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Whereas the Parliament of India has set out to provide a practical regime of right to information for citizens to secure access to information under the control of public authorities, in order to promote transparency and accountability in the working of every public authority, and whereas the attached publication of the Bureau of Indian Standards is of particular interest to the public, particularly disadvantaged communities and those engaged in the pursuit of education and knowledge, the attached public safety standard is made available to promote the timely dissemination of this information in an accurate manner to the public.

इंटरनेट मानक

“!ान $ एक न' भारत का +नम-ण”Satyanarayan Gangaram Pitroda

“Invent a New India Using Knowledge”

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“Step Out From the Old to the New”

“जान1 का अ+धकार, जी1 का अ+धकार”Mazdoor Kisan Shakti Sangathan

“The Right to Information, The Right to Live”

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“Knowledge is such a treasure which cannot be stolen”

“Invent a New India Using Knowledge”

है”ह”ह

IS 15130-3 (2002): Natural Gas - Determination ofComposition with Defined Uncertainty by Gas Chromatography,Part 3: Determination of Hydrogen, Helium, Oxygen,Nitrogen, Carbon Dioxide and Hydrocarbons up to C8 usingtwo Packed Columns [PCD 3: Petroleum, Lubricants and theirRelated Products]

IS 15130 (Part 3): 2002

iSO 6974=3 :2000

Ic&lri* $FH-$FTf

w-J13ahm-Qihlmimw?a’5qmqih-% i$mr’w , @fmfkmI

m~)m, mdd “w-s@wwT:G ~~ Cfj ii~ ~i~$$ WP$nn71w+

Indian StandardNATURAL GAS — DETERMINATION OF

COMPOSITION WITH DEFINED UNCERTAINTYBY GAS CHROMATOGRAPHY

PART 3 DETERMINATION OF HYDROGEN, HELNAVI, OXYGEN, NITROGEN, CARBONDKIXIDE AND HYDROCARBONS UP TO C8 USING TWO PACKED COLUMNS

I(X3 75.060

@ E31s2002

BUREAU OF IN DIANSTA ND ARDSMANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG

NEW DELHI 110002

April 2002 Price Group 7

Natural Gas Sectional CommiHee, PCD 24

NATIONAL FOREWORD

This Indian Standard (Part 3) which is identical with ISO 6974-3:2000 ‘Natural gas — Determinationof eamposJ\iun with defined uncertainty by gas chromatography — Part 3: Determination of hydrogen,helium, oxygen, nitrogen, carbon dioxide and hydrocarbons up to C8 wing two packed columns’ issuedby the International Organization for Standardization (ISO) was adopted by the Bureau of IndianStandards on the recommendation of the Natural Gas Sectional Cammittee and approval of theFWchm, Coal and Related Products Division Council,

The text of 1S0 Standard has been proposed to be approved as suitable for publication as IndianStandard without deviations. Certain conventions are, however, not identical to those used in IndianS!andards. Attention is particularly drawn to the following:

a) Wherever the words ‘international Standard’ appear referring tothis standard, they shouldbe road as ‘Indian Standard’.

b) Comma (,) has been used as a decimal marker while in indian Standards, the currentpractice is to use a point (.) as the decimal marker.

In this adopted standard, reference appears to the following International Standards for which IndianSi8~d~~d~ MSO wist. The ~O~~esp~nding Indian Skmdwds, which are to be substituted in their place,We @Jen below along with their degree d ecphdenm for the editions indicated, However, thatIn\erna\ional Standard cross referred in this adopted 1S0 Standard which has subsequently beenrevised, position in respect of latest 1S0 Standard has b~en given:

lntt?mathmi CWqxmihg Degree 0/standard indhm Standard Equivalence

/s0 6974-1 :2000 Natural gas — IS 15130 (Part 1) :2002 Natural gas— IdenticaiDetermination of composition with Determination of composition withdefined uncertainty by gas chromato- defined Lmcwtainty by gas chrurnatu-graphy — Part 1: Guidelines kx graphy: Part 1 Guidelines for tailoredMimed analysis analysis

1S0 6974-2:2000 Natural gas — 1S 15130 (Part 2) :2002 Natural gas — doDetermination of composition with Determination of composition withMined uncertainty by gas chromato- Mirwd uncertainty by gas ctwomato-graphy — Part 2: Measuring-system graphy: Part 2 Measuring-systemcharacteristics and statistics for data charactwistics and statistics fur datatreatment treatment

ISO 7504:7984 Gas analysis —Vucabt~lary

The Technics{ Committee responsible for the preparation of this standard wiil review the provisions of1S0 7504 and wili decide whe!ber they are acceptable for use in conjunction with this standard.

In repor!ing th~ rwults of a test or analysis made in accordance with this standard, if the final value,observed or calculated, is to be rounded off, it shall be done in accordance with IS 2:1960 ‘Rules forrounding off numericai valws (nwke@I’.

Is UH30 ( Pm 31:2002tSO 6974-3 ; 2000

lrdian Standard

NATURAL GAS — DETERMINATION OFCOMPOSITION WITH DEFINED UNCERTAINTY

BY GAS CHROMATOGRAPHYPART 3 I) ETERMINATKIN OF HY5M?OGENJ HELIUM, OXYGENJ NITROGEN, CARBON

DH3XH2E AND HYDROCARBONS UP TO C* USING TWO PACKES) COLUMNS

1 scope

This pan of 1S0 6974 d~scribes a gas cl-mmatoqraphic method for the quantitative determination of the content ofMM.mL hycimpi, uxy~en, nitqen, carbon dio~de and Cf ta C8 hydmca~!mw in natural gas samples using twopacked columm. This method k applicable to determinations made in omlhe processes or in the l~boratwy. it kq@caw to the ana@sk Of gases cunta~ning canstkuents within the mole fraction ranges given in Table 1 andwFM do not contain any hydrocarbon cundemate, These ranges cio not represent the limits of dett3ctbr?, bW ttl%Rnils within which the stated pw+%on of the method applies. AMuugh cm or more cumpcments in a sample mayrwt be Cw3md present, me I-TNmod can Em m appmmle.

This part of !S0 6974 k My applicable in conjunction with parts 1 and 2 of iSO 6974.

2 Normative references

The following normative documents contain provisions which, through reference in this text, constittite provisions ofthis @ of HX) 69?4. For dated references, subseqwmi mnendrnenls to, or revisions of, any of these publicationsdo nut apply. However, parties to a~reements based on W pari of ISO 6974 we encoumged W investigate thePOSSWity of applying Ihe must recent ecli!ions of the normafive documents indicated below. Fur undatednNQmnces, the !a~est edition of the normative ductmxmt referred to applies, Members of ISO and IEC maintain

B 15130 ( Part 3 ) :2002

1S0 6974-3:2000

1S0 6974-2+ 11, Natural gas — Determinafiofl of cc?mpcwwurl with defined Wm3tiair?ty by gas dW’7M@mphy —Part 2: Measuring-system characterktics and statistics kv data treatment.

3 Principle

Determination of nitrogen, carbon dioxide and hydrocarbons from Cl to C8 by gas chromatography using twochroma!ographic COMNK, A mcku!ar sieve 13X cuhmn coupled with a thermal conductivity defector (TCD) isused for the separation and detection of hydrogen, helium, oxygen and nitrogen, and a Porapak R column coupledwith a TCD and a frame ionization detector (IW} in series is used for the separation and detection of nitrogen,carbon dioxide and hydrocahms from +21M C3. The two analyses am canied out independently and the resultsare combined.

If uxygen k mm to be present at a mole fraction greater than 0,02 VUwhen measured using the molecular sievecolumn, then the nitrogen value shall be taken from the molecular sieve analysis. If the mole fraction of oxygen isless than 0,02 !% and aswninq thd hydrogen is absent from the gas sample, the ni~rogen vaiue can be taken fromthe Pmpak R wMysis.

Quantitative results are achieved by determining the response of the TCD detector with reference-gas mixtures andusing relative response factors of the F+3 detector.

4 Materials

4*I For the determinaticm cd helium, hydrogen, oxygen and nitrogen, (separation on mkcukir sieve 13XCokmm) consisting of the following.

4.1.1 Argon carrier gas, > 99,99?& pure, free from oxygen and water.

If the purity of Me gas is less than that specified, it is essential to check that h type d impurity present does notinterfere with the analysis. Also, even if the carrier gases argon and/or helium fall within the specification, some ofthe impurities present in the gases can nwwtheks inkrfw~ with W analysis. Under these circumstances,appropriate purification is essenth31*

4.1.2 Working-reference gas mixtures (WFWI), consisting of:

4,1.2.1 Gas mixtures containing helium and hydrogen with nitrogen or argon as the matrix gas,

4=1*2=2 Gas mixtures containing oxygen and nitrogen with argon as the matrix gas,

NOTE 1 Take care to preventexplosion of gas mixiwes.

NOTE 2 In the case uf analysis using only om instrument, the WFIM with oxygen and nitrogen as cmpmmts and argon asthe matrix gas can be mpiwed by oxygen WW Mmgen as rnalrixgas. By WMWURof helium to Me WRMthis gas could also Wused for the daily calibration.

1) To be published

2

Is 1513cu Part3] :2002

1S0 6974.3:2000

4.2 For the deteminatkm of nitrogen, carbon dioxide and hydrocarbons from ~~ to GE (separation on%rapak column), consisting of the following=

4.2.1 Helium carrier gas, Y 99,99 ?4 pure, free horn oxygen and water.

4.2.2 Working-reference gas mixtures (Wl+vl), consisting of muiti-cornponent gas mixtures containing:nitrogen, carbon dioxide and hydrocarbons from Cl to C3 (optional to C4)

An example of @ mmpos!tion of the wurking-+efermx gas mixture is given in Tab/e 2.

Table 2 — Example of the composition of the working-reference gas mixture

Nitrogen 6

MeN-w7e 80,5

Carbon dioxide 9

Ethw”w 4

Propane 0,5

r)-mtme U,5 (Qptiunai)

4,2,3 FID gases, consisting of

hydrogen, >99,99 Y. pure, free from corrosive gases and urgank compounds;

air, h-w from hy&OLXMXN7impurities.

Apparatus

Es 15130 ( RN-t 3 ) :2002

1S0 6974-3:2000

temperature controller, corwishg d a linear programmer suitable fur providing a rate of temperatureincrease of 30 “Gknin over the specified range=

b) flow regulator: capable of nmin!aining suitable carrier-gas flow rates.

5.1,1,2 hjwtion device, consisting o! a by-pass-type injector (gas-sampling valve) having an injectioncapaciky of 1 ml and capable of being heated to a temperature setting of 110 “G.

The sample volume shall be reproducible such that successive runs agree within 1 ?’6for each component.

5.1.1.3 Columns, IWOwith the same type of packing and with the same dinwnskms.

The second column is normally used fur drift curnpensation during the temperature prugramme. If drift iscumpwwted by mans of m ekxtmnic integrator, the second column k not necessary.

CUlumns shall satisfy the following requirements

a) me!ai tubingf having the Mowing chamc!erisiics:

nature: stainless steel, rmnlber 20 (AISI type 316), cleaned and degrmsed

length; 1 WI

diameter: 2 mm internal diameter (id.)

form: a~~ro~riak fur Ihe clmmakqm@

radius: appropriate for the chmrnakqraph

packing, Molecular sieve 13X, particle size from 150 pm b 1$0 pm (80 ASTM mesh to ?00 ASTM mesh);

method of packing: my s~itable packing method providing uniform column packing;

conditioning: overnight at approxhmatdy 350 “C under a flow of carefully dried carrier gas,

Nom SWIIe Mjeetiundwices we unable to deal with ternperatwes above 250 “C and may cause mnditkmingproblems.

5.1.?*4 Thermal conductivity detector (TCD).

5.1.2 For the determination of nitrogen, carbon dioxide and hydrocarbons from Cl to C8, equipped withthe Mbwing specific components and characteristics.

5.1.2.1 Gas chromatography, suilable for dual-column application and equipped in series Wi!h a TCD and anFKI.

a) mkmn own and temperature cuntmkr, CUrlSktkj &

column oven, capab!e of nmWk@ the temperature d W column to within k 0,5 ‘C over a temperaturerange from 35 “C to 230 “C.

NOTE To obtain a temperature Qf 35 “C an aCCeSSU~ w COOIing with liquid carbon tliuxkie or !iquki Mmgenmay be necessary.

— temperature fwNruHf3r, consisting of a Iinear programmer suilabb for providing a rate uf temperatureincrease of 15 ‘C/rein ov~r the specified range,

4

IS 15130 {Part 3):2002

1S0 6974+3 :2000

b) fiow regulator, capabk of maintaining suitable carriw-gas flow rates.

5,7 *2.2 Mjectiun device, consisting of a by-pass=type injector (gas-samp!ing valve) having an injectioncapacity of 1 m! and capable of being heated to a tempem!ure setting of 110 W.

S1 *2*3 Columns, two of Hw same type of packing and with the same dimensions.

The sword cukmm is mmdy used for drift compensation during the temperature prugramrne, If drift kcurnpensa{ed by means 01 an ekctrunk integrator, the second cokimn is nut necessary.

a) metal tubing, having W following characteristics:

nature: stainless steel, number 20 (AH type 316), cleaned and degreased

— length: 3 m

— diameter: 2 mm id.

— fmrn: appropriate for the chrumatograph

radius: appropriate for the chmmatograph

b) !%rapak R packing, particle size from 150pm to 180 pm (80 ASTM mesh m 100 ASTM mesh);

rmihod d packing: my suitable packing method providing uniform column packing

conditioning: overnight at approximately 230 W under a flow of carefully dried carrier gas

5.1,2.4 Detecbrs, having he following characteristics:

— for components including hydrocarbons up to C3: thermal conductivity detector (TCD)

— for hydrocarbons from CA to C8: flame ionization detector (FID)

Hhane and propane can be detected by an FW2 if the mole fraction is less than 1 ?4. In either case, the timeccms!ant shall not be greater than 0,1 s. If C3 k used as reference component, it shall be detected by m FH3.

— ha T(2D and FKI detectors shall be connected in series

6 Procedure

6.1 Gas chrunxitographic operating condition$

6.1.1 For the determination of helium, hychgenf oxygen and nitrogen

Set ~h~ operating conditions for the apparatus (5,1,1) as follows,

a) Oven and column:

initial temperature; 35 “C for 7 mh

— Mnperature rate: 30 “Wmin b 250 T

is 75130 (Pan3) :2002

!s0 6974-3:2000

set according to manufacturer’s instructions

carrier gas: argon

6*I4?.1 Gc Cmcmiom

a] ovenand column:

initial temperature: 37C for 3 nin

— temperature rate: 15 “Cknin to 200 “G

h) carrier gas: helium

— T(XI

i) Mnperatt.mx between 240 “C and 260%

6,3.2.2 Column stability check

U-wk the baselb sJabNityof the column by means of blank runs.

NCI individual peak shall originate from a constituent having a mole fraction exceeding 0,04 $%. If larger peaks aseen, repeat blank runs until satisfactory. H necessary, prepare new columns, preferably from a different batchRNapak R.

6

IS 15130 (Part3) :2002

so 6974-3:2000

NOTE 2 Baseline stability may be checked as follows:

a) raise the mm~ to the final te~pwa!ure to cl~ar any accumulated con!amina~bn;

b) COOIto the Mal ternpera[ure;

c) injwt a calibration gas mixture containing a low mole fraclkm of bu{ane and s~ati the temperature programme;

d) at the end of the calibration gas run, cool 10 the initial temperature, Perkmm a blank run by injecting carrier gas inplace of aSanple and start the @npemhm pwgwnme;

6.2 Performance requirements

6.2=1 Resolution efficiency

Assess the peak resolution in accordance with ISU 7504

Table 3 — Required peak resolution

Component 1 component 2 Resolutionm

Hydrogen Heh’n 0,1@ IEM}

62=1.2 Purapak R cuhmm

The height of the va!ley between the 2-metl@!NJtane and pen!ane peaks above the baseline shall be m greaterthan 10 % of the height of the larger peak under the operating conditions following injection of a sample. If thiscriterion is not me{, condition the packing for a longer period or prepare a new column.

6.2.2 Response

Dehxrnine W ~espunse characteristics fur each o! the gases determined in accordance with iSO 6974-2 a! leastOnce a year.

6.2,3 Relative response factor

Determine the relative response factors in accordance VW 1S0 6974-2.

B 15130 ( Part 3 ) :2002

/s0 6974-3:2000

63.1 ChNhe d W? maly$k

6*3.2 Esthnahn d Mw3r mmpment$

7 Expression of results

7.1 *I NMe fractions

Refer to Km 6974”1 *

78we =x~2 – —-%@

21

In equation(1), it h ars.med thal the TCD wspmses for N2 and 02am eqwd.

(2)

h equation (2) R iS assumed that the TCD mponses for N2 and 02 an? equal,

/l k thetotal TwTlkr d Cm-nponei-its;

II–Z is W total numbw of components except cwygen and Mrogenl determined separately on both themolecular sieve 13X and Porapak R column.

Fkfw k) MI 6974-2.

see annex B for typical precision WEST

E q5130 ( I%M%3 ) :2002

1s0 6974-3:2000

AmImc A(informative)

Singk-mm gasudmmatographic system consisting of two columns

Both ana!y-ticd columns are placed in a single culumn oven and provided with a linear temperature programmercapable of obtaining a rate of temperature increase of 30 “Chin over Ihe specified range.

A moiecu!ar sieve 13X cokmm is used fur the determination of helium, hydrogen, oxygen. The detection of thesecm-npunen!s is carried out by TCD, The gas sample is injected using a by-pass-type injector with an injectioncapacity of 1 mL Flow regulators are used to give suitable argon gas-flow rates.

A Purapak R column is used fur the determination of nitrogen, carbon dioxide, methane to normal Qctane. Thedetection is carried out by TCD in series with an FD The gas sample is injected using a by-pass-type injector (gassampling valve) with an injection capacity of I ml. Flow regulators are used to give suitable helium gas flow rates.

The ccmfigumtkm d such a chmmtugraphie system isgiveninTable A.1,

Table Ad — Configuration of the chromatographic system

1’ !~

?Wtrogm, carbon di=ide!Detmminaliurl Helium, hydrogen, oxygen

methane to normal octane

Mm-ml

Packing Molecular sieve 13X

Length

Internal diameter

ASTM mesh size 80 to 100 80 to 100

Nktd tubing stainless steel stainless sled

Carrier gas Argon; 30 ml/min Helium; 30 rnlhminw: w

ktectur TCD TCD and FID*

njection device

Capacity 1 ml

Valve temperature Ilo”cm

“temperature setting

Initial temperature 40 “c 40 ‘cInitial time 12 mitl 12 min

Temperature rate 15 ‘Chin 15 “C/rein

Final temperature 200 “G 200 ‘cFinaltkne 30 Ml 30 min

Is 15130 ( PW3 ) :2002ISO 6974-3:2000

start

11

IS 15?30[Part 3):2002

fso 6974-3:2000

Nitrogen (oxygm)

Methane

Carlxmdioxide

Emma

Necl@fltane

?

I=kptam

(octane

Figure A2 — Typical chrormtogrwn of nitrogen (QXygen)$ carbon dioxide andhydrocarbons from (21 w (28 using a Porapak R coiumn

12

E 15130 ( Part 3 ) :20021s0 6974-3:2000

Annex B(h7f0rm~tive)

Typical precision values

Typical values for repea!abili!y and reproducibility, which have been assessed in an interkboratory test project oflSO/K 158EC 2 in Udober 1986 with participa!km of gas-producing, gas-supplying, gas-shipping companies andcommercial laboratories from Be!@m, Gewnany, keland, Nmvay, the Netherlands and the UK are given in

Table B.1 — Repaatatility and reproducibility of measurement results

~ole fractionRepeatability Reproducibility

Absolute Relative Absolute Rela~ivemule fraction (“/0) 540 mole fraction (%) ‘x?

0,0Q3 0,006

0,1 CX<l 3 6

I< X<50 1 — 3

5u<xduu 0,1 0,2

These values have been obtained from ~raclkal qwrknce and indicate the @ormance of themethod. They cannot be compared as such WM precision values men~iormd h kformah annexes of ohrparts of 1S0 6974 because they result from the quality of the calibration gases and Iabmalmy skills

13

Is 15130 ( Part3) :20021s0 6974-3 : 2000

[1]

[2]

[3]

[4]

[5]

[6]

1S0 6743, Gas analysis — Determination of t)wmethods.

]So 6976, Natural LJ3S— (Mcu/atbr2 0/ cabrikcomposition.

compositbn of calibration gas mixtures — Comparison

values, density, rehthw densily and Wobbeindex from

2) To be published

j 4

Bureau d hndim standards

ENS is a statutory irw~itu~ior] es!a~lished under the Bureau of Indian Standards Act, 1985 to promoteharmonious development of the activities d standardizaticmf marking wtd quality certification of goodsartd attending to connected matters in the ccxmtry.

thpyrjght

B\S has W capyright of all its publications, No part of these pub!icaticm$ may be repmd~~~d in any

form withmt the prior permission in writing of 31S. Th!s d~es not preclude the free use, in the courseof implementing the standard, of necessary details, such as symbols and sizes, type w gradedesignations. Enquiries relating to copyright be addressed to the Director (Publications), W%

Review of Indkm Standards

Amendments are issued to standards aS the need arises CM the b~sis of comments. Standards wealso reviewed periodically; ~ standard along with amendments iS reaffirmed when such review indi-cates that m changes am needed; if the review indicates that changes are needed, it is taken up furrevision. Users of Indian Standards should ascerta}n that they are in possession of the latest amend-ments Or edition by referring to the latest issue of ‘BE Catalogw’ and ‘Skindards: Monthly Additions’.

This Indian Standard has been developed from llx : No, PCD 24 (1490).

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