Distillate Marine Research Articles

Machine Learning Approach for the Investigation of Metal Ion Concentration on Distillate Marine Diesel Fuels through Feed Forward Neural Networks

In this work, a set of Feed Forward Neural Networks (FNN) for the estimation of the metal ion concentration of diesel fuels is presented. The dataset vector is obtained through in situ measurements from distillate marine diesel fuel storage tanks all over Greece, in order to reduce the selection bias. It has been demonstrated that the most correlated ions among them are Aluminum (Al), Barium (Ba) and Calcium (Ca). Moreover, the FNN models are the most reliable models to be used for the model construction under discussion. The initial L2 error is relatively small, in the vicinity of 0.3. However, after removing a small dataset that includes 1–2 data points significantly deviating from the model trend, the error is substantially reduced to 0.05, ensuring the reliability and accuracy of the model. If this dataset is cleared, the estimated error is substantially reduced to 0.05, enhancing the reliability and accuracy of the model. The correlation between the sum of the concentrations of the model in relation with the Density and Viscosity are, respectively, 0.15 and 0.29 which are characterized as weak.

PERFORMANCE PROPERTIES OF MARINE FUEL DERIVED FROM SECONDARY POLYMER RAW MATERIALS

The article substantiates the need to determine the operational properties of shipping fuel obtained from secondary polyolefin (HDPE and PP) raw materials by catalytic pyrolysis. It is proposed to evaluate the operational properties of fuel for shipping – marine gasoil (MGO) by the value of the cetane index (CI, unit), H:C ratio, working heat of combustion (Q, MJ/kg). In view of the scheme of catalytic pyrolysis of polymeric raw materials proposed by us, which consists of two stages (I stage - the course of reactions on a mixture (1:1) of zeolitecontaining catalysts Zn-H-ZSM-5/Fe-H-ZSM-5; II stage – the course of reactions on the NiH-ZSM-5 catalyst), it is necessary to determine after each stage of the process the quality indicators of the reaction products (fractions with boiling points of -360(380) °С) given above. Also, additionally, we determined the quality indicators for the fractions obtained on the H-ZSM-5 industrial catalyst. The proposed research program, on the one hand, allows to determine the efficiency of the pyrolysis process with the selected catalysts in comparison with industrial technology, on the other hand, it will allow to adjust the process in the direction of obtaining a final product of a quality level that meets the requirements for MGO presented in ISO 8217:2017. The conducted studies showed that by the value of CI (48-50 units) and ν 40 (2,8–3,1 mm²/s) the fractions with boiling points of 180–360(380) °С, which were obtained by pyrolysis of polymer raw materials according to the two-stage technology proposed by us (on Zn-H-ZSM-catalysts 5/Fe-H-ZSM-5, Ni-H-ZSM-5) can be attributed to the brands of distillate marine fuels DMA, DFA, DMZ, DFZ (ISO 8217:2017). These fractions are also characterized by a high Н:C ratio (for HDPE – 1.62; for PP – 1.64) and working heat of combustion (for HDPE – 44.0 MJ/kg; for PP – 44.3 MJ/kg), which makes it possible to use them as fuels for shipping.

Comparison of fuel properties of alternative drop-in fuels with standard marine diesel and the effects of their blends

Drop-in fuels are biofuels or synthetic fuels designated to be blended with conventional petroleum-derived hydrocarbons. These alternative fuel blends can be used without major modifications of the engine or the fuel system. Thus, the use of drop-in fuels offers the marine sector a good first opportunity to reduce the carbon footprint and other emissions. This work investigates the miscibility and compatibility of different potential drop-in fuels with standard distillate marine diesel in order to provide an initial outlook on possible use in the maritime sector based on their fuel characteristics. The five drop-in fuels Fatty acid methyl esters (FAME), Oxymethylene ether (OME), Hydrotreated vegetable oils (HVO), Fischer-Tropsch diesel (FTD) and a pyrolysis oil (HDO) were mixed at 10, 30 and 50 % with standard marine distillate diesel and the physical and chemical properties, the distillation curves and the corrosion stability as well as the storability were analysed. All drop-in fuels can be blended with DMA. Due to the chemically different composition of OME, the distillation curve of the blends significantly differs from the distillation curve of DMA, which should be taken into consideration when using these new alternative blends. Furthermore, the blends of OME and FTD show an unexpected corrosion, which is not observed in the pure drop-in fuels. This is expected to have a considerable influence on the engine operation as well as on the storage.

Tracking Liquefied Natural Gas Fuelled Ship’s Emissions via Formaldehyde Deposition in Marine Boundary Layer

One of the reasons that anthropogenic greenhouse gas emissions estimation is imprecise is the uncertainty of aerosol impacts on cloud properties. Maritime transportation is slowly changing fuel preferences. With the policy framework changing regulations, the shipping business is going in a direction that emits less sulfur dioxide and black carbon, which are the compounds that cause linear cloud formations known as ship tracks. Aside from their effects on the total radiative forcing of a transportation mean, this phenomenon enables the detection of ships via satellite imagery sensors. The rapidly increasing trend of shifting propulsion of maritime transportation from conventional heavy fuel oil and distillate marine fuels to liquefied natural gas causes enormous hikes in methane emissions. Therefore, oxidation of the volatile organic compound in the marine boundary layer by the hydroxyl radical in the troposphere makes significant deposition of formaldehyde which causes human effects, ecosystem damage, and climate impact. The primary triggering substance among the compounds in the ship plume is methane. This paper discusses methods to assess near real time tracking of anomalies and the deposition of the short lived substance in different seasons in one of the main occurring areas, shipping corridors. The study also employs anomaly map analysis for June and December 2010 and 2020. Several global tracking methods are available with satellites, monitoring experiments, and other satellite tracking tools. Apart from a few areas the results are not indicative since the formaldehyde formations caused by LNG fueled ships are not widespread enough alongside with overall LNG fueled fleet. On the other hand, the analysis and method are promising for the follow-up of the emissions in the future.

Chemical Recycling of Plastic Marine Litter: First Analytical Characterization of The Pyrolysis Oil and of Its Fractions and Comparison with a Commercial Marine Gasoil

A detailed molecular fingerprint of raw pyrolysis oil from plastic wastes is a new research area. The present study focuses for the first time on the chemical recycling of plastic marine litter; we aim to chemically characterize the obtained raw pyrolysis oil and its distillates (virgin naphtha and marine gasoil) via GC-MS and FT-IR. For all samples, more than 30% of the detected compounds were identified. 2,4-dimethyl-1-heptene, a marker of PP pyrolysis, is the most represented peak in the chemical signature of all the marine litter pyrolysis samples, and it differentiates commercial and pyrolysis marine gasoil. The presence of naphthalenes is stronger in commercial gasoil, compared to its pyrolysis analog, while the opposite holds for olefins. The overlap between the two molecular fingerprints is impressive, even if saturated hydrocarbons are more common in commercial gasoil, and unsaturated compounds are more common in the gasoil derived from pyrolysis. A technical comparison between the commercial marine gasoil and the one obtained from the marine litter pyrolysis is also attempted. Gasoil derived from marine litter fully complies with the ISO8217 standards for distillate marine fuel. On the other hand, the virgin naphtha is particularly rich in BTX, ethylbenzene, styrene, and alpha olefins, which are all important recoverable platform chemicals for industrial upcycling.

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The economic performance of ship power plants is directly dependent on fuel consumption. Consumption is determined by the completeness of fuel combustion, which is influenced by many factors, one of which is the component composition. High molecular weight compounds, resins and asphaltenes contained in marine fuels are poorly flammable. They also form a coarse dispersed phase in the fuel, which complicates the process of hydrocarbon oxidation and leads to a decrease in its efficiency. It is known that ultrasonic influences increase the degree of fuels dispersion. The purpose of the work is to identify the regularities of ultrasound effect on the physicochemical indicators of distillate marine fuel of the DMA brand, which determine its operational properties: flammability, combustibility and pumpability. Experimental studies on the processing of marine fuel are carried out on ultrasonic devices LUK-0.125/50-O and Volna UZTA-0.4/22- 014 at a frequency of 50 and 22 kHz, respectively. For the theoretical substantiation of the observed effects, changes in the dispersed and structural-group composition of marine fuel are studied. The analysis of indicators in accordance with the regulatory documents is carried out. The greatest changes in all studied parameters are noted at an ultrasonic vibration frequency of 50 kHz. It is found that, in comparison with the initial sample, the kinematic viscosity decreases by 15 % after ultrasound exposure. The fuel density decreases by 0.002 kg / m3, the flash point of the fuel drops by 5 °C, and the cetane number shows a tendency to decrease by 2 points. The average particle size of the dispersed phase decreases by 12 %. An explanation for the improvement of the investigated fuel indicators on the basis of an increase in its degree of dispersion and redistribution of structural-group components is proposed. Ultrasonic treatment of marine fuel (50 kHz, 100 W, 43 s), carried out before feeding it to the engine on the fuel line in front of the filter and high-pressure pumps, can be used to improve the operational properties of the fuel and, consequently, reduce its consumption.

Selected Fuel Properties of Alcohol and Rapeseed Oil Blends

The alcohols ethanol and 1-butanol are interesting options as blending components for renewable fuels. We studied whether it is possible to mix these alcohols with a little refined material, rapeseed oil, to obtain stable fuel samples. At room temperature, the stable samples consisted of rapeseed oil blended with butanol at 5 vol-%, 10 vol-%, 20 vol-%, 30 vol-% and one sample of rapeseed oil with 5 vol-% of ethanol. The samples’ fuel properties analysed were kinematic viscosity (at 40 °C), density (at 15 °C) and surface tension. Cold filter plugging point was measured for rapeseed oil with 20 vol-% and 30 vol-% of butanol. Stability of butanol or ethanol and rapeseed oil blends can be achieved at the studied volumes. The density of neat rapeseed oil and all the alcohol–rapeseed oil blends met the requirements set for residual marine fuels. The 30 vol-% butanol–rapeseed oil blend met the requirements for distillate marine oil for density, and almost for kinematic viscosity. The blends appeared most suitable for power plants and marine engines. More detailed analyses of their properties are needed before recommendations for use can be given.

Avoidance tests as a tool to detect sublethal effects of oil-impacted sediments.

Currently, risk assessment for oil contamination does not consider behavioral responses of benthos to oil toxicity. Avoidance of oil-contaminated sediment by benthic amphipods, however, may be a highly sensitive endpoint for sublethal effects of commonly used distillate fuels. In the present study, the avoidance behavior of temperate freshwater (Gammarus pulex) and marine (Gammarus locusta) amphipods was tested by allowing them to choose between a reference sediment and a distillate marine grade A (DMA) oil-spiked sediment. Avoidance of DMA-spiked sediment at 1000 mg/kg dry weight was significant within the total exposure time (96 h) in G. pulex and within the first 72 h in G. locusta in 1 of 2 tests. Absence of DMA avoidance at lower concentrations (≤250 mg/kg dry wt) indicates that test species can only detect DMA above these concentrations. However, sensitivity to oil may vary according to the phenology and physiological conditions of the populations involved, such as the species temperature tolerance and reproductive stage. The results suggest that avoidance tests may be used as an alternative to traditional chronic toxicity tests provided that a causal link between avoidance and long-term effects can be established. Environ Toxicol Chem 2018;37:1757-1766. © 2018 SETAC.

Sources of variance in BC mass measurements from a small marine engine: Influence of the instruments, fuels and loads

Knowledge of black carbon (BC) emission factors from ships is important from human health and environmental perspectives. A study of instruments measuring BC and fuels typically used in marine operation was carried out on a small marine engine. Six analytical methods measured the BC emissions in the exhaust of the marine engine operated at two load points (25% and 75%) while burning one of three fuels: a distillate marine (DMA), a low sulfur, residual marine (RMB-30) and a high-sulfur residual marine (RMG-380). The average emission factors with all instruments increased from 0.08 to 1.88 gBC/kg fuel in going from 25 to 75% load. An analysis of variance (ANOVA) tested BC emissions against instrument, load, and combined fuel properties and showed that both engine load and fuels had a statistically significant impact on BC emission factors. While BC emissions were impacted by the fuels used, none of the fuel properties investigated (sulfur content, viscosity, carbon residue and CCAI) was a primary driver for BC emissions. Of the two residual fuels, RMB-30 with the lower sulfur content, lower viscosity and lower residual carbon, had the highest BC emission factors. BC emission factors determined with the different instruments showed a good correlation with the PAS values with correlation coefficients R2 >0.95. A key finding of this research is the relative BC measured values were mostly independent of load and fuel, except for some instruments in certain fuel and load combinations.

A multivariate statistical analysis to evaluate and predict ignition quality of marine diesel fuel distillates from their physical properties

Ignition quality of diesel fuels used in compression ignition engines is mainly described by their respective Cetane Number (CN). The most widely accepted method for CN measurement is the ASTM D613, involving a variable compression ratio Cooperative Fuel Research (CFR) engine. However in the recent years other alternative methods based on a Constant Volume Combustion Chamber (CVCC) concept have gained significant popularity mainly due to lower cost of acquisition, maintenance and operation, still being able to provide accurate results. Other widely accepted parameters for the characterization of ignition quality of diesel fuels are cetane indices. These are empirical mathematical equations, based on simple physicochemical properties (such as density and distillation characteristics) and usually correlate well with CN. However, they are accurate enough within narrow limits and are very prone to produce misleading results when involving modern fuels, or biofuels and their blends. In this work, an effort was made to investigate the room for improvement for the prediction of CN, apart from the use of the most widely accepted method of Calculated Cetane Index (CCI), standardized by ASTM D4737, with regard to today's used marine diesel fuels. A total of 47 distillate marine diesel fuels (with high sulfur content compared to automotive diesel fuels) has been employed in order to create multivariate regression models to predict CN equivalents. Thus, useful conclusions were drown in an attempt to evaluate the importance of various physicochemical properties with regard to ignition quality, as well as a first step to the potentiality of revaluation of empirical mathematical models currently in use.

Distillate marine fuel oil and ULSFO spills in cold climate - oil spill characteristics and response options

In 2014 the Norwegian Coastal Administration (NCA) conducted an environmental risk and oil spill response analysis related to possible oil spills from shipping in the areas of Svalbard and Jan Mayen. One of the key findings were that due to regulations to ban heavy fuel oil in protected areas, the most likely spill scenarios are spills of distillate marine fuel oils. Furthermore, the cold climate is expected to slow down oil weathering processes, and in calm weather situations this may call for active response, even to spills of light fuel oils. Also along the coast of mainland Norway, response options to spills of light fuel oils is an emerging topic. This includes not only MGO/MDO, but also several new products formulated to meet the 2015 Emission Control Areas (ECA) sulphur limit, also referred to as hybrid fuel oil / ultra low sulfur fuel oil (ULSFO). Previous experiences from spills of light fuel oils in Norwegian waters have been summarized; however, some recommendations for response remain inconclusive. Hence, the need for increased knowledge of the characteristics of light fuel oils and relevant response options is recognized. SINTEF analyzed a range of light fuel oils on behalf of NCA. This initial screening included chemical characterization (GC-MS/GC-FID) and identification of physical properties, i.e. viscosity, density, pour point, flash point, as well as emulsifying properties. Based on these results, five different fuel oils were selected for further examination, including:- Weathering predictions and improved trajectory modeling- Chemical and toxicological characterization of water accommodated fraction (WAF)- Laboratory tests of properties related to dispersant use and ignition, both in order to explore the applicability of dispersants and in-situ burning as response techniques, and to determine windows of opportunity for the different oil types. Laboratory tests are performed at 2 °C and 13 °C, reflecting “arctic” / cold climate conditions and North Sea summer conditions. Furthermore, mechanical recovery will be tested on the same oil types in the NCA test facility (abstract submitted by Holt & Frost). The results from this ongoing project will be presented from an operational viewpoint. They are expected to give insights useful to response planning, decision making during spill incidents, and enhanced response options for future spills of distillate marine fuel oils and ULSFO, especially in cold climates and arctic environment.

Lubricating Oil as a Major Constituent of Ship Exhaust Particles

A proton-transfer-reaction time-of-flight mass spectrometer combined with the novel CHARON (“chemical analysis of aerosol online”) aerosol inlet was used for characterization of submicrometer particulate organic matter in ship engine exhaust. Particles were sampled from diluted and cooled exhaust of a marine test bench engine that was operated on residual heavy fuel oil (HFO) and low-sulfur distillate marine gas oil (MGO), respectively. In both fuel operation modes, exhaust particle mass spectra were dominated by polycycloalkanes in the C20-to-C39 range, which are typical main constituents of lubricating oils. Exhaust particle mass spectra were closely reproduced when the engine’s lubricant oil was directly measured in aerosolized form. We report emission profiles of lubricant oil hydrocarbons as a function of their volatility and as a function of their carbon atom number. Total emissions of lubricant oil amounted to 183 and 74 mg kW–1 h–1 for HFO and MGO combustion, respectively. These values resemble ty...

Investigating “De Minimis” Level of Fatty Acid Methyl Esters (FAME) in Distillate Marine Gas Oil

According to the existing maritime regulation, the marine diesel equipment will be necessary to operate with low sulfur marine fuels. Low Sulfur Middle Gas Oils (MGOs) often have a viscosity that is lower than that of Heavy Fuel Oil (HFO). The problems in diesel engines are mainly related to high pressure fuel pumps that depend on the fuel oil for their lubrication. A solution to that problem probably will be the addition of Fatty Acid Methyl Esters (FAME) as an additive to the fuel. On the other hand, for the purposes of International Standard ISO 8217:2012 in the case of distillate fuels it is recommended that “de minimis” level of FAME is recommended. “De minimis” level is determined approximately as the 0.1% volume of the fuel. In this study, Distillate Marine Diesel Oil with good lubricity performance was used blended with FAME fuel, according to national and European Standard (ELOT EN 14214), was used as an additive. The FAME was stored for three months period in a plastic container. Then mixture with concentrations of 0.5%, 1.0%, 2.0%, 3.0%, 4.0% and 5.0% by volume were used. The obtained results shown that all the mixtures are within the specification limits but the tribological measurements, which were carried out with an applied load of 600 g using the High Frequency Reciprocating Rig (HFRR) with test duration for each test 150 min., revealed an increased wear. This happened because after the storage period the water content of the FAME increased significant.

Effects of Biodiesel Blend on Marine Fuel Characteristics for Marine Vessels

Biodiesel produced from vegetable oils, animal fats and algae oil is a renewable, environmentally friendly and clean alternative fuel that reduces pollutants and greenhouse gas emissions in marine applications. This study investigates the influence of biodiesel blend on the characteristics of residual and distillate marine fuels. Adequate correlation equations are applied to calculate the fuel properties of the blended marine fuels with biodiesel. Residual marine fuel RMA has inferior fuel characteristics compared with distillate marine fuel DMA and biodiesel. The flash point of marine fuel RMA could be increased by 20% if blended with 20 vol% biodiesel. The sulfur content of residual marine fuel could meet the requirement of the 2008 MARPOL Annex VI Amendment by blending it with 23.0 vol% biodiesel. In addition, the kinematic viscosity of residual marine fuel could be reduced by 12.9% and the carbon residue by 23.6% if 20 vol% and 25 vol% biodiesel are used, respectively. Residual marine fuel blended with 20 vol% biodiesel decreases its lower heating value by 1.9%. Moreover, the fuel properties of residual marine fuel are found to improve more significantly with biodiesel blending than those of distillate marine fuel.

Effect of ethylene-vinyl acetate copolymer-based depressants on the low-temperature properties of components of light- and heavy-grade marine fuels

The possibility of using ethylene copolymers with vinyl acetate as additives for light and heavy distillate marine fuels for improving their low-temperature properties has been examined. The maximum depressing effect of these additives is achieved at an optimal concentration for each distillate and a definite copolymer molecular mass and composition.

Production of marine distillate fuel oil from waste polypropylene

A semibatch distillative thermolysis of polypropylene waste under 25, 40, 60 and 80 bar was performed. The yield of the resulting products and the distillation characteristics of the liquid thermolysis products depending upon the process conditions have been investigated. It was determined that as the pressure of the thermolysis process increased from 25 to 80 bars, the yield of the liquid product decreased from 74.7 to 62.6 %, whereas the yield of the gaseous product increased by 8.3 to 21.3 %. The liquid product obtained under higher pressure had more flat distillation characteristics, especially the distillate that boils off beyond 40 %, composed of lower molecular mas compounds. In order to assess the potential yield of thermolysis products for the production of the marine distillate fuel, there was set a dependence of the flash point of the liquid fraction upon the light component cut content. According to the ISO 8217:2012 specification, the quality characteristics of the obtained fractions have been investigated. The GC of the lightest liquid fraction (naphta), not suitable for a marine fuel because of a too low frash point, showed the predominance of isoparaffins – a useful feedstock for gasoline production. Carbon residue values of the liquid thermolysis product do not comply with the standard specification because of a significant content of alkenes and alkadienes. The latter at a higher temperature are particularly apt to polymerization, cyclization, and aromatization. During these reactions, carbon residue precursors are formed. The calculated yield of the obtained polypropylene thermolysis liquid fractions compatible with distillate marine fuels of summer and winter grades was 53 % for the ISO-F-DMX category and 41 % for the ISO-F-DMA and ISO-F-DMB categories which are used in the Lithuanian shipping fleet. DOI: http://dx.doi.org/10.5755/j01.ct.63.1.4516

Improved modelling of ship SO2 emissions—a fuel-based approach

Abstract Significant variations are apparent between the various reported regional and global ship SO2 emission inventories. Important parameters for SO2 emission modelling are sulphur contents and marine fuel consumption. Since 1993, the global average sulphur content for heavy fuel has shown an overall downward trend, while the bunker sale has increased. We present an improved bottom up approach to estimate marine sulphur emissions from ship transportation, including the geographical distribution. More than 53,000 individual bunker samples are used to establish regionally and globally (volume) weighted average sulphur contents for heavy and distillate marine fuels. We find that the year 2002 sulphur content in heavy fuels varies regionally from 1.90% (South America) to 3.07% (Asia), with a globally weighted average of 2.68% sulphur. The calculated globally weighted average content for heavy fuels is found to be 5% higher than the average (arithmetic mean) sulphur content commonly used. The reason for this is likely that larger bunker stems are mainly of high-viscosity heavy fuel, which tends to have higher sulphur values compared to lower viscosity fuels. The uncertainties in SO2 inventories are significantly reduced using our updated SO2 emission factors (volume-weighted sulphur content). Regional marine bunker sales figures are combined with volume-weighted sulphur contents for each region to give a global SO2 emission estimate in the range of 5.9–7.2 Tg (SO2) for international marine transportation. Also taking into account the domestic sales, the total emissions from all ocean-going transportation is estimated to be 7.0–8.5 Tg (SO2). Our estimate is significantly lower than recent global estimate reported by Corbett and Koehler [2003. Journal of Geophysical Research: Atmospheres 108] (6.49 Tg S or about 13.0 Tg SO2). Endresen et al. [2004. Journal of Geophysical Research 109, D23302] claim that uncertainties in input data for the activity-based method will give too high emission estimates. We also indicate that this higher estimate will almost give doubling of regional emissions, compared to detailed movement-based estimates. The paper presents an alternative approach to estimate present overall SO2 ship emissions with improved accuracy.

Oil effect in freshly spiked marine sediment on Vibrio fischeri, Corophium volutator, and Echinocardium cordatum

The purpose of this study was to provide data to be used in The Netherlands for development of ecotoxicologically based quality criteria for oil-contaminated sediments and dredged material. In addition, the relation of toxicity to specific oil boiling-point fraction ranges was explored. Natural marine sediment, with a moisture, organic carbon, and silt content of approximately 80, 1.8, and 33% of the dry weight, respectively, was artificially spiked using a spiking method developed in this project. Aliquots of one part of the sediment were spiked to several concentrations of Gulf distillate marine grade A (DMA) gasoil (containing 64% C10-19) and aliquots of the other part to several concentrations of Gulf high viscosity grade 46 (HV46) hydraulic oil (containing 99.2% C19-40). Thus, for each individual oil type, a concentration series was created. Vibrio fischeri (endpoint: bioluminescence inhibition), Corophium volutator (endpoint:mortality), and Echinocardium cordatum (endpoint:mortality) were exposed to these spiked sediments for 10 min, 10 d and 14 d, respectively. Based on the test results, the effective concentration on 50% of the test animals was statistically estimated. For DMA gasoil and HV46 hydraulic oil, respectively, the effective concentrations were 43.7 and 2,682 mg/kg dry weight for V. fischeri, 100 and 9,138 mg/kg dry weight for C. volutator, 190, and 1064 mg/kg dry weight for E. cordatum. This study shows that the toxicity is strongly correlated with the lower boiling-point fractions and especially to those within the C10-C19 range.