Bsi bs en 12177 2000 (2002) bs 2000 425 2002

EUROPAISCHE NORM November 2000 KS 75160.20 Descriptors: petroleum products, gasoline, chemical lanalysis, determination of content, benzene, chromatographic analysis, gas chromatograp

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BRITISH STANDARD BS EN

12177:2000

BS 2000-425:2002

Methods of test for

petroleum and its

products

BS 2000-425: Liquid petroleum

products — Unleaded petroleum —

Determination of benzene content by

gas chromatography

(Identical with IP 425:2001)

The European Standard EN 12177:2000 has the status of a

British Standard

ICS 75.160.20

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BS EN 12177:2000

This British Standard, having

been prepared under the

direction of the Materials and

Chemicals Sector Policy and

Strategy Committee, was

published under the authority

of the Standards Policy and

Strategy Committee on

13 August 2002

© Institute of Petroleum & BSI

13 August 2002

ISBN 0 580 40272 X

National foreword

This British Standard is the official English language version of

EN 12177:2000.

The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum testing and terminology, which has the responsibility to:

A list of organizations represented on this committee can be obtained on request to its secretary.

The Institute of Petroleum publishes and sells all parts of BS 2000, and all BS EN petroleum test methods that would be part of BS 2000, both

in its annual publication “Standard methods for analysis and testing

of petroleum and related products and British Standard 2000 parts” and individually.

Further information is available from:

The Institute of Petroleum, 61 New Cavendish Street, London W1G 7AR Tel: 020 7467 7100 Fax: 020 7255 1472.

Cross-references

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Summary of pages

This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 11 and a back cover.

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Amendments issued since publication

Amd No Date Comments

EUROPEAN STANDARD EN 12177

NORME EUROPiENNE

It

EUROPAISCHE NORM November 2000

KS 75160.20

Descriptors: petroleum products, gasoline, chemical lanalysis, determination of content, benzene, chromatographic

analysis, gas chromatography

Englis#h version

Liquid petroleum products - Unleaded petrol - Determination of benzene content by gas chromatography

Produits p&roliers liquides - Essence sans plomb -

DBtermination de la teneur en benzene par

chromatographie en phase gazeuse

Fliissige Mineralijlerzeugnisse - Unverbleite Ottokraftstoffe - Bestimmurrg des Benzolgehaltes mittels Gaschromatographie

This Euroipean Standard was approved by CEN on 23 March 1998 A technical corrigendum was issued for clause

9 on 1 5th November 2000 and thiis is incorporated into the text

CEN memblers are bound to comply with the CEN/CENEL,EC Internal Regulations which stipulate the conditions for giving thns European Standard the status of a national standard without any alteration Up-to-date lists and bibliogrlaphical references concerning such national standlands may be obtained on application to the Central Secretariat

or to any CEN member

This European StIandard exists in three official versions (Einglish, French, German) A versioln in any other language made by trlanslationi unde,r the responsibility of a CEN member into its own language and notified to thle Central Secretariat has the same status as the official versions

CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and United Kingdom

European Committee for Standardization Ciomit6 Europ6en de Normalisation Europ%sches Klcrmitee ftir Normung

Central Secretariat: rue de Stassart,36 B-1050 Brussels

[a 2000CEN <AlI rights of exploitation in any form and by any means

reserved worldwide for CEN national RJlembers

Ref No EN 1217;7:2000 E

425.1

Foreword

This European Standard has been prepared by Technical Committee CEN/TC 19 “Petroleum products, lubricants and Irelated products”, the secretariat of which is held by NNI

This European Standard shall be Igiven the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 1998, and conflicting national standards shall

be withdrawn at the latest by October 1998

According tlo thie CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Czech Republic, Denmark, Finlanjd, France, Germany, Greece,, Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden,, Switzerland and the United Kingdom

In this standard annex A is informative

I Scope EN IS0 12185, Crude petrolleum and petroleum

This European standard specifies a column1

switching gas chromatographic method for the

quantitative determination of benzene content i

tlhe ranlge 0,05 % (V/V) to 6 % (V/v) in unleaded

petrol having a final boiling point not greater than

220 “c

products - Determination of density - Oscillating U-tube method (IS0 12185:1996)

IS0 3170, Petroleum liquids - Manual

sampling

The method described1 in this standard is suitable

for determining benzene in petrol, including petrol

contahng oxygenates, in line with the relevant EC

Directives?

IS0 3171, Petroleum liquids - Automatic

pipeline sampling

NOTE For the purposes of this European Standard, the

terms ” ‘% ( WV) and ” % (m/m)” are used to\ represent

respectively the volume firaction anld the masIs fraction,,

The benzene-containing fraction is isolated from the sample using a capillary column antd, in a second capillary column, the benzene is separated and detected using a flame ionizaltion detector

‘WARNING : The use of this standard may involve

hazardous materials, operations and equipment

This :standard does not purport to address all of

the safety problems associated with its use It is

the responsibility of the user of this standard to

establish appropriate safety and health practices

and determine the applicability of regulatory

limitations prior to use

NOTE 1 Some oxygenates are known to interfere with the determination of benzene using a single column gas chromatographic method

NOTE 2 Guidance on the column switching technique

is given in annex A

Use only reagents of recognized analytical grade

‘This European Standard incorporates by dated or

Iundated reference, provisions from other

publications These normative references are cited

at thle appropriate pIlaces in the text and the

publiciations are listed herreafter For dated

referenc(es, subsequent arnendments to or

revisions of any of these publications appbly to this

standard only when incorporated in it by

amendment or revision For unjdated references the

latest edition of the publicatioln referred to applies

4.1 Carrier gas

Hydrogen, helium, or nitrogen, *free of hydrocarbons

WARNING : Hydrogen iis explosive in mixtures with air at concentrations of hydrogen ranging approximately from 4 % (V/V) to 75 % (WV) All joints and lines carrying hydrogen shall be made gas tight to prevent leakage of hydrogen into a confined space

EN ISO :3675 Crude petroleum and liquid

petroleum products - Laboratory determination of density or relative density - Hydrometer method (IS0 :3675: 1993)

4.2 Reagents for the preparation of calibration samples

EN IS0 :3838, Crude p~etroleum and liquid or solid

DIetermination of density or relative density - Capillary- stoppered pyknometer and graduated bicapillary pyknometer methocls (IS0 3838: 198:3)

NOTE Calibration samples will normally be combinations

of benzene, solvent and an internal standard

4.2 I Benzene

Not less than 99,0 % (m/m) pure.’

WARNING : Benzene is toxic and carcinogenic

1) EC Directive 85/21 O/EIEX, Council Directive on the approximation of the laws of the Member States concerning the lead (content of petrol EC Directive 85,‘536/EEC, Council Directive on crude-oil savings through the use of substitute fuel components in petrol

4,2!5.3

4.2.2 Solvent

Not containting benzene or internal standard, e.g

heptane

4.3 Internal1 standard

Reaqent for wh’ich it has been established that it

is nit present in the sample

NOTE lsobutyl methyl ketone is preferred as the

internal standard

Usual laboratory apparaltus and glassware,

together witlh thie following:

51 q Gas chromatographic assembly

5.1 I Gas chromatograph, provided with a

means foIr column switchting, equipped with a

programmable oven temperature controller, or

controllers in the case of dual oven gas

chromatographs, and two flame ionization

detectors (FIID)

NOTE It is recommendled that a system constructed

entirely of glams from the sample injection port up to

the detector system is used since petrol may contain

oxygenates which can give rise to corrosion and changes of retention times in systems constructed partly using metals

51.2 Two capillary columns, of appropriate dimensions, each internally coated with a substance of different polarity, such that the resolution between the benzene peak and the matrix is at least 1 after elution from the second column

The resolution, R, between peaks A and B (see figure 1) is calculated using the equation:

+’ - +’

R= I, 18 ?i!-?!-

wA + wB

where :

t’, t’,

WA

wB

is the reduced retention time of component A;

is the reduced retention time of component B;

is the peak width at half-height of component A;

is the peak width at half-height of component B

Start

NOTE t, is the hold-up time zero of the column, i.e the tilme taken for an inert component,, such as methane, to

travel through the column without chromatography taking place

iFigure 1 - Calculation of the resolution between peaks A and B

425.4

5.1.3 Device for the lcontrol of the flow of carrier the calibration factor, f, for benzene using the

5.1 A Recorder and/m integrator

An amplifier and potentiometric recording device,,

or an integrator or data processor systeim, giving

area values corresponding to the peak area in

square millimetres

f=

m, x A2

A, x m;

where :

ml is the mass of benzene in the

calibration sample, in grams;

5.2 Injection deviice

5.3 Test sample container, norma~lly with a

capacitld of between IO ml and 100 ml, fitted with

a sellf sealing rubber septum coat:ed with

polytetrafluoroethylent3 (PTFE)

is the peak area of the internal standard, in square millimetres;

Al is the peak area of benzene, in

square millimetres;

Unless otherwise specified in the commodity

specificat:ion, samples shall be taken as Idescribed

in IS0 3170 or IS0 3171, and/or in accordance,

with thte requirements of natiional standards or

regulations for the sampling of petrol

m2 is the mass elf the internal

standard in the calibration sample,

in grams,

7.3 Determination of density

71 Setting up the apparatus

7.1 I General

Determine the density at 15 “C, F’S, of the sample

in accordance with either EN IS0 3675, EN IS0 3838

or EN IS0 12185 and record the result to the nearest 0,l kg/m3

7.4 Preparation of test sample

Prepare the equipmenit and set the test condit-

ions iin accordance with thle manufacturer’s

instructions

Cool the sample to between 5 “C ancl 10 C Weigh, to the nearest 0,l mg, the test sample container (5.3) and its rubber septum without sealing it

7 I 2 Carrier gas

Adjust the pressure and flow rate of the carrier

gas to levels such sthat the resolution is in

aiccordance with 5.1 2

7.2 Clalibration

Prepare the calibration sarnple by combining

known masses of benzene (4.2.1) and internal

standarid (4.3) in a suitable solvent (4.2,,2)

Transfer a quantity of the internal standard (4.3)

to the test sample container and weigh, to the nearest 0,l mg, the tesIt sample container with contents and septum, without sealing the sample container The mass, m,,, in grams, of the internal standard shall amount to between 2 % (m/m) and

5 % (m/m) of the sample,, m,, but shall not be less than 0,050 g

Inject a suitable quantity of the prepared

calibrat.ion sample intlo the gas chromatograph

such that the capacity of the columns and other

clomponents is nIot exoeeded and the linearity of

the detector is not impaired

Transfer a quantity, normally between 5 ml and

100 ml, of the cooled sample to the test sample container and seal immediately with the septum Weigh, to the nearest 0,l mg, the test sample container and contents Record the mass, m,, in

grams, of the test sample taken, to the nearest

0, 1 mg

Determime and record the retention times for

bIenze?ne and for the internal standard Calculate

Record the amount of internal standard in the prepared test sample as a percentage by mass Mix the contents of the test sample container by shaking untit homogeneous

42!5”5

7.5 introduction of test portion

inject a suitable quantity of the prepared test

sample (7,,43 ilnto the gas chromatograph Ensure

that the test portion size is such that the capacity

of the columns and other clomponents of the gas

chromatograph is not exceeded and that the

linearity of the detector is not impaired

7.6 Examination of the gas chromatogram

Examine the qas chromatoIgram and identify the

benzene and ‘the internal standard by means of

their retention times (see 7 ,,2),

81 Calculation of mass of benzene in the

test sample

Calculate the m ass,, /n3, in grams

the test sample using th e followin

where :

f

mg =

f x A, >r: m4 A4

is the benzene ,’

is the square

9

calibration

peak area millimetres

of benzen equation:

factor

e in

for

of benzene, in

is the mass of the internal standard in the test sample (see

7.4), in grams;

is the peak: area of the internal standard, in! square millimetres

8.2 Calculation of volume of benzene in

the test sample

Calculate the volume, V,, ini millilitres, of benzene

in the test sample using the following equation:

m3 x 1000

“/, = - -

pb

where :

is the mass of benzene in the test sample (see 8 I), in grams;

pb is the density of lbenzene at 15

“C, i.e 884,3 kg/m3

8.3 Calculation of volume of test sample

Calculate the volume, V2, in millilitres, of the test sample using the following equation:

where :

rns x 1000 v2 = ~ _ ~-~

P S

m5 is the mass of the test sarnlple

(see 7.4), in grams;

P S is the density at 15 “C of the

sample, in kilograms per culbic metre

8.4 Calculation of benzene content as

96 (V/v)

Calculate the benzene content, @, of the sample

as a percentage by volume using the following {equation:

Iwhere :

CP

v, x 100

= -. -_ - _

4

VP is the volume of benzene in the

test sample (see 8.2), in millilitres;

is the volume of the test sample (see 8.3), in millilitres

IReport the benzene content to the nearest 0,Ol % (V/l/)

‘10.1 Repeatability, r

The difference between two test results, obtained

by the same operator with the same apparatus under constant operating conlditions on ident:ical test material, would in the long run, in #the normal and correct operation of the test method, exceed the values given in table 1 only in one case in twenty

10.2 Reproducibility, R

The difference between two siingle and independent results, obtained by different

operators working in differlent laboratories on

iidentkal test material, would in the Iontg run, in

the normal and correct operation of the test

mnethodl,, exceed the values given in tablie 1 only in

one case in twenty

b) a reference to thiis European Standard; b) the sampling procedure used (see 6);

d the density of the sample (see 7.3);

The report shall include at least the following

informat:ion:

e) any deviation from the procedure

described;

a 1 the type and identification of the product

under tIest ;

f) the date of test

Table 1 - Repeatabillity and reproducibility

Benzene content

?h w/w

Repeatiabilityl r

% (V/v)

Reproducibility, R

% w/w

I > O,l5 to 1,510 I OF03 I O,lOl I

I > I,50 to 6,OO I 10,ro5 I O/25 I

42!5.7