Fuel Quality Update - Intertanko · Fuel Quality Update 24 September 2009 3 DNV – DNVPS global...

Håkon B. Thoresen24 September 2009

Fuel Quality UpdatePresentation for INTERTANKO Bunker Subcommittee. Nafplia, Greece

© Det Norske Veritas AS. All rights reserved.

Fuel Quality Update

24 September 2009

2

Fuel Quality Agenda

5. Regulatory consequences

4. Chemical contamination

3. Fuel Quality parameters

2. Fuel Quality key trends 2005-2008

1. Introduction


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3

DNV – DNVPS global presenceDNVPS OSLO

DNVPS SINGAPORE

DNVPS HOUSTON

DNVPS FUJAIRAH

DNVPS ROTTERDAM

DNVPS Laboratories & Regional offices


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24 September 2009

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Fuel QualityFuel quality governed by :

ISO 8217 international fuel standard

MARPOL Annex VI

EU Directive 2005/33 EC

Local regulations e.g. - California- Svalbard


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CLAUSE 5 : GENERAL REQUIREMENTS

5.1 The fuels shall be homogenous blends of hydrocarbons derived from petroleum refining. This shall not preclude the incorporation of small amounts of additives intended to improve some aspects of performance. The fuels shall

be free from inorganic acid and from used lubrication oils.

The fuel should not include any added substance or chemical waste which:

-

jeopardises the safety of ships or

-

adversely affects the performance of the machinery; or

-

is harmful to personnel; or

-

contributes overall to additional air pollution.

ISO 8217:2005 Int. Standard ISO 8217 – 2005Petroleum Products -- Fuels (class F) -- Specifications of Marine FuelsThird Edition2005-11-01


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REGULATION 18 (in force 19 May 2005) maintained in revised MARPOL Annex VI (in force 1 July 2010)

Fuel oil for combustion purposes delivered to and used on board ships which this Annex applies shall meet the following requirements:

the fuel oil shall be blends of hydrocarbons derived from petroleum refining. This shall not preclude the incorporation of small amounts of additives intended to improve some aspects of performance;

the fuel oil shall be free from inorganic acid;

the fuel oil shall not include any added substance or chemical waste which either:

- jeopardizes the safety of ships or adversely affects the performance of the machinery, or

- is harmful to personnel, or- contributes overall to additional air pollution

MARPOL Annex VI (Statutory)

http://search.kvasir.no/query?what=show_image&imgurl=http://merrac.nowpap.org/img/k1/03_img.gif&url=http%3A%2F%2Fmerrac.nowpap.org%2Fhtml%2Fk_3_center.html&img=http://merrac.nowpap.org/img/k1/03_img.gif&w=88&h=87


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Current EU legislation

EU Directive EC 2005/33:

1.50% sulphur limit in IMO SECA’s.

1.50% sulphur limit for passenger vessels in the EU.

0.10% sulphur limit for DMA in EU territory (12 nm zone) from 1.January 2008 until 1. January 2010).

0.1% sulphur limit for any fuel used onboard ships in EU ports as of 1. January 2010.


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Revised MARPOL Annex VI

Sulphur limit for fuel oil Sulphur content Enforcement

Global 4.50%3.50%0.50%

[Prior to 1 January 2012][1 January 2012][1 January 2020]*

ECA (SECA) 1.50%1.00%0.10%

[Prior to 1 July 2010][1 July 2010]

[1 January 2015]

Abatement technology (eg Scrubbers) is an "equivalent measure".

This means that an Administration may allow abatement technologies, but the Administration (and not the ship) have to acknowledge that:

They have equivalent efficiency in terms of SOx, PM and NOx emissions.

That they operate within the requirements of the IMO guidelines

That they do not harm the environment.

Adopted 9 October 2008 - IMO MEPC58 -– Enter into force 1 July 2010

*Subject to a review of fuel availability in 2018, with the option to delay the 0.5% sulphur global cap by five years



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Fuel Quality Agenda





1. Introduction


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HFO 2005-2008

Specification Not Met

0%

5%

10%

15%

20%

25%

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

% o

f all

deliv

erie

s


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HFO 2005-2008

Sulphur "Off Spec"

24.4%23.0%

15.0% 15.8%16.9% 17.3%

18.5%

0.07% 0.03% 0.03% 0.01% 0.01% 0.01% 0.03%0%

5%

10%

15%

20%

25%

30%

2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

BDN=<S1.50% - S>1.50%BDN>S1.50% - S>4.50%


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HFO 2005-2008

Period Average

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

S %

Global sulphur average per sample tested


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Distillates 2005-2008

Distilates Specifications Not Met

0%

2%

4%

6%

8%

10%

12%

14%

2005 2006 2007 2008

Spec Not Met


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Off Specification Parameters

0.0%

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

2005 2006 2007 2008

H2O>0.5%H2O>1.0%FP<60


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BDN S=<0.10%

0%

5%

10%

15%

20%

25%

30%

35%

40%

2005 2006 2007 2008

BDN S=<0.10%S>0.10%


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Fuel Quality Agenda





1. Introduction


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18

Fuel Quality - Norway and Germany proposal



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Fuel Quality – Norway and Germany proposal



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Fuel Quality - Norway and Germany proposal



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HFO 2005-2008 – Off Spec parameters

0%

1%

2%

3%

4%

5%

6%

7%

8%

9%

10%

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

% o

f all

deliv

erie

s

H2O > 0.5%H2O >1%TSP >0.1


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HFO 2005-2008 – Aluminium + Silicon content

Al+Si Content

0%

1%

2%

3%

4%

5%

6%

7%

8%

9%

10%

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

% o

f all

deliv

erie

s

>80>60>50


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HFO 2005-2008 – Potassium, MCR, & “ULO”

0%

1%

2%

3%

4%

5%

6%

7%

8%

9%

10%

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

% o

f all

deliv

erie

s

"ULO"MCR>18K>=3


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HFO 2005-2008 – CCAI

Period Average

840

841

842

843

844

845

846

847

848

849

850

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

CCAI


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HFO 2005-2008 – CCAI

CCAI

0.1%

0.10

%

0.03

%

0.10

%

0.03

%

0.05

%

0.04

%

0.05

%2.

16%

2.29

%

2.49

%

1.90

%

2.06

%

1.9%

2.10

%

1.7%

0%

5%

10%

15%

20%

25%

30%

35%

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

% o

f all

deliv

erie

s

>870>860>850


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HFO 2005-2008 – CCAI

CCAI

0.1% 0.10

%

0.03

%

0.10

%

0.03

%

0.05

%

0.04

%

0.05

%

1.7%

2.10

%

1.9% 2.

06%

1.90

%

2.49

%

2.29

%

2.16

%

0.0%

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

2005 I 2005 II 2006 I 2006 II 2007 I 2007 II 2008 I 2008 II

% o

f all

deliv

erie

s

>870>860


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Off Specification Parameters

0.0%

0.5%

1.0%

1.5%

2.0%

2.5%

3.0%

2005 2006 2007 2008

H2O>0.5%H2O>1.0%FP<60


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Fuel Quality Agenda





1. Introduction


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Solvent Contaminant in Singapore Port Bunker Fuels

2001


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Summary - Solvent Contaminant in SingaporeSingapore, October 2001 :

A fully loaded VLCC bunkered 3000 MT of HFO

Soon after : Auxiliary and main engine breakdown

Result : Full black-out in Malacca Straits

Cause : Sticking fuel pumps and clogged filters

Investigation revealed :

Fuel apparently within ISO specification, but quite ‘aggressive’

Solvent-like organic contaminants detected by sophisticated additional analyses

At least 10 ships affected

Rapid identification limited further major damages and accidents


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Solvent Contaminants in Fujairah Bunker Fuels

2004


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Summary Solvent Contaminants in FujairahBunkering at Fujairah in March - April 2004. More than 20 vessels received contaminated fuels

One supplier and two barges were involved

Nine Vessels reported Engine Problems

At least one had to be towed

Problems in Fuel Pumps of

Main & Auxiliary Engines

were reported. Engines

failed to start.


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Fujairah Contamination ~ 2004DNVPS identified following chlorinated contaminants using advanced Analytical Techniques of GC-MS*:

1,2-dichloroethane1,1,2-trichloroethane

These low boiling point contaminants are known to be used in the

industry as a solvent, degreaser, paint stripper etc. and is a serious health hazard.

A Bunker Alert was issued by DNVPS on 08-April-2004.

Based on the above Bunker Alert Ship managers stopped consuming the contaminated bunkers and several ships de-bunkered without using the fuel.

* Gas Chromatography and Mass Spectroscopy


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Solvent Contaminant in Gulf of Guinea Bunker Fuels

2007


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Bunkers in Nigeria, Gabon & Angola July 2007 - Several ships affected

Higher level of TSP/TSE/Vanadium

Typical problems encountered:1.

Filter problems2.

Purifying problems3.

Deposits on Injector Nozzles4.

Fuel Pump Injector Problems5.

Complete Blackout

Solvent Contaminant – Gulf Of Guinea

Summary


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GC-MS- Vacuum distillate with boiling temperature < 250°C

Detected- Terpenes

(mainly in the form of Pinene)-- Phenolic

compound [4-(1-methylethyl)-phenol]“

Use of Pinene- Solvents for paints,- Coatings and wax formulations. - Intermediate for resins and for camphor, - Menthol Campholenic

aldehyde

and terpineol. Used as lube-oil additives“

Solvent Contaminant – Gulf Of Guinea


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Fuel Pump Plungers Lacquering

Balboa, Panama


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Bunker Alert Ref : 39/2007


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Four Vessels Experience - Fuel Lifted in Balboa

Vessel #1

10 July 07

Vessel #2

14 Aug 07

Vessel #3

2 Aug 07

Vessel #4

Approx 20 Aug 07

M/E Fuel pump problems. 3 Replaced

Aft preheating stage; Oil get sticky

Purifier and Filter clogged

Aft Final preheating; Filter, valves and other moving parts got stuck.

M/E and A/E Severe Fuel Pump and nozzle problems

Fuel pump problems;

Stuck fuel pumps and exhaust valves

A/E Fuel pump stuck

M/E exhaust temp drop

M/E fuel pump plungers lacquered


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Further Testing; GCMS; Results

The common GCMS results for the three vessels- Styrene- Alpha-methyl-benzene methanol

- Also known as alpha-Methyl-benzyl alcohol- Benzeneethanol

- Also known as Phenylethyl

Alcohol

In addition

#1- Phenolic

compound (dimethyl-phenol)

#2- Phenolic

compounds (Phenol, Ethyl-phenol)

#2&3- Phenoxy

Propanol

(1-Phenoxy-2-propanol)


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Added Substance -

Polystyrene


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SUSPECTED SHALE OIL

BALTIC PORT


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VENTSPILS AUGUST 2007

LSFO & HSFO bunkered 28 and 29 august 2007

Problems reported :- Excessive quantity of solid

sludge; sediments, asphalt- Drain hole plugged by sludge - Not possible to operate purifier- Poor combustion M/E & A/E- Changed over to MDO


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Tested Results - HSFO vs LSFOTested Results Units RMG380

-------------- ----- ------

Density @ 15C kg/m3 982.0 970.0 991.0

Viscosity @ 50C mm2/s 361.0 177.2 380.0

Water %V/V LT 0.1 0.3 0.5

Micro Carbon Residue %m/m 11 8 18

Sulfur %m/m 2.36 1.41 4.50

Total Sediment Potential %m/m LT 0.01 0.03 0.10

Ash %m/m 0.04 0.05 0.15

Vanadium mg/kg 121 68 300

Sodium mg/kg 24 53

Aluminium mg/kg 5 11

Silicon mg/kg 8 27

Iron mg/kg 14 22

Nickel mg/kg 38 25

Calcium mg/kg 2 15

Magnesium mg/kg 1 4

Lead mg/kg LT 1 LT 1

Zinc mg/kg LT 1 LT 1

Phosphorus mg/kg LT 1 LT 1

Potassium mg/kg 1 6


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GCMS Analysis

GC-MS analysis performed on the vacuum distillate <250°C of the sample detected monophenols

and diphenols

which are not normally found in residual fuels.

The types of phenols detected are listed below:

-

Monophenols

(Phenol, methyl phenols, dimethyl

phenols and methyl-ethyl phenols)

-

Diphenols

(5-methylresorcinol (also known as Orcinol), dimethylresorcinol, other alkyl-substituted resorcinols)

The concentration of monophenols

and diphenols

in the sample was estimated to be at 0.4% and 0.2% respectively.

Apart from phenols, GC-MS analysis also detected a significant level of alkenes (estimated 0.9%) in the sample.


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Contaminated Diesel Oil St. Petersburg

2007/8


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Contaminated Diesel Oil - St. Petersburg

After nine days one ship experienced black out!

The DO in question had a strong chemical odour

After this, several samples from this delivery was tested extensively


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Acid Number- ≈16 mg KOH/g (very high)

FTIR- Unusual, Strong Carbonyl absorption at 1745 cm-1

GC-MS- On Acid Extract

- 2-ethylhexanoic acid-Concentration estimated to 3.0% by wt- Headspace Analysis (Concentration estimate not possible)

- Butanal- 1-Propanol, 2-methyl- 1-Butanol- 2-Ethylhexenal- 2-Ethylhexanol- Various esters of Ethylhexanoic

acid (e.g. Butyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate)- Other complex chemical mixtures which could not be identified

Contaminated Diesel Oil Test Results - St. Petersburg


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Screening for chemical contamination in HFO

Large number of possible contaminants.

High boiling point contaminants more difficult to detect.

Limited knowledge regarding effect on engines in different concentrations and combinations of contaminants.

Important to ensure that screening does not give false sense of security.

Combination of different screening techniques give better results.


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FT-IR Spectrometer


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-

FT-IR Scan

is used for characterizing and identifying organic

compounds present in marine fuels

-These compounds have different chemical bonding and molecular structures, which exhibit unique absorption when a fuel sample is exposed to infra-red (IR) radiation.

-

Examples of organic compounds are alcohols, esters and acids, which are indicative of the inclusion of chemical waste products in the fuel.

FTIR Spectroscopy (Fourier Transform Infra Red)


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GC-MS Instrument

Headspace Analyzer

Mass Spectrometer

Gas Chromatograph


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Types of GC-MS Analysis

Different Analysis methods:

Headspace GC-MS Analysis

GC-MS Analysis on sample distillate

Headspace can be performed using different Headspace conditions (e.g. sample heating temperature, heating duration)

Use of higher heating temperature will enable more components to

be vapourised

into the Headspace & hence subsequently screened for presence of contaminants compared to when lower sample heating temperature is used.


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Components of Headspace GC-MS Instrument

Vial with

sample

Aluminium

crimped

cap

Sample

Headspace

Sample Loop Transfer Line

GC inlet

GC OvenCapillary ColumnMS

Needle

Headspace Oven

Headspace Analyzer

Mass Spectrometer

Gas Chromatograph


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GC-MS Chromatogram of the Distillate Fraction of a Contaminated HFO

10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.000

10000 20000 30000 40000 50000 60000 70000 80000 90000

100000 110000 120000 130000 140000 150000 160000 170000 180000 190000

Time-->

Abundance TIC: F301016056 Distillate <250°C

3.55

4.33

5.03 7.41

8.79

14.67

15.39

24.88

29.24

31.94

36.22

37.83

41.87

48.24

60.20 71.55

77.31

80.79

80.96

83.48

85.79

GC/MS Scan on Distillate Cut Below 250°C of Sample F301016056 ex M/V “M F”

Dimethyl esterof

Hexanedioicacid


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Fuel Quality Agenda





1. Introduction


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Fuel Quality – Regulatory consequencesMARPOL Annex VI and EU Directive 2005/33 EC

- Fuel quality has become a statutory matter (not only commercial)- Increase in Off-Spec related to Sulphur (MARPOL Annex VI/EU Directive) HFO/MGO/MDO- Increase in Off-Spec related to Flash Point (EU Directive sulphur) MGO/MDO

Experience current enforcement wrt compliance to MARPOL Annex VI- Statistics shows high frequency of non-compliant fuels being supplied to ships in major

ports which could indicate insufficient enforcement.


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Fuel Quality – Way forwardISO

- Evaluation of the Draft International Standard (DIS) ISO 8217 through the national ISO body prior to balloting December 2009

IMO- Fuel Quality

- Following on the work of ISO, it is expected that IMO will make a decision how to address parameters relevant for environment, ship safety, human health in MARPOL Annex VI.

- Enforcement - One administration has indicated that the Guidelines for Port State control

should be amended to require Port States to perform testing of statutory samples at ISO 17025 accredited laboratories.

- To address substandard fuel quality/suppliers & ships- To create level playing field

- Expected that IMO will respond to H2S challenge from ISO


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