ISO 23306 2020 (En)

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INTERNATIONAL ISO
STANDARD 23306

First edition
2020-10

Specification of liquefied natural gas


as a fuel for marine applications
Spécification du gaz naturel liquéfié comme carburant pour les
applications maritimes

Reference number
ISO 23306:2020(E)

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ISO 23306:2020(E)


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ISO 23306:2020(E)


Contents Page

Foreword......................................................................................................................................................................................................................................... iv
Introduction...................................................................................................................................................................................................................................v
1 Scope.................................................................................................................................................................................................................................. 1
2 Normative references....................................................................................................................................................................................... 1
3 Terms and definitions...................................................................................................................................................................................... 1
4 General requirements...................................................................................................................................................................................... 2
5 Sampling......................................................................................................................................................................................................................... 3
6 Requirements, limit values and related test methods................................................................................................... 3
7 Main compounds removed by liquefaction process......................................................................................................... 4
Annex A (normative) Propane knock index: Methane number calculation method........................................... 6
Annex B (informative) Examples of LNG composition......................................................................................................................12
Annex C (informative) Methane number (knock resistance) and Wobbe index (thermal
input through a restriction)....................................................................................................................................................................15
Annex D (informative) LNG ageing along the bunkering chain...............................................................................................17
Annex E (informative) Particles...............................................................................................................................................................................18
Annex F (informative) Melting and boiling points of pure components and impurities that
can be present in different LNG..........................................................................................................................................................19
Bibliography.............................................................................................................................................................................................................................. 21

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ISO 23306:2020(E)


Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular, the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www​.iso​.org/​directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www​.iso​.org/​patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation of the voluntary nature of standards, the meaning of ISO specific terms and
expressions related to conformity assessment, as well as information about ISO's adherence to
the World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT), see
www​.iso​.org/​iso/​foreword​.html.
This document was prepared by Technical Committee ISO/TC 28, Petroleum and related products, fuels
and lubricants from natural or synthetic sources, Subcommittee SC 4, Classifications and specifications,
in collaboration with the European Committee for Standardization (CEN) Technical Committee
CEN/TC 408, Natural gas and biomethane for use in transport and biomethane for injection in the natural
gas grid, in accordance with the Agreement on technical cooperation between ISO and CEN (Vienna
Agreement).
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing of these bodies can be found at www​.iso​.org/​members​.html.

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ISO 23306:2020(E)


Introduction
Due to numerous economic and environmental factors, the use of liquefied natural gas (LNG) as fuel
for marine applications has increased. The 0,10 % sulfur limit, in the sulfur emission controlled areas
in Europe and the US, which entered into force on 1 January 2015 has been one of the major driving
forces for using LNG as fuel for marine applications. The decision for the 0,50 % global sulfur limit from
1 January 2020 by the International Maritime Organization (IMO) might further increase the interest
in LNG. The International Code of Safety for Ships using Gases or other Low-flashpoint Fuels (IGF Code)
was a response to the need of guidance in this emerging market. Since LNG-fueled vessels are likely
to bunker LNG in different parts of the world, a common specification is needed for ship owners, ship
operators and LNG suppliers. It would help engine manufacturers and ship designers and it is beneficial
for the development of this new alternative marine fuel market.
In 2018, IMO adopted an initial strategy on reduction of greenhouse gas (GHG) emissions from ships.
The strategy includes the objective to peak GHG emissions from international shipping as soon as
possible, whilst pursuing efforts towards decarbonizing the sector as soon as possible in this century.
It also includes the objectives to reduce the CO2 emissions per transport work and total annual GHG
emissions from international shipping by 2050, with an interim target in 2030. Thus, LNG produced
from renewable sources as biomethane that can reduce CO2 emissions when used as marine fuel is also
addressed in this document.
LNG is produced in different locations in the world in liquefaction plants. Large scale production
facilities are often dedicated to specific markets such as natural gas grids and large power plants
that use their own standards. This document takes into consideration this major constraint for any
adaptation to marine applications specificities/requirements.

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INTERNATIONAL STANDARD ISO 23306:2020(E)

Specification of liquefied natural gas as a fuel for marine


applications

1 Scope
This document specifies the quality requirements for Liquefied Natural Gas (LNG) used as a fuel for
marine applications. It defines the relevant parameters to measure as well as the required values and
the test reference methods for all those parameters.
This document applies to LNG from any source, e.g. gas from conventional reservoirs, shale gas, coalbed
methane, biomethane, synthetic methane. LNG described in this document can come from synthesis
process out of fossil fuels or renewable sources.
This document identifies the required specifications for fuels delivered at the time and place of custody
transfer (at the delivery point).

2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 6578, Refrigerated hydrocarbon liquids — Static measurement — Calculation procedure
ISO  6974 (all parts), Natural gas  — Determination of composition and associated uncertainty by gas
chromatography
ISO 6976, Natural gas — Calculation of calorific values, density, relative density and Wobbe indices from
composition
ISO  8943, Refrigerated light hydrocarbon fluids — Sampling of liquefied natural gas — Continuous and
intermittent methods
EN 16726, Gas infrastructure — Quality of gas — Group H

3 Terms and definitions


For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://​w ww​.iso​.org/​obp
— IEC Electropedia: available at http://​w ww​.electropedia​.org/​
3.1
biomethane
methane rich gas derived from biogas or from gasification of biomass by upgrading with the properties
similar to natural gas
[SOURCE: ISO 14532:2014, 2.1.1.15]

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3.2
liquefied natural gas
LNG
natural gas that has been liquefied after processing
[SOURCE: ISO 14532:2014, 2.1.1.12, modified — Definition has been shortened, note to entry has been
deleted.]
3.3
methane number
MN
rating indicating the knocking characteristics of a fuel gas
Note 1 to entry: It is comparable to the octane number for petrol. One expression of the methane number is the
volume percentage of methane in a methane-hydrogen mixture, that in a test engine under standard conditions
has the same tendency to knock as the fuel gas to be examined.

[SOURCE: ISO 14532:2014, 2.6.6.1]


3.4
natural gas
complex gaseous mixture of hydrocarbons, primarily methane, but generally includes ethane, propane
and higher hydrocarbons, and some non-combustible gases such as nitrogen and carbon dioxide
Note  1  to  entry:  Natural gas can also contain components or contaminants such as sulfur compounds and/or
other chemical species.

[SOURCE: ISO 14532:2014, 2.1.1.1]


3.5
Wobbe index
calorific value on a volumetric basis at specified reference conditions, divided by the square root of the
relative density at the same specified metering reference conditions
[SOURCE: ISO 14532:2014, 2.6.4.3, modified — Note to entry has been deleted.]

4 General requirements

4.1 The LNG at the delivery point shall conform with the characteristics and limits given in Table  1
when tested in accordance with the specified methods.

The components listed in Table 1 and Table 2 shall be measured to enable the calculation of the physical
properties of the LNG at the delivery point.

4.2 The LNG delivered shall be free from any material at a concentration that causes the LNG to be
unacceptable for use, 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.

4.3 Physicochemical characteristics not requiring measurement are listed in Table 3.

It is not practical to require detailed chemical analysis for each delivery of fuels beyond the
requirements listed in Table 1 or Table 2. Instead, a liquefaction plant, LNG terminal or any other supply
facility, including supply barges and truck deliveries, shall have in place adequate quality assurance
and management of change procedures to ensure that the resultant LNG is in conformance with the
requirements of this document.
Examples of LNG compositions are given in Annex B.
Information on ageing of LNG can be found in Annex D and information on particles can be found in
Annex E.

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4.4 The reference conditions shall be 288,15 K,  101,325  kPa (see ISO 13443:1996, Clause 3) in the
gaseous phase.

5 Sampling
Samples for quality verification are not mandatory but can be taken at various locations as agreed
among the parties concerned. Samples, if any, can also be taken at multiple moments in time, as LNG
has distinct different ageing characteristics than traditional hydrocarbon maritime fuels (with regards
to ageing reference is made to Annex D). In order to ensure a representative sample, proper sampling
procedures should be followed.
When sampling of LNG for analysis is carried out, it shall be in accordance with the procedures
provided in ISO 8943 or an equivalent national standard agreed between the parties concerned. Where
specific sampling requirements are documented, the relevant parties should agree on the reference
test methods. The LNG collected in liquid state shall be instantly conditioned to gaseous state without
any partial vaporization or loss of molecular components to ensure a representative sample.
There are two methods for sampling LNG as defined in ISO 8943, continuous and intermittent. Both
methods obtain LNG from the LNG cargo/bunker line and then it is gasified in a vaporizer. The
continuous method collects the gasified LNG in a sample holder at a constant flow rate for offline
analysis. The intermittent method collects gasified LNG and directs it to an on-line analyzer at
predetermined intervals. Please refer to ISO 8943 for more details on these methods.
The requirements for sampling LNG for marine applications can vary throughout the industry,
depending on availability and equipment. Load port samples can be used for quality determination if
the sampling equipment is not available and if it is agreed between the parties.

6 Requirements, limit values and related test methods


The components and physicochemical characteristics that shall be measured or calculated using the
related test methods are given in Table 1 and Table 2.
NOTE Information can be found in ISO 6975[1].

Information on MN and Wobbe index can be found in Annex C.

Table 1 — Physicochemical characteristics requiring measurement/calculation with limit values


Characteristic Unit Limit Value Test method
Net Calorific Value (NCV) MJ/m3 (s) Min 33,6a ISO 6976
Nitrogen % (mol) Max 1,0 ISO 6974 (all parts)
b Annex A (Propane knock
Methane Number (MN) no unit Min
index) or EN 16726
a Calculated for a theoretical mixture of 99  %  (mol) methane and 1  %  (mol) nitrogen in liquid phase. The
Gross Calorific Value can be calculated from the Net Calorific Value (see ISO 13443:1996).
b Both the method used for determining the MN and the minimum value shall be agreed between supplier and user.

The fuel supplier shall calculate the actual MN at the delivery point and provide this information to the
user (see Clause 5 for sampling location). This information shall be given as MN (PKI) or MN (EN 16726).
For guidance on the MN applicability to a specific application, Original Equipment Manufacturer (OEM)
specifications should be considered.

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Table 2 — Physicochemical characteristics requiring measurement without limit values


Characteristic Unit Test method Value
Densitya kg/m3 ISO 6578 Report
Methane (CH4) % (mol) ISO 6974 (all parts) Report
Ethane (C2H6) % (mol) ISO 6974 (all parts) Report
Propane (C3H8) % (mol) ISO 6974 (all parts) Report
n-Butane (C4H10)
% (mol) ISO 6974 (all parts) Report
i-Butane
Pentane(C5H12) % (mol) ISO 6974 (all parts) Report
a Density at temperature of the liquid phase.

7 Main compounds removed by liquefaction process


Natural gas is liquid at around −160  °C under atmospheric pressure and becomes Liquefied Natural
Gas (LNG). To avoid freezing and plugging in the liquefaction plant's cryogenic heat exchangers,
usual impurities or compounds that are present in the natural gas from various sources are removed
upstream from the liquefaction process below their solubility level. Some LNG components (e.g. ethane,
propane, butane and pentane) are possibly removed for commercial reasons or to achieve a targeted
calorific value range.
LNG composition is therefore within more narrow limits compared to natural gas. The compounds
that can be considered as harmful for marine applications are removed or reduced to very low levels
(trace) so that they are no more a concern. They shall comply with 4.2. The main compounds removed
by liquefaction are listed in Table  3 and below for information and reference. The measurement of
these species is not required. However, if the parties concerned agree to measure them, they should be
measured according to the referenced methods listed in Table 3.
The melting and boiling points for a range of compounds, including those possibly present in biomethane,
are available in Table F.1.

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Table 3 — Main compounds removed by liquefaction and not requiring measurement


Solubility limit
in LNG (around Typical value out
Characteristic Unit Test method Remarks
−160 °C, atm. of LNG plant
Pressure)
Hexane and % (mol) ISO 6974 (all n.a. n.a. n.a.
higher parts)
hydrocarbons
Total sulfur mg(S)/m3 ISO 19739[5] (n.a.) Max 30 mg(S)/m3 Depends on LNG
(gas) contracts. Actual
ISO 20729[6]
value very often
much lower.
Hydrogen sulfide mg/m3 ISO 19739 n.a. 4,29 mg/m3 (N) Removed in Acid
Gas Removal Unit
(AGRU) in liquefac-
tion plant for safety
purposes.
Mercaptan mg/m3 ISO 19739 Depends on size n.a. Removed in AGRU or
of molecule in heavy hydrocar-
bon removal unit in
liquefaction plant.
Carbon dioxide % (mol) ISO 6974 (all Around 0,02 % 0,005 % (mol) Removed in AGRU in
parts) (mol) liquefaction plant.
Oxygen % (mol) ISO 6974 (all n.a. n.a. Removed in
parts) liquefaction plant
Water mg/m3 ISO 10101[3] Below 0,74 mg/ 0,74 mg/m3 or Removed in
m3 below dehydration unit in
liquefaction plant
Mercury µg/m3 ISO 6978-2[2] n.a. 0,01 μg/m3 Removed in
liquefaction plant
NOTE   See Annex F for components in low concentration or absent, e.g. siloxanes.
n.a.   Not available.

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Annex A
(normative)

Propane knock index: Methane number calculation method

The MN of a gaseous fuel can be calculated from its composition according to several different methods,
all of which can give different results. The methodology described in this Annex shall be employed to
calculate MN (PKI).
For components listed in Table 3, the mole fraction can be taken as equal to "0".
DNV GL®1) developed a MN method (“PKI MN”) that characterizes gases for their knock resistance
based on the combustion properties of the fuel mixtures themselves. The PKI MN method is based on a
methane-propane scale (PKI, Propane Knock Index)[8] where the knock resistance of gas composition is
compared to the knock resistance of a methane-propane gas mixture under identical engine conditions.
To calculate the PKI values a polynomial, Formula (A.1) is used:

PKI = ∑ α n Xin + ∑ β n X n X m (A.1)


i i * jm i j

where

  X is the (normalized) mole fraction,

  i = CH4, C2H6, C3H8, i-C4H10, n-C4H10, n-C5H12, i-C5H12, neo-C5H12, CO2, CO, H2 and N2;

  j = C2H6, C3H8, i-C4H10, n-C4H10, n-C5H12, i-C5H12, neo-C5H12, CO2, CO, H2 and N2;

  n = 1 to 4;

  m = 1, 2;

  α and β values are given in Table A.2.


The calculation is valid for PKI values ≤20 (or MN (PKI)≥ 53, see below) and the gas composition range in
Table A.1.

Table A.1 — Gas composition range


Species Min, mol % Max, mol %
CH4 65 100
C2H6 0 20
C3H8 0 20
i-C4H10 0 5
n-C4H10 0 5
n-C5H12 0 2
i-C5H12 0 2
neo-C5H12 0 2
C6 + 0 1,5
H2 0 20

1) DNV GL is a trademark of DNV GL AS. This information is given for the convenience of users of this document
and does not constitute an endorsement by ISO.

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Table A.1 (continued)


Species Min, mol % Max, mol %
CO 0 10
CO2 0 20
N2 0 20
H2 S 0 0,5

To account for the presence of C6+ and H2S in the gas mixture scaling factors are derived based on
autoignition measurements in a rapid compression machine at DNV GL®1). These scaling factors are
used in the algorithm to translate the effect of C6+ and H2S on the knock resistance of a gas mixture
to an equivalent fraction of n-C5H12. The factors are used to correct the methane and n-pentane mole
fractions as in Formulae (A.2) and (A.3).
XCH 4 ,new = XCH 4 in gasmixture − 0 , 3× XC 6+ (A.2)

XnC 5 H 12 ,new = XnC 5 H 12in gasmixture + X H 2 S + 1 , 3× XC 6+ (A.3)

Where X denotes the mole fraction. Here we note that the results of the algorithm are only valid if the
total mole percentages of the gas mixture is 100 %.

Table A.2 — α and β coefficients in Formula (A.1)


Coefficient Value Description
αCH4 569,285 536 016 002 0 CH4
α(CH4) 2 −650,854 339 490 7 CH4^2
α(CH4) 3 64,359 575 257 386 2 CH4^3
α(CH4) 4 17,214 959 222 053 6 CH4^4
αC2H6 −645,099 966 662 855 0 C2H6
α(C2H6) 2 694,229 376 857 102 0 C2H6^2
α(C2H6) 3 −675,381 075 231 165 0 C2H6^3
α(C2H6) 4 1 474,790 791 373 33 C2H6^4
αC3H8 499,398 492 651 52 C3H8
α(C3H8)2 −576,665 945 472 394 0 C3H8^2
α(C3H8) 3 252,193 674 060 28 C3H8^3
α(C3H8) 4 593,958 975 466 507 0 C3H8^4
αn-C4H10 934,466 273 223 240 0 N_C4
α(n-C4H10)2 −86,872 357 077 023 8 N_C4^2
α(n-C4H10)3 −20 418,906 767 397 9 N_C4^3
α(n-C4H10) 4 633 286,561 358 521 0 N_C4^4
αiso-C4H10 735,223 884 113 728 0 I_C4
α(iso-C4H10) 2 −3 182,614 393 379 67 I_C4^2
α(iso-C4H10)3 20 945,186 725 021 9 I_C4^3
α(iso-C4H10)4 159 067,868 032 595 0 I_C4^4
αn-C5H12 2 571,930 793 605 35 N_C5
α(n-C5H12) 2 10 516,494 109 227 50 N_C5^2
α(n-C5H12) 3 −770 539,377 197 693 N_C5^3
α(n-C5H12)4 28 633 475,586 565 4 N_C5^4
αiso-C5H12 −3 582,967 844 353 79 I_C5
α(iso-C5H12) 2 0 I_C5^2

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Table A.2 (continued)


Coefficient Value Description
α(iso-C5H12) 3 403 155,950 864 334 I_C5^3
α(iso-C5H12)4 −11 917 333,837 932 9 I_C5^4
αneo-C5H12 1 123,396 367 098 65 NEC5
α(neo-C5H12) 2 1 679,728 075 248 10 NEC5^2
α(neo-C5H12) 3 −172 182,649 067 176 NEC5^3
α(neo-C5H12) 4 3 467 918,607 466 990 NEC5^4
α N2 −469,428 097 827 742 N2
α(N2)2 352,688 107 288 763 N2^2
α(N2) 3 −220,491 687 402 358 N2^3
α(N2) 4 1 419,680 053 962 420 N2^4
αCO2 −953,460 328 339 263 CO2
α(CO2)2 1 148,487 258 682 280 CO2^2
α(CO2)3 −601,339 855 375 907 CO2^3
α(CO2) 4 448,125 565 457 084 CO2^4
αCO −5 813,759 963 900 21 CO
α(CO) 2 5 511,721 025 828 67 CO^2
α(CO)3 1 647,043 065 843 26 CO^3
α(CO)4 −3 471,241 525 554 25 CO^4
α H2 −906,859 878 136 883 H2
α(H2) 2 1 059,747 810 140 28 H2^2
α(H2) 3 −1 302,861 581 498 63 H2^3
α(H2)4 3 639,859 493 045 20 H2^4
βCH4×C2H6 201,788 909 592 169 CH4*C2H6
βCH4 •C3H8 −865,856 657 223 225 CH4*C3H8
βCH4 •n-C4H10 −1 210,227 541 932 4 CH4*N_C4
β(CH4 •n-C4H10) 2 1 331,555 523 696 450 (CH4*N_C4)^2
βCH4 •iso-C4H10 −1 023,278 147 470 3 CH4*I_C4
β(CH4 × iso-C4H10) 2 1 550,095 184 612 58 (CH4*I_C4)^2
βCH4 × n-C5H12 −2 811,677 404 325 23 CH4*N_C5
βCH4 × iso-C5H12 3 363,981 505 063 56 CH4*I_C5
βCH4 × neo-C5H12 −1 534,525 674 887 23 CH4*NEC5
βCH4 × N2 −1,053 973 329 306 09 CH4*N2
βCH4 × CO2 473,574 764 109 71 CH4*CO2
β(CH4 × CO2) 2 −308,259 010 229 21 (CH4*CO2)^2
βCH4 × CO 5 356,433 570 549 5 CH4*CO
βCH4 × H2 118,685 621 913 274 CH4*H2
βCH4 × (H2)2 252,885 168 496 247 CH4*(H2^2)
β(CH4) 2 325,305 174 695 724 (CH4^2)*H2
× H2
βC2H6 × C3H8 0 C2H6*C3H8
βC2H6 × n-C4H10 −437,695 363 730 406 C2H6*N_C4
βC2H6 × iso-C4H10 −109,983 789 902 769 C2H6*I_C4
βC2H6 × n-C5H12 −1 870,347 465 005 63 C2H6*N_C5
βC2H6 × iso-C5H12 3 909,509 060 762 45 C2H6*I_C5
βC2H6 × neo-C5H12 −886,578 525 827 322 C2H6*NEC5

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Table A.2 (continued)


Coefficient Value Description
βC2H6 × N2 968,887 620 927 515 C2H6*N2
β(C2H6)2 × N2 267,472 766 191 96 (C2H6^2)*N2
βC2H6 × (N2)2 337,464 863 958 288 C2H6*(N2^2)
βC2H6 × CO2 1 431,950 116 993 15 C2H6*CO2
βC2H6 × CO 6 463,144 442 956 27 C2H6*CO
βC2H6 × H2 1 865,090 903 843 57 C2H6*H2
βC3H8 × n-C4H10 −118,490 180 710 956 C3H8*N_C4
βC3H8 × iso-C4H10 0 C3H8*I_C4
βC3H8 × n-C5H12 −1 734,805 682 394 27 C3H8*N_C5
βC3H8 × (n-C5H12) 2 127 551,642 193 201 C3H8*(N_C5^2)
β(C3H8) 2 11 318,418 395 072 2 (C3H8^2)*N_C5
× n-C5H12
βC3H8 × iso-C5H12 3 318,968 208 193 38 C3H8*I_C5
βC3H8 × neo-C5H12 0 C3H8*NEC5
βC3H8 × N2 13,345 337 812 469 C3H8*N2
βC3H8 × CO2 292,275 289 330 565 C3H8*CO2
βC3H8 × CO 5 403,502 607 948 29 C3H8*CO
β(C3H8)2 × CO 2 333,823 463 429 21 (C3H8^2)*CO
βC3H8 × H2 957,887 281 487 301 C3H8*H2
βn-C4H10 × iso-C4H10 3 500,702 828 522 74 N_C4*I_C4
βn-C4H10 × n-C5H12 −4 737,328 494 949 99 N_C4*N_C5
βn-C4H10 × (n-C5H12) 2 525 591,310 711 326 NC4*(NC5^2)
β(n-C4H10)2 × n-C5H12 297 556,039 242 685 (NC4^2)*NC5
βn-C4H10 × iso-C5H12 6 095,059 988 750 87 N_C4*I_C5
βn-C4H10 × neo-C5H12 −953,002 183 779 388 N_C4*NEC5
βn-C4H10 × N2 0 N_C4*N2
βn-C4H10 × CO2 −103,571 484 346 062 N_C4*CO2
βn-C4H10 × CO 5 869,190 506 527 74 N_C4*CO
βn-C4H10 × H2 1 267,619 534 835 89 N_C4*H2
βiso-C4H10 × n-C5H12 5 056,603 091 637 61 I_C4*N_C5
βiso-C4H10 × iso-C5H12 6 619,278 776 370 44 I_C4*I_C5
βiso-C4H10 × neo-C5H12 −1 363,961 016 448 41 I_C4*NEC5
βiso-C4H10 × N2 14,803 895 799 972 4 I_C4*N2
βiso-C4H10 × CO2 211,752 602 673 394 I_C4*CO2
βiso-C4H10 × CO 5 786,325 257 174 88 I_C4*CO
βiso-C4H10 × H2 1 458,460 720 431 54 I_C4*H2
βn-C5H12 × iso-C5H12 12 268,283 772 748 N_C5*I_C5
βn-C5H12 × neo-C5H12 0 N_C5*NEC5
βn-C5H12 × N2 −1 573,688 937 706 25 N_C5*N2
βn-C5H12 × CO2 −898,466 856 535 774 N_C5*CO2
β(n-C5H12) 2 −42 401,411 139 182 4 (N_C5^2)*CO2
× CO2
βn-C5H12 × CO 3 985,110 420 511 03 N_C5*CO
β(n-C5H12)2 × CO 48 265,319 103 373 7 (N_C5^2)*CO
βn-C5H12 × H2 −1 112,443 527 705 6 N_C5*H2
β(n-C5H12) 2 99 558,333 341 943 2 (N_C5^2)*H2
× H2

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Table A.2 (continued)


Coefficient Value Description
βiso-C5H12 × neo-C5H12 3 773,449 267 853 97 I_C5*NEC5
βiso-C5H12 × N2 4 490,678 300 326 75 I_C5*N2
βiso-C5H12 × CO2 5 122,009 935 455 09 I_C5*CO2
β(iso-C5H12) 2 −28 087,848 186 432 6 (I_C5^2)*CO2
× CO2
βiso-C5H12 × CO 10 248,340 825 423 2 I_C5*CO
βiso-C5H12 × H2 5 464,934 669 232 21 I_C5*H2
βneo-C5H12 × H2 −642,170 828 416 611 NEC5*N2
βneo-C5H12 × CO2 0 NEC5*CO2
β(neo-C5H12) 2 −11 320,112 689 948 1 (NEC5^2)*CO2
× CO2
βneo-C5H12 × CO 4 772,677 301 186 82 NEC5*CO
βneo-C5H12 × H2 0 NEC5*H2
β N2 × CO2 1 156,200 327 160 21 N2*CO2
β(N2)2 × CO2 359,342 203 118 816 (N2^2)*CO2
β N2 × CO 6 076,818 092 916 31 N2*CO
β(N2) 2 389,853 153 629 781 (N2^2)*CO
× CO
β N2 × (CO)2 367,319 351 280 689 N2*(CO^2)
β N2 × H2 1 506,655 641 914 57 N2*H2
βCO2 × CO 6 557,376 349 418 7 CO2*CO
β(CO2 × CO) 2 1 824,585 879 374 03 (CO2*CO)^2
βCO2 × H2 1 924,917 595 080 54 CO2*H2
β(CO2 × H2) 2 −1 656,219 745 263 47 (CO2*H2)^2
βCO × H2 6 896,458 388 070 18 CO*H2
β(CO × H2) 2 911,791 848 875 967 (CO*H2)^2

To put the method on a scale analogous to the currently used methane number methods, the propane-
based scale (PKI) has been converted to a 0 - 100 scale, referred to as MN (PKI)in Formula (A.4):
MN (PKI)= a1 PKI+ a2 PKI^2+ a3 PKI^3+ a4 PKI^4+ a5 PKI^5+ a6 PKI^6+b (A.4)

By using Formula (A.4) and the coefficients presented in Table A.3, the PKI values calculated by using
Formula (A.1) are converted to a MN (PKI).

Table A.3 — coefficients in Formula (A.4) for conversion of PKI into MN (PKI)


Coefficients Values
a1 −9,757 977
a2 1,484 961
a3 −0,139 533
a4 0,007 031 306
a5 −0,000 177 002 9
a6 0,000 001 751 212
b 100

EXAMPLE  

In general, α values are for the individual components and β values are for the interaction between individual
components.

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For example, if we consider a mixture of 90  % CH4 and 10  % C2H6 then the PKI can be calculated using
Formula (A.1) in the document.

XCH4 = 0,9

XC2H6 = 0,1

PKI = XCH4*αCH4 + (XCH4)^2*(αCH4)2 +(XCH4)^3*(αCH4)3 +(XCH4)^4*(αCH4)4 + XC2H6*αC2H6 + (XC2H6)^2*(αC2H6)2 +


(XC2H6)^3*(αC2H6)3 + (XC2H6)^4*(αC2H6)4 + XCH4*XC2H6*βCH4xC2H6 =

(see also values in Table A.2)

0,9*569,285  536  016  002  0 + (0,9*0,9)* −650,854  339  490  7 + (0,9*0,9*0,9)* 64,359  575  257  386  2 +
(0,9*0,9*0,9*0,9)* 17,214  959  222  053  6+ 0,1*−645,099  966  662  855  0 + (0,1*0,1)* 694,229  376  857  102  0 +
(0,1*0,1*0,1)* −675,381 075 231 165 0 + (0,1*0,1*0,1*0,1)* 1 474,790 791 373 33 +

0,1*0,9*201,788 909 592 169 = 3,4

Thus, a PKI value of 3,4 is calculated for this mixture.

Next, using Formula (A.4), we can calculate the MN (PKI) using the values from Table A.3:

MN (PKI)=a_1 PKI+a_2 PKI^2+a_3 PKI^3+a_4 PKI^4+a_5 PKI^5+a_6 PKI^6+b

=−9,757  977*3,4 + 1,484  961*(3,4*3,4) + −0,139  533*(3,4*3,4*3,4)+ 0,007  031  306*(3,4*3,4*3,4*3,4) +


−0,000 177 002 9*(3,4*3,4*3,4*3,4*3,4) + 0,000 001 751 212*(3,4*3,4*3,4*3,4*3,4*3,4) + 100 = 79

Please note that 0,9*0,9 is mathematically equal to (0,9)2. In Formula (A.1), this is shown as (for example in this
case with XCH4 = 0,9) XCH4^2 or (XCH4)2.

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Annex B
(informative)

Examples of LNG composition

The examples given in Table B.1 of LNG composition are given by GIIGNL (International Group of LNG
Importers) in its annual report[9]. They are only coming from fossil sources. The data have last been
updated in 2012. The average composition is chosen as being representative among compositions
reported by the different receiving terminals. Additional information on the energy quantity of LNG
can be found in the GIIGNL LNG Custody Transfer Handbook[8].
Columns have been added for Methane Number, Net Calorific Value, Gross Calorific Value and Wobbe
index in the ISO reference conditions. The column on the expansion ratio was removed.

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Table B.1 — Examples of LNG composition
Meth-
Nitro- Meth- Pro- LNG Gas Wobbe Wobbe
Ethane Gas NCV ane Methane
Origin gen ane pane
C2 % MJ/m3(n) MJ/m3(s) (MJ/kg) num-
Gas GCVb Gas GCVc
N2 % C1 % C3 % kg/m3 kg/m3(n) 3
MJ/m (n) MJ/m3(s)
C4+ % Densitya Densityb indexb indexc
numbere
berd
Australia - 0,04 87,33 8,33 3,33 0,97 467,35 0,83 45,32 42,88 49,2 56,53 53,49 68 69
NWS

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Australia - 0,10 87,64 9,97 1,96 0,33 461,05 0,81 44,39 42,00 49,3 56,01 53,00 71 73
Darwin
Algeria - 0,63 91,40 7,35 0,57 0,05 446,65 0,78 42,30 40,02 49,1 54,62 51,69 79 80
Skikda
Algeria - 0,64 89,55 8,20 1,30 0,31 454,50 0,80 43,22 40,89 49,0 55,12 52,16 75 76
Bethioua
Algeria - 0,71 88,93 8,42 1,59 0,37 457,10 0,80 43,48 41,14 48,9 55,23 52,26 74 74
Arzew
Brunei 0,04 90,12 5,34 3,02 1,48 461,63 0,82 44,68 42,27 49,3 56,18 53,16 69 68


Egypt - 0,02 95,31 3,58 0,74 0,34 437,38 0,76 41,76 39,51 49,6 54,61 51,68 83 83
Idku
Egypt - 0,02 97,25 2,49 0,12 0,12 429,35 0,74 40,87 38,67 49,8 54,12 51,21 90 91
Damietta
Equatorial 0,00 93,41 6,52 0,07 0,00 439,64 0,76 41,95 39,69 49,7 54,73 51,79 85 84
Guinea
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Indonesia - 0,08 91,86 5,66 1,60 0,79 450,96 0,79 43,29 40,96 49,4 55,42 52,44 75 74
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Arun
Indonesia - 0,01 90,14 5,46 2,98 1,40 461,07 0,82 44,63 42,23 49,3 56,17 53,15 69 69
Badak
Indonesia 0,13 96,91 2,37 0,44 0,15 431,22 0,74 41,00 38,79 49,7 54,14 51,23 88 89
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- Tangguh
Malaysia - 0,14 91,69 4,64 2,60 0,93 454,19 0,80 43,67 41,32 49,3 55,59 52,60 73 72
Bintulu
a Calculated according to ISO 6578 [T = −160 °C].
b Calculated according to ISO 6976 [0 ºC / 0 °C, 1,013 25 bar].
c Calculated at 15 °C / 15 °C, 1,013 25 bar.
d Calculated by method in EN 16726.
ISO 23306:2020(E)

13


e Calculated by PKI method in Annex A.



Table B.1 (continued)

14
Meth-
Nitro- Meth- Pro- LNG Gas Wobbe Wobbe
Ethane Gas NCV ane Methane
Origin gen ane pane
C2 % MJ/m3(n) MJ/m3(s) (MJ/kg) num-
Gas GCVb Gas GCVc
N2 % C1 % C3 % kg/m3 kg/m3(n) 3
MJ/m (n) MJ/m3(s)
C4+ % Densitya Densityb indexb indexc
numbere
berd
Nigeria 0,03 91,70 5,52 2,17 0,58 451,66 0,79 43,41 41,07 49,5 55,50 52,52 75 74
ISO 23306:2020(E)

Norway 0,46 92,03 5,75 1,31 0,45 448,39 0,78 42,69 40,39 49,2 54,91 51,96 77 77
Oman 0,20 90,68 5,75 2,12 1,24 457,27 0,81 43,99 41,62 49,2 55,73 52,74 72 71
Peru 0,57 89,07 10,26 0,10 0,01 451,80 0,79 42,90 40,59 49,1 55,00 52,04 77 78
Qatar 0,27 90,91 6,43 1,66 0,74 453,46 0,79 43,43 41,09 49,3 55,40 52,42 74 74
Russia - 0,07 92,53 4,47 1,97 0,95 450,67 0,79 43,30 40,97 49,4 55,43 52,45 75 74
Sakhalin
Trinidad 0,01 96,78 2,78 0,37 0,06 431,03 0,74 41,05 38,84 49,8 54,23 51,32 88 89
USA - Alas- 0,17 99,71 0,09 0,03 0,01 421,39 0,72 39,91 37,76 49,8 53,51 50,63 99 99
ka
Yemen 0,02 93,17 5,93 0,77 0,12 442,42 0,77 42,29 40,01 49,6 54,91 51,96 80 81


a Calculated according to ISO 6578 [T = −160 °C].
b Calculated according to ISO 6976 [0 ºC / 0 °C, 1,013 25 bar].
c Calculated at 15 °C / 15 °C, 1,013 25 bar.
d Calculated by method in EN 16726.
e Calculated by PKI method in Annex A.
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Annex C
(informative)

Methane number (knock resistance) and Wobbe index (thermal


input through a restriction)

C.1 Methane number


The ability of a fuel to resist engine knock for given conditions in the cylinder of an engine is referred to
as its knock resistance. The knock resistance for a gaseous fuel is usually characterized using a methane
number. The knock resistance of the fuel is an important parameter for engine operation; the maximum
non-knocking power output of many marine engine types can depend on the methane number.
Originally, the methane number was derived in analogy with the octane number for gasoline; it is a
measure for the specific knock intensity in a reference engine. The knock intensity for a given fuel is
compared to a mixture of reference fuels. For the methane number, pure methane was assigned the
value of "100", while pure hydrogen was assigned the value of "0".
There are several calculation tools for determining the methane number, which often give different
methane numbers for the same fuel composition. The same method can for some gas compositions
overestimate the methane number and for other gas compositions underestimate it. The differences
between the tools reflect different engine conditions for which the tools are intended (e.g., stoichiometric
vs. lean-burn) and differences in how the methane numbers are derived from experimental, empirical
and theoretical data. This results in different approaches for how the effects of higher hydrocarbons
and their isomers, as well as the impact of inert gases, are incorporated in the tools.
NOTE In EN 16726:2015, the MWM method has been used to calculate the Methane Number.

C.2 Wobbe index


While the net calorific value (NCV) is important for characterizing LNG for reciprocating engines,
natural gas for other end-use equipment (e.g. boiler) is characterized by the Wobbe index. At constant
pressure drop, the heat input to such end-use equipment is proportional to the Wobbe index.
The gross Wobbe index is the gross calorific value (GCV) divided by the square root of the relative
density (d) of the fuel as shown in Formula (C.1):

grossWI = GCV / d (C.1)

While the methane number decreases, and the Wobbe index increases, with an increasing fraction of
higher hydrocarbons (ethane, propane, butanes, etc.), the methane number, which depends upon the
detailed composition of the fuel, is not reliably predicted by the Wobbe index. For LNG compositions,
the methane number can vary by 5-10 points for fuels having similar Wobbe index, as illustrated in
Figure C.1, below, showing the methane number for the 2018 GIIGNL list as a function of Wobbe index.
NOTE The different methods to calculate the methane number show similar results when plotted vs. Wobbe
index; the results shown reflect the MWM method.

Since specifications for MN are given to whole numbers, using a correlation with Wobbe index does not
possess enough predictive power for this purpose.

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Key
X Wobbe index [MJ/m3] (15 °C/15 °C)
Y methane number [-] (EN 16726)
The data come from Table B.1.

Figure C.1 — Methane number plotted vs. Wobbe index

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Annex D
(informative)

LNG ageing along the bunkering chain

D.1 Ageing
Ageing of LNG throughout the supply chain is the gradual change in the molecular composition caused
by differential evaporation because LNG has components with different boiling points. The components
in the LNG with lower boiling points (Nitrogen, Methane) evaporate preferentially and produce boil off
gas (BOG). This reduces the proportion of the most volatile components and increases relatively the
less volatile molecules (C2+) in the LNG, thus changing the overall molecular composition. This change
in the composition has a direct impact on the LNG properties usually increasing the density and heating
values and decreasing Methane Number.

D.2 Composition change due to ageing


The ageing of LNG takes place at every stage of the supply chain: during storage, transportation and
cargo transfer operations. Depending on the stage of the supply chain, various factors can impact the
ageing of the composition. The change is dependent on the original composition of the LNG and amount
of boil off that occurs. There are boil off design specifications for both storage tanks and vessel tanks
based on their construction, however, external forces, such as weather, sea condition or cargo handling
can impact the result of ageing. The impact of the LNG heel before loading can also be important for the
final LNG composition at destination.

D.3 Importance of understanding and managing LNG ageing


As the process of LNG ageing occurs throughout the supply chain, it is important for all parties to
understand the possible change in the composition. The commercial concerns on impact of ageing of
LNG can be for conformance to specification and value of the cargo. A loaded LNG cargo can be within
the delivery specification, however, ageing in transit can cause various parameters to be out of the
requirements once delivered. Various prediction tools can be applied to calculate the amount of boil off
and simulate the rate of ageing once the original LNG composition is measured and the heat ingress is
estimated. These tools can predict and estimate the LNG quality at the delivery point and help to manage
the ageing during the operation. These tools can be based on historical data or various algorithms, but
as external forces can also impact the ageing process, accuracy of these predictions could vary.

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Annex E
(informative)

Particles

LNG is a homogenous liquid, which does not contain particles after the liquefaction process. However,
contamination can occur in shipyards during construction or maintenance, during bunkering and in
storage. Solid contaminants, e.g. metal shavings, welding debris, insulation (i.e. perlite), dust, sand,
cloth and oil, which are solid at cryogenic temperatures, should be removed since these could block fuel
filters, and ultimately damage equipment on-board if in large concentrations.
It is important to note that the quality and degree of contamination can vary among the suppliers due
to differences in handling and the type of bunkering/transfer process (e.g. terminal tank to vessel,
truck to vessel, vessel to vessel, portable tank transfer). Hence it is important that the supplier and the
end-user agree on, and utilize industry-best practices to ensure that particles and debris are removed
from the LNG fuel system.
Proper cleaning procedures are especially important for new installations, e.g. new barges, loading
lines, pipes, tanks and valves, etc. Particle contamination should be monitored when commissioning
new parts and/or replacing malfunctioning equipment.
More detailed information on cleaning procedures, filters and maintenance should be available from
equipment suppliers.

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Annex F
(informative)

Melting and boiling points of pure components and impurities


that can be present in different LNG

The following table is a non-exhaustive list of some of the components (e.g. methane, ethane) and
impurities (e.g. siloxanes, ammonia) which could be present in LNG originating from natural gas
and biomethane, with their respective melting point and boiling points. Additional information on
biomethane components can be found in EN 16723-2[7].
LNG is stored at around −160 °C and at atmospheric pressure and exists in equilibrium with its vapour.
During the operation of an LNG facility non-equilibrium conditions can exist transiently but the liquid
and vapour phases will ultimately return to equilibrium. Since LNG is a multi-component mixture
the vapor phase, or flash gas, will contain a greater percentage of the more volatile compounds (e.g.
nitrogen) and a lower percentage of the less volatile components relative to the liquid phase with which
it is in thermodynamic equilibrium.
Melting and boiling points are taken from References [11] and [12].

Table F.1 — Boiling and melting points for pure components and impurities that can be present
in different LNG, ordered according to boiling point in descending order.
Compound Molecular Boiling Melting Remarks
formula point, °C point, °C
Hexamethylcyclotrisiloxane (D3) C6H18O3Si3 134 64,5 In biomethane
Water H 2O 100 0 Can cause ice-blockages
Benzene C6H6 80 6 Solubility in LNG (abt.
−160 °C at 1 bar) is around
1 ppm. Can cause ice
blockages.
Methyl ethyl ketone (2-butanone) C4H8O 79 −86 In biomethane
Pentane C5H12 36 −130 Could be present in LNG in
very low concentrations up
to 0,1 %
Dichloromethane CH2Cl2 40 −95 In biomethane
Methylmercaptan CH3SH 6 −123 Sometimes present in
natural gas
Butane C4H10 −1 −138 Could be present naturally
in LNG in low concentra-
tions up to 1,5 %[8]
Ammonia NH3 −33 −78 Corrosive, toxic, In
biomethane
Propane C3H8 −42 −188 Could be naturally present
in LNG, low concentrations
up to 3,3 %[8].
Hydrogen sulfide H2 S −60 −86 Referred to as acid gas,
extremely toxic.
Carbon dioxide CO2 −78 −57 −78 °C is the sublimation
temperature. −57 °C is
at 5,1 bar. Referred to as
acid gas

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Table F.1 (continued)


Compound Molecular Boiling Melting Remarks
formula point, °C point, °C
Hydrogen chloride HCl −85 −114 Reactive, corrosive, In
biomethane
Ethane C2H6 −89 −183 Present in LNG.
Methane CH4 −162 −182 Major compound in LNG.
Oxygen O2 −183 −219 Usually not present in LNG.
Nitrogen gas N2 −196 −210 Present in LNG.
Hydrogen H2 −253 −259 Would boil off
instantaneously.

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Bibliography

[1] ISO 6975, Natural gas — Extended analysis — Gas-chromatographic method


[2] ISO  6978-2, Natural gas — Determination of mercury — Part 2: Sampling of mercury by
amalgamation on gold/platinum alloy
[3] ISO 10101, Natural gas — Determination of water by the Karl Fischer method
[4] ISO 14532:2014, Natural gas — Vocabulary
[5] ISO 19739, Natural gas — Determination of sulfur compounds using gas chromatography
[6] ISO  20729, Natural gas — Determination of sulfur compounds — Determination of total sulfur
content by ultraviolet fluorescence method
[7] EN 16723-2, Natural gas and biomethane for use in transport and biomethane for injection in the
natural gas network — Part 2: Automotive fuels specification
[8] Gersen S., Essen M., Levinsky H., Dijk G., Characterizing Gaseous Fuels for Their Knock
Resistance based on the Chemical and Physical Properties of the Fuel", SAE Int. J. Fuels Lubr.
9(1):2016
[9] The LNG industry GIIGNL Annual Report 2018
[10] GIIGNL LNG Custody Transfer Handbook 2017
[11] Handbook of Chemistry and Physics 64 Th Edition 1983-1984
[12] Siloxanes Environmental Danish Ministry of the Environment Project n°1531, 2014
[13] ISO 13443:1996, Natural gas — Standard reference conditions

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ISO 23306:2020(E)


ICS 75.160.30
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