Bunker Fuel Quality. Ian Workman Account Manager VPS Testing & Inspection Inc

Transcription

1 Bunker Fuel Quality Ian Workman Account Manager VPS Testing & Inspection Inc

2 Veritas Petroleum Services - Using Established Knowledge to Solve Problems Established in 1981, VPS pioneered marine fuel testing industry Test Volume: > 100 million tons Marine Fuels bunkered annually. Aprox. 50% Highly Experienced Personnel 24/7 Advisory Service 250 Employees Worlds Largest Fuel Quality Database VPS supply IMO with Sulphur Data from worldwide supplies Represented at IMO, CIMAC, IBIA, ISO, ASTM, IP and other Associations

3 VPS Services Marine Fuel Quality Testing (FQT & FSM) 4 x ISO17025 Accredited Laboratories Oil Condition Monitoring (OCM) Fully independent lubricating and hydraulic/gear oil testing Technical Advisory Service Expert team of marine engineers that understands the application Interpretation of every OCM and FQT report Investigative Analysis and Troubleshooting Bunker Quantity Survey (BQS) Mass Flow Meter Investigations Data Analytics Software and Reporting Sampling Equipment In House Training & Fuel Management Courses Bunker Alerts & Circulars

4 The Fuel Supply Chain Today s Marine Fuel Supply Chain can be very complex, with many participants: Refining Trading Blending Supply Shipping As fuels pass through this chain there is little in the way of: Regulation Traceability Transparency Quality Control/Assurance checking

5 Percent % Crude Oil & Refining On average, crude oils are made of the following elements or compounds: Carbon - 84% Hydrogen - 14% Sulphur Species- 1 to 3% Nitrogen compounds- <1% Oxygen - <1% (organic compounds such as carbon dioxide, phenols, ketones, carboxylic acids) Metals - <1% Salts - <1% Global Crude Composition varies widely Crude Oil is a very poor fuel: Wide boiling range can t burn cleanly or effectively Wide variation in composition & quality Contains many impurities ( S, N, metals) Refining is necessary to convert crude oil into useable and marketable products: Shipping - LNG, MGO/Distillate, Residual & Lubricants Crude Oil Composition West Texas Brent Arab Lt Maya Duri Residue Gas Oil Kerosene Gasoline Gas/LPG

6 Marine Fuel Production: Complex Refinery Processes (Catalytic Cracking & Vis-breaking) Distillates Light Cycle Oil Crude Oil Atmospheric Distillation Unit Fluidised Bed Catalytic Cracking Heavy Cycle Oil Typical Blending Components: Light Cycle Gas Oils (60% Aromatics) Heavy Cycle Gas Oils Residue Vacuum Distillation Unit Additional Processing: Hydro-desulphurisation Can also remove O & N species affecting Fuel lubricity & stability. Visbreaker Residue

7 Blending At the Refinery stage & onwards, marine fuels are subject to blending processes, as the fuel moves through the supply chain. Cutter stocks, diluents, additives can all be added to achieve certain specification limits, comply with legislation, improve performance, improve profit margins. Too many cooks spoil the broth!! Also the big questions: are such cutter stocks, diluents, additives quality control checked, traceable, regulated, or even known to the next person in the chain? Are potential side-effects of what s been blended known? Do suppliers really know what they are adding? Blending can change the chemistry of the original fuel, causing instability, sludging & unexpected chemical reactions.

8 Fuel Oil composition Aromatics: Improves stability Negative impact on ignition properties Paraffins: May disturb stability Improves ignition properties Expensive product GOAL: Balance between Paraffins and Aromatics

9 Fuel Stability & Compatibility Residual fuels contain long chain heavy molecules, Asphaltenes, which are polycyclic aromatic compounds held within the solution of the fuel as they are soluble in aromatic solvents but not in aliphatic ones. The ability of residual fuel to retain asphaltenes in solution is known as the fuels Stability Reserve. Mixing with other fuels can upset the fuel chemistry and cause the asphaltenes to fall out of solution forming a sludge. ie, the fuels are not compatible with each other. Similarly adding various cutter stocks or blending products can alter the fuel s chemistry and also cause asphaltenic drop-out and sludging. In addition, such cutter stocks may lead to sidereactions dependent upon fuel handling, storage, temperatures, engine-types, etc. and Styrene polymerization leading to blocked piping and filters.

10 Separability Number Two separate stable fuels when mixed can completely de-stabilise. In addition when, blending fuel to meet ISO8217, stability is a concern. What is it? Separability number (SN), or Reserve Stability Number (RSN), indicates the resistance of a residual fuel oil to form sludge. What does it tell us? Hot filtration methods such as TSP will indicate the amount of sediment present in a fuel oil. SN will indicate the likelihood that this sediment will flocculate and form fuel sludge. The results of the test are expressed on a scale from 0 to 15, where: <5 = Good stability reserve >5 - <10 = Intermediate stability reserve >10-15 = Poor stability reserve

11 TSP % Separability Number Why is it requested? Separability number is an excellent accompaniment to the routine hot filtration methods. It can identify potentially troublesome fuels (unstable) even when the HFT method is indicating a low sediment content. Conversely, it may indicate that a high sediment fuel is in fact quite stable and unlikely to form sludge. This information in combination, is extremely useful from an operational perspective, as it will indicate in advance if and what mitigation steps are appropriate Operational Problems Likely Operational Problems Unlikely Separability Number

12 No. of Alerts Enviro-Legislation & Blending Impact on Fuel Quality 70 ECA Limit 1.0% sulphur VPS Past 5-year Bunker Alert History ECA Change to 0.1% Sulphur Residual Distillate Total

13 No. of alerts No. of Alerts Global Fuel Quality Currently 15% of all residual fuels and 9% of all distillates fuels tested exceed the ISO8217 test specification for at least one parameter. In 2017 VPS released 58 Bunker Alerts of which 36 (62%) were related to Residual fuel & 22(38%) related to Distillate fuel quality. This was a 70% increase on 2016 Distillate Bunker Alerts, and a 30% increase on 2016 for Residual Bunker Alerts 2017: More fuel issues in Europe & Americas than AMEA. H1-2018: 33 Bunker Alerts 18 x Residual (55%), 15 x Distillate (45%) 14 x Americas, 13 x Europe, 6 x AMEA Key Parameters, Contaminants, Cat-Fines, FP VPS Bunker Alerts by Test Parameter Residual Distillate VPS Bunker Alert Volumes by Region Residual Distillate Residual Distillate Residual Distillate Residual Distillate Q1 Q1 Q2 Q2 Q3 Q3 Q4 Q4 Americas Europe Middle East Asia

14 Forensic Detection of Fuel Contaminants 2020 will see an increase in Number & Types of Fuel, wider use of Diluents, Cutter Stocks, Additives, Blending. All the above can alter the fuels chemistry, potentially destabilising, and even damaging side-effects. Original Fuel source and refining also influences fuel quality: Eg Crude types and regions, Shale Oil, Tall Oil etc. There will be an increase in fuel quality issues. Estimated Average Cost of each fuel Mgmt issue = $300K Laboratories are now using many high-end analytical techniques and methods to identify the cause of fuel problems: Gas Chromatography- Mass Spectrometry (GCMS): Chemical Screening, Extended Head-Space, Acid Extraction, Vacuum distillation Fourier Transform Infrared (FTIR), Solids contamination, Polymers Microscopy Solids and polymer identification Separability No., Reserve Stability No. (RSN) Compliment TSP/TSA/TSE CHNO Analysis (Carbon, Hydrogen, Nitrogen, Oxygen) Steel Corrosion

15 Potential Fuel Contaminants Chemical Group CHLORINATED HYDROCARBONS ALDEHYDE Comment Chlorinated hydrocarbons do not originate from any refinery processes and are therefore an indication that the fuel is possibly contaminated. Based on VPS experience, these contaminants may result in damages to fuel injection equipment. Aldehydes do not originate from normal petroleum refining and are therefore an indication that the fuel is possibly contaminated. Based on VPS experience, these contaminants may result in damages to fuel injection equipment. ALCOHOL Alcohol does not originate from normal petroleum refining. Based on VPS experience, these contaminants may result in increased sludge formation and possibly laquering and/or deposit formation. STYRENES TERPENES CYCLOPENTADIENE PHENOLS KETONES Styrenes do not originate from normal petroleum refining but are known to be present in some blend stocks for fuel oils. Based on VPS experience, these contaminants may result in increased sludge formation and possibly laquering and/or deposit formation. Terpenes do not originate from any refinery processes and are therefore an indication that the fuel is possibly contaminated. Based on VPS experience, these contaminants may result in increased sludge formation and /or damages to fuel injection equipment. DCPD does not originate from normal petroleum refining but are known to be present in some blend stocks for fuel oils. Based on VPS experience, these contaminants may result in increased sludge formation and possibly laquering and/or deposit formation. Phenols do not originate from normal petroleum refining. Based on VPS experience, these contaminants may result in increased sludge formation and /or damages to fuel injection equipment. Ketones do not originate from any refinery processes and are therefore an indication that the fuel is possibly contaminated. Based on VPS experience, these contaminants may result in damages to fuel injection equipment.

16 The Common Denominator Probable Culprit 4-Cumyl-Phenol CAS # Industrial uses for cumyl phenol include the manufacture of epoxy resins and as an emulsifier in pesticides, both of which utilise the adhesive (sticky) qualities 4-cumyl-phenol exhibits. Component is only detectable using the sophisticated GCMS technique, GCMS acid extraction

17 Fuel Specification ISO 8217 Test Parameters Test Methods Residual Fuel Distillate DMA DMZ DMB Density, kg/m 15C ISO12185/ASTM D7042 X X X X Viscosity, mm 2 /s at 50 o C ISO 3104/ASTM D7042 X Viscosity, mm 2 /s at 40 o C ISO 3104/ASTM D7042 X X X Typical specification tables do not address individual chemical contaminants by name. Protections against harmful chemical contaminants are contained in the verbiage of ISO Important for buyers and consumers to understand the specification. Water content, % V/V ISO 3733/ASTM D 6304 Proc.C X X B Micro Carbon Residue, % m/m ISO X X Micro Carbon Residue, 10% distillation residue, % m/m ISO X X Sulphur, % m/m ISO 8754 X X X X Total Sediment Potential, % m/m ISO * X Total Sediment Existent, %m/m ISO X B Ash, % m/m LP 1001 ** X X X X Vanadium, mg/kg LP 1101/IP 501 X X A Sodium, mg/kg LP 1101/IP 501 X X A Aluminium, mg/kg ISO 10478/IP 501 X X A Silicon, mg/kg ISO 10478/IP 501 X X A Iron, mg/kg LP 1101/IP 501 X X A Nickel, mg/kg LP 1101/IP 501 X X A Calcium, mg/kg LP 1101/IP 501 X X A Magnesium, mg/kg LP 1101 *** X X A Zinc, mg/kg LP 1101/IP 501 X X A Phosphorus, mg/kg LP 1101/IP 501 X X A Potassium, mg/kg LP 1101 *** X X A Flash Point, Deg C ISO (A / B)/LP 1503 X X X X Pour Point, Deg C ISO 3016/LP 1304/LP 1305 X X X X Visual Appearance Proprietary (LP 1902) X X X Specific Energy (net), MJ/kg ISO 8217 Annex A X X X X Calculated Carbon Aromaticity Index ISO 8217, Annex B X Calculated Cetane Index, CCI ASTM D4737 X X X Fatty Acid Methyl Ester (FAME) EN 14078/LP 2403 X X X Acid Number LP 2403/LP 2404/ASTM D664/LP 2003 X X X X FTIR Screening LP 2403 X X X

18 ISO-8217:2017 Edition 5.2 The fuel shall be free from any material at a concentration that causes the fuel to be unacceptable for use in accordance with Clause 1 (i.e. material not at a concentration that is harmful to personnel, jeopardizes the safety of the ship, or adversely affects the performance of the machinery). Your shield against chemically contaminated fuels. Review Your Purchasing Contract Terms and Language

19 What is or rather isn t happening?

20 Identification of Fuel Oil Contaminants by GC-MS Chromatography = Separation Mas Spec = Identification

21 GCMS-HS Screening & Extended HS GCMS-Head Space Screening detects only volatile organic components within residual fuels GCMS-HS Screening should detect around 70% of most fuel contaminants In 2018, YTD Samples tested show: 92% PASS 8% Caution The distribution of detected component groups based on GCMS HS-Extended testing where Screening shows Caution :

22 Five Flavors of GCMS Testing GCMS Screen Headspace Test Turnaround Time Description 2 Working Days This is a quick and economical test used to detect the presence of the most common chemical contaminants in fuels. It does not identify the contaminant nor provide quantification GCMS Extended Headspace 3 Working Days This test identifies the names of the contaminants but does not quantify the concentration level. GCMS Vacuum Distillate 5 Working Days This test identifies the contaminants and also quantifies the concentration level in most cases of the above 2 tests. GCMS Acid Extraction 10 Working Days This test is used for isolating organic acids from a sample. The concentrated acid extract is then analyzed by GCMS. This method will identify the names of the contaminants but will not provide concentration level GCMS Acid Extraction With Quantification 10 Working Days This test is used for isolating organic acids from a sample. The concentrated acid extract is then analyzed by GCMS. This method will identify the names of the contaminants and will also provide concentration level of each contaminant in % m/m

23 VPS Technical Focus: ASTM test method for contaminated bunkers limited ASTM D , also known as the Standard Test Method for Determination of Chemical Species in Marine Fuel Oil by Multidimensional Gas Chromatography/Mass Spectrometry (GCMS), has been developed to quantify chemical species at low levels in marine fuels oils and cutter stocks. However, it seems there are certain limitations of this test method. Dr Malcolm Cooper, the Group Managing Director of marine fuel testing and inspection agency Veritas Petroleum Services (VPS) explains to Manifold Times readers the limitation of using ASTM D as a test method for detecting 4-cumyl phenol found in contaminated marine fuel: The test method ASTM D7845 lists 29 specific chemicals that may be detected and measured within the test method, and this is a good method when looking for these compounds. However, this is not an exhaustive list and does not cover how to handle any unknowns which may be present in the fuel sample. Since there are literally thousands of possible organic contaminants that may be present in the fuel, the specific 29 chemicals named in the test method is a major limitation. Also, since 4-cumyl phenol is not amongst the 29 named chemicals, and this was the major compound we detected in the Houston fuel issue, this indicates another of the limitations of using this method. These limitations are the reason that VPS does not use this method. ASTM D uses direct injection onto a GCMS via a Deans valve-switching arrangement, whereby a sample is injected onto a pre-column prior to an analytical column, with the pre-column being back-flushed to remove heavy fuel oil components (as the only sample preparation prior to analysis). This valve-switching pre-column arrangement eliminates the higher boiling hydrocarbons in the fuel oil and can prevent high boiling chemicals from reaching the analytical column. The D7845 method detects 4-isopropyl phenol (Boiling Point 212C), but not 4-cumyl phenol (Boiling Point 335C). The method lists 29 specific compounds that can be detected, which are quantified using Single Ion Monitoring (SIM). In order to apply SIM then the organic compound must be known prior to analysis (in order to identify the SIM mass number) and when dealing with problem fuel samples then this organic contaminant is not known, which is a limitation of the method. It should be noted that the VPS Acid-Extraction GCMS method, transfers all acidic compounds from the fuel oil through extraction as a sample clean-up and extraction treatment prior to the sample being directly injected into the GCMS. This sample pretreatment method eliminates all hydrocarbon compounds in the fuel oil since they are not acidic and do not enter the aqueous phase during extraction. The method is semi-quantitative and highly selective for acidic compounds such as carboxylic acids, phenols, etc. Also, the total acidic content in the fuel oil is quantitatively measured.

24 Quality Issues - HOUSTON Jan-May over 100 vessels suffered fuel pump failure issues from fuel supplied in Houston To date, approximately 150 vessels affected. VPS investigated fuel-pump failures >50 vessels on our testing programme VPS Bunker Alerts released, 26 th April, 29 th May, 25 th June. Fuel is not single supplier specific. 10 suppliers 20 Delivery Barges Indications suggest Upstream somewhere between Refinery but before final supplier? 4-Cumyl Phenol found in Concentration range ppm. Detected by VPS In-house proprietary method utilising Acid Extraction/Gas Chromatography Mass Spectrometry. Findings Verified in two VPS laboratories (Singapore & Fujairah) Verified 4-cumyl phenol only seen in Houston fuels. 4-cumyl phenol used to manufacture resins and emulsifiers due to its sticky properties. Phenolic compounds found in fuel since All resulted in sticking fuel pumps.

25 VPS Issued a Number of Bunker Alerts

26

27 Other Quality Issues Corpus Christi Sludging of Fuel/filter blocking: 4 vessels with Petroleum Coke contamination Panama Poly-methacrylate found in fuel via solids contamination analysis - sticking fuel pumps. Plus 20 vessels affected by Houston-type contaminants Singapore 10 vessels affected by Houston-type contaminants Colombo Contaminated fuel but limited number & low concentrations of chemicals. Of all the AE-GCMS tests undertaken by VPS in 5 months: 17% cases were linked to serious damage on the associated vessels. Columbia: 10 cases of (very) high sediment fuels Not all vessels having these fuels have already burnt the fuel, the majority do not report problems. Feedback from one vessel (out of 10 high sediment fuels) is that they needed to clean the separators more often, but other than that, experienced no problems burning the fuel.

28 Seized Fuel Pump

29 Barrels Require Forced Jacking To Remove

30 Heavy Deposits On Screw Pump

31 Distillates As a result of local and global emissions legislation the demand for distillate fuels in the marine market will increase substantially. The perception has been, Distillates are Problem Free??? Not All Distillates are Low in Sulphur and require some degree of treatment. On 1 st Jan 2015 VPS saw sample submissions move from: 80:20 Residual:Distillate to 60:40 Residual:Distillate. What will we see on 1 st Jan 2020? Fuel Change-over issues Low viscosity issues Hydro-desulphurisation Decreased Lubricity o Reduced Stability Wax Precipitation due to Cold-flow properties Low Flash Point FAME: Increase in oxidative capabilities Instability Erosion of metal Deterioration of engine seals Increases fuels affinity for water leading to microbial growth & corrosion Microbial contamination Distillate quality problems may become much more common with increased demand.

32 ULSFO/Hybrids The 0.1% S ECA limit was an opportunity for suppliers who have direct contact with refineries to launch a number of new fuels In many cases these fuels were just heavier grades of gas oil that have been around for a long time The principle purpose of these new grades was to provide a fuel that met the ECA sulfur limit but had a relatively high viscosity, overcoming the potential risks associated with very low viscosity gas oils A significant characteristic of some of these new ECA fuels is that the cold flow properties, stability and compatibility, could present a challenge on some ships. Density Kg/m3, Viscosity 8-50 CSt Low Metals, Low Sediment Potential High Energy Content, High Pour Point Compatibility? Stability?

33 Typical Specs All Over The Board Parameter Unit limit Fuel A Fuel B Fuel C Fuel D Fuel E Fuel F Fuel G 15 C kg/m³ max Kin. 40 C / 50 C mm²/s min/max 40-75/ Ash % m/m max < Micro carbon residue % m/m max < < Al + Si mg/kg max <0.3 5 LT Pour point C max Flash point C min > Total sediment % m/m max < CCAI Parameter Unit limit Fuel H Fuel I Fuel J Fuel K Fuel L Fuel M Fuel N 15 C kg/m³ max Kin. 40 C / 50 C mm²/s min/max Ash % m/m max < <0.001 Micro carbon residue % m/m max < Al + Si mg/kg max <15 <15 Pour point C max Flash point C min >60 70 >70 >70 >65 60 >110 Total sediment % m/m max CCAI *Above obtained results are typical results hence subject to changes and therfore connot by guarenteed by VPS.

34 ULSFOs ? As we approach 2020, its likely more new fuels will come to the market offering compliance at <0.5% S Like New ECA fuels these will likely be Blended products (ULS distillates + LS residues) Hydro treated vacuum gas oils Hydrocracker fractionator bottoms Potentially more residual-based materials may be used and therefore: Higher viscosity to normal distillates which eliminates fuel pump leakage and damage issues Normal flash point Blending residual components with proportions of distillates could result in Reserve Stability issues and sludging.

35 Testing Recommendations Circular Friday 11 th Jan 2019

36 Testing Recommendations Residual Fuels ISO8217:2010/12,17 Chemical Screening (GCMS-HS) Separability Number (RSN) TSA/TSE Asphaltenes Fuel System Checks Distillate Fuels ISO8217:2010/12,17 Cold-Flow (CP, CFPP) Lubricity (Sulphur<500ppm) FTIR Bio/FAME Emergency Equipment Testing VLSFO s/ulsfo s Since 2015 tested to RMD80 spec. Depends upon constituent make-up of fuel. Can be a mix of the Residual & Distillate tests Compatibility & stability always a concern. No ISO8217 Specification at present

37 Oil Majors BP displayed 2 samples of new Hybrid Fuels that they have developed. They performed nearly 100 hand blends in the research process. One of them is a cracked aromatic with very low pour (-30C?). The other is highly paraffinic with high pour (18 C?) Paraffinic fuel has better combustion characteristics. BP wants the industry to look at the possibility of developing Aromaticity and Paraffinic ratings that could be assigned to hybrid fuels in order to help predict compatibility among them. ExxonMobil has announced that all of their hybrid fuels will be compatible with each other. ExxonMobil has also advised that some of the new 0.5% sulfur fuels could contain elevated levels of catfines.

38 FSC Sample Points A recommended set of Fuel System Check samples consists of one sample taken from each of the following locations: As a minimum before and after separator samples should be drawn and forwarded to the laboratory for analysis.

39 Handling / Operational Issues Always segregate bunker lots. No mixing. New fuel should not be used before analysis results are known If mixing is unavoidable perform a compatibility test beforehand. Use empty tanks or ensure tanks are drained as much as possible before loading a new fuel Be aware of specific heating requirements for hybrid fuels due to varying viscosities. Minimum storage temp should be 10 C above pour point. Low viscosity ECA distillates may require chilling for proper viscosity control prior to injectors. Some ECA fuels have a cleansing effect on storage tanks and pipelines. Suggest cleaning tanks in advance. If not possible, be prepared for additional sludge at the purifier. Consider reducing sludge cycle time at purifiers during initial changeover. In-line auto filters may backwash more frequently due to cleansing effect. VPS DATA SHOWS THAT HYBRID FUELS ARE MORE SENSITIVE TO MIXING

40 BlockChain BlockChain Processes: Applied to fuel supply could assist with improving: Product Quality Transparency & Traceability Identification of end-user problem by identifying common source in fuel supply chain Corporate Governance Ethics & Integrity Health & Safety Environmental Protection Insurance Implications

41 Summary Heading towards 2020 & Beyond Fuel Supply Chain Challenges will only increase and become more complex. Greater regulation with higher levels of Traceability & Transparency of all fuel treatments and blending components would help safeguard both suppliers and purchasers of fuel. We are already seeing a major increase in fuel quality issues, which will continue. Wider range/choice of fuels available with many technical considerations. Greater understanding of the Stability & Compatibility of fuels will assist fuel management, ie TSP/TSA/TSE/RSN. The increasing and widening types of base fuels, cutter stocks, blending agents & additives will lead to wider chemistry issues and the need for higher analytical testing techniques. Work with a Fuel & Oil Management Partner to effectively measure and monitor fuel quality, to improve operational efficiency, protect your assets, comply with legislation and ultimately save money!!

42 Thank you for your attention! YOUR FUEL MANAGEMENT PARTNER Ian Workman Questions?? Please drop me an