve fuel economy and significantly lower emissions. Long term ocean-going test results and certified independent laboratory reports have verified fuel economy improvements of 4-7% and emission reductions of Nitrogen Oxides (15-25%), Sulfur Oxides (10-25%), and Particulate Matter (10-20%).

Liquid fuel catalyst

caption level to "unbundle" the tangle of complex hydrocarbon molecules that make up marine fuels. This unbundling allows more oxygen to reach the fuel and thus it burns more completely. With more oxygen available to the fuel, more energy is being released more quickly at the initiation of the burn when the piston head is at top center. In addition, the catalytic oxygenation allows the fuel to burn more rapidly and thoroughly to provide greater thrust and hence convert more energy to work. The more complete, torque as well as 10% lower exhaust temperatures, which clearly signal a better conversion of energy to work. In boilerbased engines, Green Plus allows the air/fuel mixture to be adjusted to decrease the amount of fuel required to achieve similar performance levels.

The secret behind these results lies in the fact that Green Plus is a true combustion

Not a typical additive

Recently, Biofriendly completed a multiyear test on a 45,000-tonne container vessel with a major shipping company com-

Long Term Tests Confirm Results

Additives promoted as solution to SECA dual tank lube dilemma

A
s the implementation date of the world's first Sulphur Emissions Control Area (SECA) nears, suppliers and shipowners are increasing their focus on the practical requirements involved in meeting the much-publisised regulations. An array of outstanding technical questions remain in terms of how bunker suppliers and ship operators will manage to meet the IMO legislation MARPOL Annex VI's measures for Sulphur Oxide (SOx) capping at 1.5%. However, a solution to one increasingly complex and potentially costly dilemma facing ship operators - that of alternating marine lubricants when switching fuel tanks upon entering and departing SECAs - may be at hand, according to one UK additive manufacturer. Technical experts have raised awareness about the effects of using LSFO on an engine's lubrication system, but comparatively little attention has been given to the issue of lubrication when using LSFO. Most solutions to the problem have centred around the development of marine lubricants specifically designed for use with LSFO, but Infineum Marine Additive Technology Group (Infineum) says there is an alternative. One of the main performance features of marine diesel cylinder lubricants (MDCLs) is to provide protection against cylinder liner corrosive wear from sulphur acids produced when fuel oil is combusted in a marine cross-head engine. Most 70 base number (BN) MCDL products currently on the market have been developed on the basis of fuel oil with 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 on sulphur content means that changes to MDCL quality and/or feed rates are necessary to avoid over-lubrication and the formation of calcium carbonate deposits on the piston that may lead to piston crown burning, bore polish and/or scuffing. Meanwhile, marine lubricant manufacturers have been developing new lubricants specifically designed for use in engines burning LSFO. One operator, Wallenius Wilhelmsen has adopted a policy of burning LSFO as standard. As such, its lubrication management is quite straight-forward. Others, however, have installed dual fuel and lubricant storage systems to cope with the changes between high and low sulphur fuel oil when moving to and from SECAs. Infineum claims that it is possible to switch between high and low sulphur fuel oils without the need for complicated dual lubricant control systems. By using a fuel additive in the fuel oil, the company claims it is possible to optimise the MDCL feed rate to accommodate changes in fuel sulphur level without exposing the engine to the risk of increased cylinder liner corrosive wear or deposit build-up on the piston. Infineum presented a paper at the CIMAC Congress in Kyoto, Japan which showed additive delivered via the fuel allowed a 30% decrease below the normal MDCL feed rate without scuffing (in a Bolnes 1 DNL 190 cross-head engine). Because the additive is introduced into the combustion zone via the fuel, the efficiency of acid neutralisation is enhanced, and thus a single MDCL grade can be specified for both high and low sulphur fuels without the need for duel lubricant control systems, according to Infineum. www.infineum.com

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bunkerworld w
prising over 30 voyages over more than 125,000 miles at sea. The results showed a fuel economy improvement of more than 7%, even after factoring in variables such as container loads, slip, speed, etc. Other long-term tests on vessels ranging up to 155,000 tons show fuel economy improvements from 4-7%. Emissions reductions due to Green Plus have shown the following results: NOx reductions of 15-25%, SOx reductions of 10-25% and Particulate Matter reductions of 10-20%. These levels could helpoperators achieve IMO standards.

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 reducing certain key emissions to meet IMO and

other standards. As a nanotechnology, very small amounts of the catalyst are necessary to treat large amounts of fuel. A few barrels of Green Plus will treat many thousands of tonnes of fuel. It can be injected into fuel lines or even added to bunkers through sounding tubes depending on the application.

A fuel catalyst could be the breakthrough the industry has been seeking. More information can be obtained at www.biofriendly.com or www.greenplus.co.uk

To go along with its impressive results in the maritime world, Green Plus was recently approved by the State of Texas as a viable emissions reduction solution to meet the State's new stringent Texas Low Emission Diesel (TxLED) law. After passing a series of complex Federal heavy-duty diesel engine emissions tests, the Texas Commission on Environmental Quality (TCEQ) approved Green Plus as the first additivebased alternative diesel formulation solution for both on and off road (including marine and locomotive) diesel fuels. The TxLED law, which goes into effect October 1, 2005, requires Texas diesel producers and importers to supply a diesel fuel formulation that meets the Texas Low Emission Diesel requirements in the 110 counties in Texas designated as U.S. EPA non-attainment areas (areas which have consistently surpassed the ozone and other air pollution levels). Producers and importers may now use Green Plus as their solution to meet the requirements of Texas Low Emission Diesel in the 110 affected counties. As a result, the use of Green Plus as part of TxLED fuel will reduce all of the harmful gaseous and pollutant emissions from current diesel fuel. Most importantly, Green Plus could potentially help Texas reduce smog-causing Nitrogen Oxides (NOx) by over 13,000 tonnes per year. The notification of approval can be found on the State of Texas web site at http://www.tnrcc. state.tx.us/oprd/sips/cleandiesel.html#Formulations

Green Plus Government Approved

The key to our success...

At Deltaven we pride ourselves on our dedication and commitment to providing the best service to our clients. You will always come first when you buy bunkers at any one of our 30 PDV supply points on the Venezuelan coast or the Caribbean. We can supply all ranges of gas-oil, diesel oil, intermediate and heavy fuels as well as marine lubricants for every vessel. All of our products meet with international specification ISO8217, so that when you use PDV products, youll know youre using the best. Think Quality Think quality - ThinkDeltaven. - Think Deltaven
Avenida Francisco de Miranda Tore Peqiven, #17-44 Chacao Caracas Venezuela Tel: +58 212 201 4212 After Hours: +58 416 620 9826 Email: bunkers@pdvsa.com Fax: +58 212 201 4242 Web: www.pdvsa-deltaven.com

PDVSA
DELTAVEN

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