INTERNATIONAL

STANDARD
First edition
1993-12-15

Liquid Petroleum products -

Determination of hydrocarbon types -
Fluorescent indicator adsorption method
iTeh STANDARD PREVIEW
(standards.iteh.ai)
Produits p6 troliers liquides - Determination
d h ydrocarbures - Methode par adsorption
des groupes
en pkence d’indicateurs
fluorescen ts
ISO 3837:1993
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e4ffe643d99c/iso-3837-1993

Reference number
ISO 3837:1993(E)
ISO 3837:1993(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. Esch 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
(1EC) on all matters of electrotechnical standardization.

Draft International Standards adopted by the technical committees are

circulated to the member bodies for voting. Publication as an International
Standard requires approval by at least 75 % of the member bodies casting
a vote. iTeh STANDARD PREVIEW
International Standard (standards.iteh.ai)
ISO 3837 was prepared by Technical Committee
ISO/TC 28, Petroleum products and lubricants.
ISO 3837:1993
Annex A of this International https://standards.iteh.ai/catalog/standards/sist/bef60153-9be0-4690-94c4-
Standard is for information only.
e4ffe643d99c/iso-3837-1993

0 ISO 1993
All rights reserved. No part of this publication may be reproduced or utilized in any form or
by any means, electronie or mechanical, including photocopying and microfilm, without per-
mission in writing from the publisher.
International Organization for Standardization
Case Postale 56 l CH-1 211 Geneve 20 l Switzerland
Printed in Switzerland

ii
 ISO 3837:1993(E)

Introduction
The determination of the total volume percent [% (VW)] of saturates,
olefins and aromatics in Petroleum fractions is important in characterizing
the quality of Petroleum fractions as gasoline blending components and
as feeds to catalytic reforming processes, and in characterizing Petroleum
fractions and products from catalytic reforming and from thermal and
catalytic cracking as blending components for motor and aviation fuels.
This information is also important as a measure of the quality of aviation
turbine fuels.

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ISO 3837:1993
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ISO 3837:1993
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e4ffe643d99c/iso-3837-1993
INTERNATIONAL STANDARD ISO 3837:1993(E)

Liquid Petroleum products - Determination of

hydrocarbon types - Fluorescent indicator adsorption
method

WARNING - 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. lt is the
responsibility of the User of this Standard to consult and establish appropriate safety and health
practices and determine the applicability of regulatory limitations Prior to use.

1 Scope cohol desorbent. Other oxygenated compounds must be

iTeh STANDARD PREVIEW individually verified. When samples containing oxygenated
blending components are analyzed, the hydrocarbon type
This International Standard specifies a fluorescent in- results tan be reported on an oxygenate-free basis or, when
dicator adsorption method (standards.iteh.ai)
for the determination of the oxygenate content is known, the results tan be cor-
hydrocarbon types over the concentration ranges rected to a total-sample basis.
from 5 % (VW) to 99 % (WV) aromatic hydrocarbons, ISO 3837:1993 6 Samples containing dark-coloured components that in-
0,3 % (VW) to 55 % (V/V) olefins, and 1 % (VIV) to
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terfere with reading the chromatographic bands cannot be
95 % (V/v) saturated hydrocarbons in Petroleum frac-
e4ffe643d99c/iso-3837-1993
analyzed.
tions that distill below 315 “C.

Restrittions inherent in the method and the determi-

nation of precision may limit its application as noted. 2 Normative references
NOTES
The following Standards contain provisions which,
1 This method may apply to concentrations outside these through reference in this text, constitute provisions
ranges, but the precision has not been determined. of this International Standard. At the time of publi-
cation, the editions indicated were valid. All Standards
2 This test method is intended for use with full boiling are subject to revision, and Parties to agreements
range products. Cooperative data have established that the based on this International Standard are encouraged
precision Statement does not apply to Petroleum fractions to investigate the possibility sf applying the most re-
with narrow boiling ranges near the 315 “C limit. Such
samples are not eluted properly, and results are erratic.
cent editions of the Standards indicated below.
Members of IEC and ISO maintain registers of cur-
3 The applicability of this test method to products derived rently valid International Standards.
from fossil fuels other than Petroleum, such as coal, shale
or tar Sands, has not been determined and the precision ISO 756-1 :1981, Propan-2-01 for industrial use -
Statement does not apply to such products. Methods of test - Part 1: General.

4 The precision of this test method has not been deter- ISO 3171:1988, Petroleum liquids - Automatic pipe-
mined with oxygenated fuels and thus does not apply to line sampling.
automotive gasolines containing lead anti-knock mixtures.

5 The oxygenated blending components methanol,

ASTM D 3663-84, Test method for surface area of
ethanol, methyl tert-butyl ether, tert-amyl methyl ether and ca talys ts.
ethyl tefi-butyl ether do not interface with the determi-
nation of hydrocarbon types at concentrations normally ASTM D 4815-89, Test method for analysis of C, to
found in commercial Petroleum blends. These oxygenated C4 alcohols and MTBE in gasoline by gas
compounds are not detected since they elute with the al- chromotograph y.
ISO 3837:1993(E)

3 Dedinitions the analyzer outlet. The column tip attached to the

12/2 socket shall have a 2 mm inside diameter. Clamp
For the purposes of this International Standard, the the ball and socket together and ensure that the tip
following definitions apply. does not tend to slide from a Position in a direct line
with the analyzer section during the packing and sub-
3.1 saturates: Volume percent [% (VW)] of alkanes sequent use of the column.
plus cycloalkanes.
For convenience, adsorption columns with Standard
wall tubing, as shown on the left in figure 1, may be
3.2 olefins: Volume percent [% (WV)] of alkenes
used. When using Standard wall tubing for the ana-
plus cycloalkenes plus some alkadienes.
lyzer section, it is necessaty to select tubing of uni-
form bore and to provide a leakproof connection
3.3 aromatics: Volume percent [% (WV)] of con-
between the separator and the analyzer sections.
densed monocyclic and polycyclic aromatic hydro-
Calibrations of Standard wall tubing would be imprac-
carbons plus aromatic olefinic hydrocarbons, some tical; however, any variations of 0,5 mm or greater,
dienes, compounds containing Sulfur and nitrogen, or
as measured by ordinary calipers, in the outside di-
higher-boiling oxygenated compounds (excluding
ameter along the tube may be taken as an indication
those listed in Note 5).
of irregularities in the inside diameter and such tubing
should not be used. Draw out one end of the tubing
4 Principle selected for the analyzer section to a fine capillaty to
retain the gel. Connect the other end of the analyzer
Approximately 0,75 ml of Sample is introduced into a section to the separator section with a 30 mm length
special glass adsorption column packed with activated of polyvinyl tubing, making certain that the two glass
silica gel. A small layer of the silica gel contains a sections tauch. To ensure a leakproof glass-to-
mixture of fluorescent dyes. When all the Sample has polyvinyl seal with the analyzer section, it is necessary
been adsorbed onto the gel, alcohol is added to to heat the upper end of the analyzer section until it
desorb the Sample down the column. The hydro- is just hot enough to melt the polyvinyl, then insert
iTeh STANDARD PREVIEW
carbons are separated, according to their adsorption the upper end of the analyzer section into the poly-
affinities, into aromatics, olefins and saturates. The Vinyl sleeve. Alternatively, this seal tan be made by
(standards.iteh.ai)
fluorescent dyes are also separated selectively with securing the polyvinyl sleeve to the analyzer section
the hydrocarbon types, and render the boundaries of by wrapping it tightly with soft wire.
the aromatic, Olefin and saturate zones visible underISO 3837:1993
ultraviolet light. The volume percentage [% (VW)] of 52. Zone-measuring-device.
https://standards.iteh.ai/catalog/standards/sist/bef60153-9be0-4690-94c4-
each hydrocarbon type is calculated from the e4ffe643d99c/iso-3837-1993
length
of each zone in the column. The zones may be marked with glass-writing pencil
and the distances measured with a metre rule, with
NOTE 7 Errors leading to high saturate values and low the analyzer section lying horizontally. Alternatively,
aromatic and low Olefin values tan result if the Sample the metre rule may be fastened adjacent to the col-
contains C3 or lighter hydrocarbons, or more than 5 % C, umn. In this case, it is convenient to have each rule
hydrocarbons, or more than 10 % C, and C, hydrocarbons. fitted with four movable metal index Clips (figure 1) for
Such samples should be depentanized as specified in marking zone boundaries and measuring the length
ANSI/ASTM DZ001 (see annex A).
of each Zone.

5 Apparatus 5.3 Ultraviolet light Source, with radiation pre-

dominantly at wavelength 365 nm.
5.1 Adsorption columns, either with precision bore
tubing, as shown on the right in figure 1, made of A convenient arrangement consists of one or two
glass and consisting of a charger section with a units 915 mm or 1 220 mm in length mounted verti-
capillary neck, a separator section, and an analyzer cally alongside the apparatus. Adjust to give the best
section; or with Standard wall tubing, as shown on the fluorescence.
left in figure 1.
5.4 Electric Vibrator, for vibrating the individual col-
The inside diameter of the analyzer section for the umns or for vibrating the frame supporting multiple
precision bore tubing shall be I,60 mm to I,65 mm columns.
and an approximately 100 mm thread of mercuty shall
not vary by more than 0,3 mm in any patt of the ana- 5.5 Hypodermic Syringe, of capacity 1 ml, gradu-
lyzer section. In glass-sealing the various sections to ated to 0,OI ml or 0,02 ml, with needle 102 mm in
each other, long-taper connections shall be made in- length, with an inside diameter of 0,7 mm to
stead of shouldered connections. Support the silica I,2 mm.
gel with a small piece of glass wool located between
the ball socket of the 12/2 spherical joint and covering Needles of No. 18, 20 or 22 gauge are satisfactory.
 ISO 3837:1993(E)

Dimensions in millimetres
unless otherwise indicated
Pressuring gas

Spherical joint S 29
@ int. 12 w @ int. 12

Pack gel to this Level ‘-1

J
int. 2Y

iTeh STANDARD PREVIEW

(standards.iteh.ai)
a Cr1
s
Dyed gel
Q>int. 5
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Iw<
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Lorig taper

j @ ext. 3,5
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Polyvinyl tubing - t
110 in device (optional)

1,60 - 1,65
precision bore
capillary tubing

Spherical joint S 13
Standard wall tubing - \ I

-\Tipdrawnout to
fine capillary

Standard column Precision bore column

Figure 1 - Adsorption columns with Standard wall (left) and precision bore (right) tubing in analyzer
section
ISO 3837:1993(E)

6 Reagents 6.3 Propan=2=ol, 99 % pure, as specified in

ISO 756-1.

6.4 Pressurizing gas, air (or nitrogen) delivered to

6.1 Silica gel 1), manufactured to conform to the the top of the column at pressures controllable over
specifications shown in table 1. The surface area of the range from 0 kPa gauge to 103 kPa gauge.
the gel is determined in accordance with ASTM D
3663. Determine the pH of the silica gel by placing
5 g of the gel Sample in a 250 ml beaker. Add 7 Sampling
IO0 ml of water and a stirring bar. Standardize the pH
meter with Standards of pH 4 and pH 7. Stir the slurty Obtain a representative Sample in accordance with
with the magnetic stirrer for 20 min and then deter- sampling procedures given in ISO 3171. Store the
mine the pH. Before use, dry the gel in a shallow Sample at 2 “C to 4 “C until ready for analysis.
vessel at 176 “C for 3 h. Transfer the dried gel to an
airtight Container while still hot, and protect it from
atmospheric moisture. 8 Test procedure
NOTE 8 Some batches of silica gel that otherwise meet
specifications have been found to produce Olefin-boundary 8.1 Mount the apparatus assembly in a room or area
fading. The exact reason for this phenomenon is unknown darkened to facilitate observations of zone bound-
but will affect accuracy and precision. aries. For multiple determinations, assemble an ap-
paratus that includes the ultraviolet Source, a rack to
hold the columns, and a gas manifold System with
Table 1 - Silica gel specifications spherical joints to connect to the desired number of
columns.
Surface area: 430 to 530 m*/g
pt-l of 5 % water slurry: 5,5 to 7,0iTeh STANDARD
Loss on ignition at 955 “C: 4,5 to IO,0 mass % clamp
PREVIEW
8.2 Freely
placed
suspend the column from a loose-fitting
immediately below the spherical joint
Iron as Fe,O,, dry basis: 50 max. mass ppm (standards.iteh.ai)
of the charger section. While vibrating the column
along its entire length, add small increments of silica
gel through a glass funnel into the charger section
Particle size distribution ISO 3837:1993
until the separator section is half full. Stop the Vibrator
w Sieve number https://standards.iteh.ai/catalog/standards/sist/bef60153-9be0-4690-94c4-
Mass % and add a 3 mm to 5 mm layer of dyed gel. Start the
Vibrator and vibrate the column while adding additional
e4ffe643d99c/iso-3837-1993
250 on 60 silica gel. Continue to add silica gel until the tightly
packed gel extends 75 mm into the charger section.
180 on 80 100
Wipe the length of the column with a damp cloth
150 on 100 95 min. while vibrating the column. This aids in packing the
75 through 200 15 max. column by removing static electricity. Vibrate the col-
umn for about 4 min after filling is completed.

NOTE 9 More than one column tan be prepared simul-

taneously by mounting several on a frame or rack to which
an electric Vibrator is attached.
6.2 Fluorescent indicator-dyed gel*), a Standard
dyed gel, consisting of a mixture of recrystallized
Attach the filled column to the apparatus assembly in
Petrol red AB4 and purified portions of Olefin and
the darkened room or area. If a permanently mounted
aromatic dyes obtained by chromatographic adsorp-
metre rule is used, fasten the lower end of the col-
tion following a definite, uniform procedure, and de-
umn to the fixed rule with a rubber band.
posited on silica gel. The dyed gel must be stored in
a dark place under an atmosphere of nitrogen. When
stored under these conditions, dyed gel tan have a 8.3 Chill the Sample and a hypodermic Syringe to
shelf life of at least five years. lt is recommended that 2 “C to 4 “C. Draw 0,75 ml & 0,03 ml of Sample pet-
portions of the dyed gel be transferred as required to roleum fraction into the Syringe and inject the Sample
a smaller working vial from which the dyed gel is 30 mm below the surface of the gel in the charger
routinely taken for analyses. section.

1) Available from W.R. Grate Co., Davison Chemical Division, Baltimore, MD 21203, USA by specifying Code 923. This is an
example of a suitable product available commercially. This information is given for the convenience of users of this International
Standard and does not constitute an endorsement by ISO of this product.
2) Available from UOP Organics Dept., 25 E. Algonquin Rd., Des Plaines, IL 60017-5017, USA by requesting “FIA Standard
Dyed Gei”, UOP Product No. 675. This is an example of a suitable product available commercially. This information is given for
the convenience of users of this International Standard and does not constitute an endorsement by ISO of this product.

4
 ISO 3837:1993(E)

8.4 Fill the charger section to the spherical joint with analysis. With Standard wall tubing, this criterion of total
propan-2-01. Connect the column to the gas manifold Sample length is not strictly applicable because the inside
and supply 14 kPa gauge gas pressure for 2,5 min to diameter of the analyzer section is not the same in all col-
move the liquid front down the column. Increase the umns. For samples containing substantial amounts of ma-
terial boiling above 205 “C, the use of Z-methylbutan-1-01
pressure to 34 kPa gauge for another 2,5 min and instead of propan-2-01 may improve elution.
then adjust the pressure required to give a column
transit time of about 1 h. Usually 28 kPa to 69 kPa
gauge gas pressure is needed for gasoline-type sam- 8.6 Release the gas pressure and disconnect the
ples and 69 kPa to 103 kPa gauge gas pressure for jet column. To remove used gel from the precision bore
propulsion fuels. The pressure required will depend column, invert it above a sink and insert through the
on the tightness of packing of the gel and the molec- wide end a long piece of hypodermic tubing of 1 mm
ular mass of the Sample. A transit time of 1 h is opti- to 1,5 mm nominal external diameter with a 45” angle
mum; however, high-molecular mass samples may tip. By means of 6 mm topper tubing at the opposite
require longer transit times. end, attach a rubber tube, connect to a water tap and
flush with a rapid stream of water. Rinse with
residue-free acetone and dry by evacuation.
8.5 After the red, alcohol-aromatic boundary has
advanced 350 mm into the analyzer section, make a 9 Calculation
set of readings by quickly marking the boundary of
each hydrocarbon-type zone observed in ultraviolet
light in the sequence given below. Avoid touching the 9.1 For each set of observations, calculate the
column with the hands during this Operation. hydrocarbon types to the nearest 0,l % (WV) as fol-
lows:
WARNING - Direct exposure to ultraviolet light
tan be harmful, particularly to the eyes. Operators aromatics, % (VW) = (LJL) x 100
should avoid such exposure as much as possible.
olefins, % (VW) = (L,/L) x 100
iTeh STANDARD
For the nonfluorescent saturate Zone, mark the front
PREVIEW
saturates, % WV) = (LJL) x 100
of the Charge and the Point where the(standards.iteh.ai)
yellow fluor-
escence first reaches its maximum intensity; for the
upper end of the second, or Olefin Zone, mark the
Point where the first intense blue fluorescence ISOoc- 3837:1993 is the length of the aromatic Zone, in i; ...
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curs; finally, for the upper end of the third, or aromatic metres;
Zone, mark the upper end of a reddish or brown e4ffe643d99c/iso-3837-1993
Zone.
With colourless distillates, the alcohol-aromatic LO is the length of the Olefin Zone, in milli-
boundary is clearly defined by a red ring of dye. metres
However, impurities in cracked fuels often obscure
is the length of the saturate Zone, in milli-
this red ring and give a brown coloration, which varies
in length, but which shall be counted as a patt of the metres;
aromatic Zone, except that when no blue fluorescence L is the sum of La + L. + Ls, in millimetres.
is present, the brown or reddish ring shall be consid-
ered as part of the next distinguishable zone below it Calculate the mean of the respective values for ea\
in the column. If the boundaries have been marked type and include it in the test report. lf necessary,
off with index Clips, record the measurements. adjust the result for the largest component so that the
sum of the means of the components is 100 %.
When the Sample has advanced another 50 mm
down the column, make a second set of readings by
marking the zones in the reverse Order to that de- 9.2 The equations given in 9.1 calculate concen-
scribed above so as to minimize errors due to the trations on an oxygenate-free basis and are correct
advancement of boundary positions during readings. only for samples that are composed exclusively of
If the marking has been made with a glass-writing hydrocarbons. For samples that contain oxygenated
pencil, two colours tan be used to mark off each set blending components (see Note 5), the above results
of measurements and the distances measured at the tan be corrected to a total Sample basis as follows:
end of the test with the analyzer section lying hori-
zontally on the bench top. If the boundaries have been
marked off with index Clips, record the measure-
ments. where

NOTE 10 Erroneous results tan be caused by Impfoper is the concentration of hydrocarbon type
packing of the gel or incomplete elution of hydrocarbons by [% (VW)] on a total Sample basis;
the alcohol. With precision bore columns, incomplete
elution tan be detected from the total length of the several c is the concentration hydrocarbon type
zones, which must be at least 500 mm for a satisfactory [% (VYV)] on an oxygenate-free basis;