Bunker Fuel Quality - Ian Workman Account Manager VPS Testing & Inspection Inc - DNVGL.us
←
→
Page content transcription
If your browser does not render page correctly, please read the page content below
Bunker Fuel
Quality
Ian Workman
Account Manager
VPS Testing & Inspection Inc
DNVGL FEB 7th 2019
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
DNVGL FEB 7th 2019
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
DNVGL FEB 7th 2019
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
DNVGL FEB 7th 2019
Crude Oil & Refining
• On average, crude oils are made of the
following elements or compounds:
• Carbon - 84%
• Hydrogen - 14%
Crude Oil Composition
• Sulphur Species- 1 to 3%
100
• Nitrogen compounds-
Marine Fuel Production: Complex Refinery
Processes (Catalytic Cracking & Vis-breaking)
Distillates
Light Cycle Oil
Fluidised
Bed
Catalytic
• Crude Oil Atmospheric Cracking
Distillation
Unit
Heavy Cycle Oil
Residue Vacuum
Typical Blending Components: Distillation
Light Cycle Gas Oils (60% Aromatics) Unit
Heavy Cycle Gas Oils
Additional Processing:
Visbreaker
Hydro-desulphurisation Residue
Can also remove O & N species
affecting
Fuel lubricity & stability.
DNVGL FEB 7th 2019
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.
DNVGL FEB 7th 2019
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
DNVGL FEB 7th 2019
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 “side-
reactions” dependent upon fuel handling, storage,
temperatures, engine-types, etc. and Styrene
polymerization leading to blocked piping and filters.
DNVGL FEB 7th 2019
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 - 10-15 = Poor stability reserve
DNVGL FEB 7th 2019Separability 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.
0.20
Operational Problems Likely
TSP %
0.10
Operational Problems
0.01 Unlikely
5 10 15
Separability Number
DNVGL FEB 7th 2019Enviro-Legislation & Blending Impact on Fuel Quality
VPS Past 5-year Bunker Alert History
70
ECA Limit 1.0% sulphur
60
50
ECA Change to 0.1% Sulphur
No. of Alerts
40
30
20
10
0
2013 2014 2015 2016 2017
Residual Distillate Total
DNVGL FEB 7th 2019Global Fuel Quality
• Currently 15% of all residual fuels and VPS Bunker Alerts by Test Parameter - 2017
9% of all distillates fuels tested exceed 14
12
the ISO8217 test specification for at
No. of Alerts
10
8
least one parameter. 6
4
• In 2017 VPS released 58 “Bunker Alerts” 2
0
of which 36 (62%) were related to
Residual fuel & 22(38%) related to
Distillate fuel quality.
Residual Distillate
• This was a 70% increase on 2016
Distillate Bunker Alerts, and a 30%
VPS Bunker Alert Volumes by Region - 2017
increase on 2016 for Residual Bunker 7
Alerts 6
5
No. of alerts
• 2017: More fuel issues in Europe & 4
Americas than AMEA. 3
2
• H1-2018: 33 Bunker Alerts 1
0
• 18 x Residual (55%), 15 x Distillate (45%) Residual Distillate Residual Distillate Residual Distillate Residual Distillate
• 14 x Americas, 13 x Europe, 6 x AMEA Q1 Q1 Q2 Q2 Q3 Q3 Q4 Q4
Americas Europe Middle East Asia
• Key Parameters, Contaminants, Cat-Fines, FP
DNVGL FEB 7th 2019Forensic 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
DNVGL FEB 7th 2019Potential Fuel Contaminants
Chemical Group Comment
Chlorinated hydrocarbons do not originate from any refinery processes and are therefore an indication
CHLORINATED
that the fuel is possibly contaminated. Based on VPS experience, these contaminants may result in
HYDROCARBONS damages to fuel injection equipment.
Aldehydes do not originate from normal petroleum refining and are therefore an indication that the
ALDEHYDE fuel is possibly contaminated. Based on VPS experience, these contaminants may result in damages to
fuel injection equipment.
Alcohol does not originate from normal petroleum refining. Based on VPS experience, these
ALCOHOL contaminants may result in increased sludge formation and possibly laquering and/or deposit
formation.
Styrenes do not originate from normal petroleum refining but are known to be present in some blend
STYRENES 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
TERPENES 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
CYCLOPENTADIENE 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
PHENOLS 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
KETONES fuel is possibly contaminated. Based on VPS experience, these contaminants may result in
damages to fuel injection equipment.
DNVGL FEB 7th 2019The Common Denominator – Probable Culprit
4-Cumyl-Phenol CAS # 599-64-4
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
DNVGL FEB 7th 2019Fuel Specification – ISO 8217
Distillate
Test Parameters Test Methods Residual Fuel
DMA DMZ DMB
Density, kg/m3 @ 15C ISO12185/ASTM D7042 X X X X
Viscosity, mm2/s at 50oC ISO 3104/ASTM D7042 X
Viscosity, mm2/s at 40oC ISO 3104/ASTM D7042 X X X
Water content, % V/V ISO 3733/ASTM D 6304 Proc.C X XB
Typical specification tables do not address
Micro Carbon Residue, % m/m ISO 10370 X X
individual chemical contaminants by name.
Micro Carbon Residue,
Protections against harmful chemical ISO 10370 X X
10% distillation residue, % m/m
contaminants are contained in the verbiage of Sulphur, % m/m ISO 8754 X X X X
Total Sediment Potential, % m/m ISO 10307-2 * X
ISO-8217. Important for buyers and
Total Sediment Existent, %m/m ISO 10307-1 XB
consumers to understand the specification.
Ash, % m/m LP 1001 ** X X X X
Vanadium, mg/kg LP 1101/IP 501 X XA
Sodium, mg/kg LP 1101/IP 501 X XA
Aluminium, mg/kg ISO 10478/IP 501 X XA
Silicon, mg/kg ISO 10478/IP 501 X XA
Iron, mg/kg LP 1101/IP 501 X XA
Nickel, mg/kg LP 1101/IP 501 X XA
Calcium, mg/kg LP 1101/IP 501 X XA
Magnesium, mg/kg LP 1101 *** X XA
Zinc, mg/kg LP 1101/IP 501 X XA
Phosphorus, mg/kg LP 1101/IP 501 X XA
Potassium, mg/kg LP 1101 *** X XA
Flash Point, Deg C ISO 2719 - (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
LP 2403/LP 2404/ASTM
Acid Number X X X X
D664/LP 2003
FTIR Screening LP 2403 X X X
DNVGL FEB 7th 2019ISO-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
DNVGL FEB 7th 2019What is or rather isn’t happening?
DNVGL FEB 7th 2019Identification of Fuel Oil Contaminants by GC-MS
Chromatography = Separation Mas Spec = Identification
DNVGL FEB 7th 2019GCMS-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”:
DNVGL FEB 7th 2019Five Flavors of GCMS Testing
Test Turnaround Time Description
This is a quick and economical test used to detect the
presence of the most common chemical contaminants in
GCMS Screen Headspace 2 Working Days
fuels. It does not identify the contaminant nor provide
quantification
This test identifies the names of the contaminants but does
GCMS Extended Headspace 3 Working Days
not quantify the concentration level.
This test identifies the contaminants and also quantifies the
GCMS Vacuum Distillate 5 Working Days
concentration level in most cases of the above 2 tests.
This test is used for isolating organic acids from a sample. The
concentrated acid extract is then analyzed by GCMS. This
GCMS Acid Extraction 10 Working Days
method will identify the names of the contaminants but will
not provide concentration level
This test is used for isolating organic acids from a sample. The
concentrated acid extract is then analyzed by GCMS. This
GCMS Acid Extraction With Quantification 10 Working Days method will identify the names of the contaminants and will
also provide concentration level of each contaminant in %
m/m
DNVGL FEB 7th 2019VPS Technical Focus:
ASTM test method for contaminated bunkers ‘limited’
ASTM D7845-17, 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 D7845-17 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 D7845-17 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 pre-
treatment 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.
DNVGL FEB 7th 2019Quality 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, 26th April, 29th May, 25th 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 300-1000ppm.
• 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 2007. All resulted in sticking fuel pumps.
DNVGL FEB 7th 2019VPS Issued a Number of Bunker Alerts
DNVGL FEB 7th 2019DNVGL FEB 7th 2019
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.
DNVGL FEB 7th 2019Seized Fuel Pump
DNVGL FEB 7th 2019Barrels Require Forced “Jacking” To Remove
DNVGL FEB 7th 2019Heavy Deposits On Screw Pump
DNVGL FEB 7th 2019Distillates
• 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 •
Fuel Change-over issues
Low viscosity issues
“Problem Free”??? • Hydro-desulphurisation
o Decreased Lubricity
• Not All Distillates are Low in Sulphur and o Reduced Stability
require some degree of treatment. • Wax Precipitation due to Cold-flow properties
• Low Flash Point
• On 1st Jan 2015 VPS saw sample submissions
move from: 80:20 Residual:Distillate to • FAME:
Increase in oxidative capabilities
60:40 Residual:Distillate. Instability
Erosion of metal
• What will we see on 1st Jan 2020? 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.
DNVGL FEB 7th 2019ULSFO/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 860-920Kg/m3, Viscosity 8-50 CSt
• Low Metals, Low Sediment Potential
• High Energy Content, High Pour Point
• Compatibility? Stability?
DNVGL FEB 7th 2019Typical Specs – All Over The Board Parameter Unit limit Fuel A Fuel B Fuel C Fuel D Fuel E Fuel F Fuel G Density @ 15°C kg/m³ max 895-915 936 850-890 923 858 870 910 Kin. Visco @ 40°C / 50°C mm²/s min/max 40-75/25-45 17 6-13 61 17 8 65 Ash % m/m max
ULSFOs - 2020? • As we approach 2020, its likely more new fuels will come to the market offering compliance at
Testing Recommendations – Circular Friday 11 th Jan 2019
DNVGL FEB 7th 2019Testing Recommendations • Residual Fuels • Distillate Fuels • ISO8217:2010/12,17 • ISO8217:2010/12,17 • Chemical Screening (GCMS-HS) • Cold-Flow (CP, CFPP) • Separability Number (RSN) • Lubricity (Sulphur
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.
DNVGL FEB 7th 2019FSC 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.
DNVGL FEB 7th 2019Handling / 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
DNVGL FEB 7th 2019BlockChain
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
DNVGL FEB 7th 2019Summary
• 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!!
DNVGL FEB 7th 2019Thank you for your attention!
YOUR FUEL MANAGEMENT PARTNER
Ian Workman Questions?? Please drop me an e-mail
Ian.workman@v-p-s.com
914 764 7053762
DNVGL FEB 7th 2019You can also read
