SIST EN 17178:2019

Liquid petroleum products - Determination of the total volatile sulfur content in liquefied petroleum gases by ultraviolet fluorescence spectroscopy

This document specifies an ultraviolet (UV) fluorescence test method for the determination of the sulfur content of liquefied petroleum gases (LPG) containing up to 0,35 % (m/m) halogens, and having sulfur contents in the range of 2 mg/kg to 50 mg/kg.
This test method does not detect sulfur compounds that do not vaporize under the conditions of the test.
NOTE   For the purposes of this document, the terms "% (m/m)" and "% (V/V)" are used to represent respectively the mass fraction and the volume fraction.
WARNING - The use of this standard can involve hazardous materials, operations and equipment. This standard does not purport to address all the safety problems associated with its use. It is the responsibility of users of this standard to take appropriate measures to ensure the safety and health of personnel prior to the application of the standard, and fulfil statutory and regulatory requirements for this purpose.

Flüssige Mineralölerzeugnisse - Bestimmung des Gesamtgehaltes an flüchtigem Schwefel in Flüssiggas (LPG) durch Ultraviolettfluoreszenz-Spektroskopie

Diese Dokument legt ein Ultraviolettfluoreszenz-Prüfverfahren zur Bestimmung des Schwefelgehaltes von Flüssiggasen (en: liquefied petroleum gases, LPG) fest, die bis zu 0,35 % (m/m) Halogene enthalten und einen Schwefelgehalt im Bereich von 2 mg/kg bis 50 mg/kg aufweisen.
Dieses Prüfverfahren detektiert keine Schwefelverbindungen, die unter den Prüfbedingungen nicht verdampfen.
ANMERKUNG   Für die Zwecke dieses Dokuments wird zur Angabe des Massenanteils einer Substanz der Ausdruck "% (m/m)" und für den Volumenanteil einer Substanz der Ausdruck "% (V/V)" verwendet.
WARNUNG - Die Anwendung dieser Norm kann die Anwendung gefährlicher Stoffe, Arbeitsgänge und Geräte mit sich bringen. Diese Norm beansprucht nicht, alle damit verbundenen Sicherheitsprobleme zu behandeln. Es liegt in der Verantwortung des Anwenders dieser Norm, vor ihrer Anwendung geeignete Maßnahmen für die Sicherheit und den Gesundheitsschutz des Personals zu ergreifen, und dafür Sorge zu tragen, dass behördliche und gesetzliche Maßnahmen eingehalten werden.

Produits pétroliers liquides - Détermination de la teneur en soufre volatil dans les gaz de pétrole liquéfiés par spectroscopie de fluorescence ultra-violette

Le présent document spécifie une méthode d'essai par fluorescence ultra-violette (UV) qui permet la détermination de la teneur en soufre dans les gaz de pétrole liquéfiés (GPL) contenant jusqu'à 0,35 % (m/m) d'halogènes et dont les teneurs en soufre se trouvent dans l’intervalle de 2 à 50 mg/kg.
Cette méthode d'essai ne détecte pas les composés soufrés qui ne se vaporisent pas dans les conditions de l'essai.
NOTE 1   Le GPL est défini comme un gaz liquéfié à basse pression composé d'un ou plusieurs hydrocarbures légers qui sont affectés uniquement aux UN 1011, 1075, 1965, 1969 ou 1978 et qui se compose principalement de propane, de propène, de butane, d'isomères du butane, de butènes avec des traces d'autres hydrocarbures des gaz.
NOTE 2   Pour les besoins de la présente norme, les termes « % (m/m) » et « % (V/V) » sont utilisés pour représenter, respectivement, la fraction massique, µ, et la fraction volumique, φ.
AVERTISSEMENT — L'utilisation du présent document peut impliquer l'intervention de produits, d'opérations et d'équipements à caractère dangereux. Le présent document ne prétend pas aborder tous les problèmes de sécurité associés à son utilisation. Il est de la responsabilité de l'utilisateur de la présente norme de prendre les mesures appropriées pour assurer la sécurité et préserver la santé du personnel avant l’application de la norme, et satisfaire aux exigences légales et réglementaires applicables à cet effet.

Tekoči naftni proizvodi - Določevanje skupne vsebnosti hlapnega žvepla v utekočinjenih naftnih plinih z ultravijolično fluorescentno spektroskopijo

Ta dokument določa vsebnost žvepla v utekočinjenih naftnih plinih (LPG) za motorna vozila s pomočjo ultravijoličnih fluorescentnih tehnik. Ciljna vrednost merjenja mora biti med 10 mg/kg in 100 mg/kg.

General Information

• Status: Published
• Public Enquiry End Date: 30-Nov-2017
• Publication Date: 10-Oct-2019
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: NAD - Petroleum products, lubricants and related products
• Current Stage: 6060 - National Implementation/Publication (Adopted Project)
• Start Date: 02-Oct-2019
• Due Date: 07-Dec-2019
• Completion Date: 11-Oct-2019
• Ref Project: EN 17178:2019 - Liquid petroleum products - Determination of the total volatile sulfur content in liquefied petroleum gases by ultraviolet fluorescence spectroscopy

Overview

EN 17178:2019 - published by CEN - specifies an ultraviolet fluorescence (UVF) spectroscopy method for the determination of the total volatile sulfur content in liquefied petroleum gases (LPG). The standard covers LPG streams containing up to 0,35 % (m/m) halogens and quantifies sulfur in the range 2 mg/kg to 50 mg/kg. It is intended for process feeds and finished product testing and can be used for compliance where accepted by regulators. Note: sulfur compounds that do not vaporize under test conditions are not detected.

Key topics and technical requirements

• Analytical principle: sample injection → high‑temperature combustion (≈900–1 100 °C, typical 1 075 °C) → oxidation of sulfur to SO2 → water removal → UV excitation → fluorescence detection of SO2 by photomultiplier tube.
• Scope limits: applicable sulfur range 2–50 mg/kg; LPG defined per UN listings (propane, butanes, propene, etc.).
• Apparatus: furnace and combustion tube, flow controllers, vapour drier, UV fluorescence detector, heated sample inlet/expansion chamber and PC/data system.
• Reagents and gases: high‑purity inert gas (Ar or He ≥99,9 % V/V), oxygen (≥99,75 % V/V, low moisture), certified calibration standards (e.g., dimethyl sulfide in n‑butane/iso‑butane/propane matrices).
• Calibration: multi‑point and one‑point techniques allowed; standards should bracket sample concentrations. Typical calibration concentrations (representative): blank, 5, 15, 30, 45, 60 mg/kg.
• Quality control (QC): run QC samples after each calibration and at least daily; use facility QC/QA protocols or Annex A guidance.
• Sampling: follow EN ISO 4257 for LPG sampling; analyse samples promptly and use sulfur‑inert cylinders/fittings if needed.
• Safety: warns about hazardous materials, high temperatures, oxygen‑accelerated combustion and UV exposure - users must apply appropriate safety measures.

Applications and practical value

• Accurate measurement of sulfur content in LPG for:
  • fuel quality control at refineries and LPG bottling plants
  • environmental and emissions compliance (SOx contribution)
  • protecting catalysts and engine/exhaust systems from sulfur poisoning
  • feedstock quality verification in chemical processes
• Useful for laboratories performing routine LPG analysis, instrument manufacturers, quality managers and regulatory bodies.

Who should use this standard

• Accredited fuel testing laboratories
• LPG producers, distributors and terminal operators
• Refinery analytical teams
• Automotive and catalyst developers concerned with sulfur poisoning
• Environmental compliance officers

Related standards

• EN ISO 4257 - Liquefied petroleum gases - Method of sampling (referenced by EN 17178).
• Other LPG sulfur test methods (national or international) may be used for comparison where appropriate.

Keywords: EN 17178:2019, ultraviolet fluorescence, UVF, LPG sulfur determination, liquefied petroleum gas, sulfur content in LPG, CEN standard, sulfur analysis.

Standards Content (Sample)

SLOVENSKI STANDARD
01-november-2019
Tekoči naftni proizvodi - Določevanje skupne vsebnosti hlapnega žvepla v
utekočinjenih naftnih plinih z ultravijolično fluorescentno spektroskopijo
Liquid petroleum products - Determination of the total volatile sulfur content in liquefied
petroleum gases by ultraviolet fluorescence spectroscopy
Flüssige Mineralölerzeugnisse - Bestimmung des Gesamtgehaltes an flüchtigem
Schwefel in Flüssiggas (LPG) durch Ultraviolettfluoreszenz-Spektroskopie
Produits pétroliers liquides - Détermination de la teneur en soufre volatil dans les gaz de
pétrole liquéfiés par spectroscopie de fluorescence ultra-violette
Ta slovenski standard je istoveten z: EN 17178:2019
ICS:
75.160.20 Tekoča goriva Liquid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 17178
EUROPEAN STANDARD
NORME EUROPÉENNE
September 2019
EUROPÄISCHE NORM
ICS 75.160.20
English Version
Liquid petroleum products - Determination of the total
volatile sulfur content in liquefied petroleum gases by
ultraviolet fluorescence spectroscopy
Produits pétroliers liquides - Détermination de la Flüssige Mineralölerzeugnisse - Bestimmung des
teneur en soufre volatil dans les gaz de pétrole Gesamtgehaltes an flüchtigem Schwefel in Flüssiggas
liquéfiés par spectroscopie de fluorescence ultra- (LPG) durch Ultraviolettfluoreszenz-Spektroskopie
violette
This European Standard was approved by CEN on 20 June 2019.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 17178:2019 E
worldwide for CEN national Members.

Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Principle . 5
5 Reagents and materials . 6
6 Apparatus . 6
7 Sampling . 7
8 Calibration . 7
8.1 Calibration range . 7
8.2 Calibration techniques allowed . 8
8.2.1 Multi-point calibration . 8
8.2.2 One-point calibration . 8
9 Quality control . 8
10 Apparatus preparation . 9
11 Procedure . 9
12 Calculation . 10
13 Expression of results . 11
14 Precision . 11
14.1 General. 11
14.2 Repeatability . 11
14.3 Reproducibility . 11
15 Test report . 12
Annex A (informative) Quality control monitoring . 13
Bibliography . 14

European foreword
This document (EN 17178:2019) has been prepared by Technical Committee CEN/TC 19 “Gaseous and
liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat
of which is held by NEN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by March 2020 and conflicting national standards shall be
withdrawn at the latest by March 2020.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN not be held responsible for identifying any or all such patent rights.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia,
Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland,
Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of North
Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United
Kingdom.
Introduction
The sulfur content of LPG used for fuel purposes contributes to SO emissions and can lead to corrosion
x
in engine and exhaust systems. Sulfur also acts as catalyst poison, blocking and damaging catalysts like
catalytic converters in cars and process catalysts in the chemical industry where LPG is used as feedstock.
Due to the need for lower sulfur limits, this document was developed in order to solve precision issues
with existing test methods [3, 4].
1 Scope
This document specifies an ultraviolet (UV) fluorescence test method for the determination of the sulfur
content of liquefied petroleum gases (LPG) containing up to 0,35 % (m/m) halogens, and having sulfur
contents in the range of 2 mg/kg to 50 mg/kg.
This test method does not detect sulfur compounds that do not vaporize under the conditions of the test.
NOTE 1 LPG is defined as low pressure liquefied gas composed of one or more light hydrocarbons which are
assigned to UN 1011, 1075, 1965, 1969 or 1978 only and which consists mainly of propane, propene, butane, butane
isomers, butenes with traces of other hydrocarbon gases.
NOTE 2 For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent
respectively the mass fraction, µ, and the volume fraction, φ.
WARNING — The use of this standard can involve hazardous materials, operations and equipment. This
standard does not purport to address all the safety problems associated with its use. It is the
responsibility of users of this standard to take appropriate measures to ensure the safety and health of
personnel prior to the application of the standard, and fulfil statutory and regulatory requirements for
this purpose.
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.
EN ISO 4257, Liquefied petroleum gases — Method of sampling (ISO 4257)
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Principle
This test method is used to determine sulfur in process feeds and in finished products and can also be
used for compliance determinations when acceptable to a regulatory authority.
An appropriate sample is taken from the sample container and introduced into the analyser. The gaseous
sample then enters a high temperature (900 °C – 1 100 °C) combustion tube where sulfur is oxidized to
sulfur dioxide (SO ) in an oxygen rich atmosphere.
Water produced during the sample combustion is removed and the remaining sample combustion gases
are exposed to UV light. The SO absorbs the energy from the UV light and is converted to excited sulfur
dioxide (SO *). The fluorescence emitted from the excited SO * molecules as they return to a stable state
2 2
SO is detected by a photomultiplier tube and the resulting signal is a measure of the sulfur contained in
the sample.
5 Reagents and materials
5.1 Inert gas, argon or helium, high purity grade with a minimum purity of 99,9 % (V/V).
5.2 Oxygen, high purity grade with a minimum purity of 99,75 % (V/V), maximum moisture content of
5 mg/kg preferably dried over an additional molecular sieve.
CAUTION — Oxygen vigorously accelerates combustion.
5.3 Calibration standards.
Certified LPG calibration standards from commercial sources or calibration gases prepared using
certified permeation tube devices are recommended. Table 1 lists the sulfur source material and diluent
matrices proven to give good results.
Table 1 — Standard materials
Sulfur source Diluent
Dimethyl sulfide Mixture of n-butane, iso-butane, propylene, propane
Other sulfur sources and diluent materials may be used if precision and accuracy are not degraded.
NOTE Calibration standards are typically re-mixed and re-certified on a regular basis depending upon
frequency of use and age. These calibration standards have a useful shelf life of about 6 to 12 months.
Due to the reactive nature of the sulfur components, it is recommended to measure the calibration
standards shortly after they have been prepared and pour these into a suitably passivated LPG sampling
cylinder.
5.4 Quality control samples, preferably portions of one or more gas or LPG materials, stable and
representat
...