Ip v IP 143JOl !

{I/$ ASTM 06560-00 psg BS 2000-143 : 2001

Determination of asphaltenes (heptane insolublesl) in

crude petroleum and petroleum products
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This standard does not purport to address all of the safety problerns 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.
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1 Scope products - Laboratory determination of density

or relative density - Hydrometer method.
This standard specifies a procedure for the (= IS0 3675)
determination of the heptane insoluble asphaltene
content of gas oil, diesel fuel, residual fuel oils, IP 365, Crude petroleum and liquid petroleum
lubricating oil, bitumen and crude petroleum products - Determination of den&y - QsciIJating
which has been topped to an oil temperature of U-tube method. (- IS0 12185)

260 “C (see A.2.1).

3 Diefinitions
The prelcision is applicable to values between
0,50 ?h(M//;n) and 30,O %(m/m). Values outside For the purposes of this standard, the following
this range may stlill be valid, but may not give the definitions apply:
same precision values.
31.
Oils containing additives may give erroneous asphaltenes
results. wax-free organic material insoluble in heptane,
but soluble in hot toluene.
2 Normative references
NOTE. 1 l-lot benzene appeared in the original definition
asphaltenes, but for health reasons, this material is no
The following normative documents contain
longer used. The precision of this method, when using
provisions which, through reference in this text, toluene, has been found to be the same as when using
constitute provisions of this standard. For dated benzene.
references, subsequent amendments to, or
revisions of, anty of these publications do not 3.2
apply. However, p#arties to agreements based on crude petroleum residue
this standard are encouraged to investigate the residue from distillation to an oil temperature of
possibility of applyiing the most recent editions of 260 “C carried out under the conditions of the
the normative documents indicated. For undated speciific plreparatory procedure described in annex A.
referelnces, the latest edition of the normative
document referenced applies.
4 Principle

IS0 3 170, PetroJeum liquids - Manual sampling.

A test portion of the sample is mixed with
heptane and the mixture heated under reflux, and
IS0 3171, Petroleum liquids - Automatic
the precipitated asphaltenes, waxy substances
pipeline samp,ling.
and inorganic material collected on a filter paper.
The waxy substances are removed by washing
IP 123, Petroleum products - Determination of
with hot heptane in an extractor.
dis tilla tiion characteristics at atmospheric
pressure. (E IS0 3405)
After removal of the waxy substances, the
asphaltenes are separated from t,he inorga~nic
IP 160, Crude petroleum and liquid petroleum
material by dissolution in hot toluene, the

143.1
 ASPHALTENES (HEPTANE INSOLUBLES), IPI

extraction solvent is evaporated,, the 6.2, Condenser

asphaltenes weighed.
With a coil or double surface,, fitted with a 34/45
5 Reagents and materials or 34/35 ground-glass joinit at the bottoim to fit
the top of the extractor. Minimum length 300 mm.
51. Methylbenzene (toluene) [C,H,CH,]
6.3 Reflux extractor
Analytical reagent grade, or nitration grade.
Conforming to the dimensions given in Fiigure 1.
5.2 Heptane [C,H, 6l Tolerances are k 1 mm on the height and OD of
the extractor body, and t 0,5 mm on all other
Analytical reagent grade. dimensions. The female ground-glass joint at the
top shall match the male ai: tlhe bottom1 of the
condenser, and the male ground-glass joint at the
6 Apparatus
bott:om shall match the female of the conical
flask.
61. General

6.4 Conical flasks

Ground-glass joints from different sources may
have one of two diameter to length ratios. For the
Of borosilicate glass of appropriate capacity (see
purposes off this standard , either is suitable, and
10.2 and Table I), with ground-glass joints to fit
for some applications, the diameter itself can be
the bottom of the extractor.
one of two. However, it is critical that the male
and female parts of each joint is from the same
NOTE 2 Sizes 24/39, 24/29, 2!3/43 or 29/32 are
series to avoid recession or protuberance.
suitalble.

-5-7 DIA
HOLE

Figure 1 - Extractor Figure 2 - Filter paper

143.2
 ASPHALTENES (HEPTANE INSOLUBLES), IP143

6.5 Stopper 6.16 Mlixer

Of borosilicate glass of a size to fit the conical High-speeid, non-aerating.

flask.
7 Sampling
6.6 Evaporating vessel
Unless otherwise specified, samples shall be
Of borosilicate glass. Either a hemispherical dish taken by the procedures described in IS0 3170 or
of 90 mm t 5 mm diameter, or another suitable is0 3171 .
vessel used in conjunction with a rotovapor.
8 Test Portion Preparation
NOTE 3 A rotovapor in conjunction with a nitrogen
atmosphere reduces the hazard of toluene evaporation
81. Test portions from the laboratory samples
(see 10.7)L
shall be drawn after thorough mixing and
subdivision. Heat viscous samples of residual
6.7 Filter funinel
fuels to a temperature which renders the sample
liquid, but not above 80 “C, anid Ihomogenize
Of borosilicate glass, 100 mm t 5 mm diameter.
using the mixer (6.16) as necessary.

6.8 Filter papers

8.2 Heat samples of penetration grade
bitumens to a temperature not exceeding 120 “C,
Whatman grade 42, 110 mm or 125 mm
and stir well before taking an aliquot.
diameter.

8.3 Samples of hard bitumens shall be ground

6.9 Analytical balance to a powder before an aliquot is takern.

Capable of weighing with an accuracy of 0,l mg. 8.4 Samples of crude petroleum shall be
prepared in accordance with the procedure
6.10 Forceps descriibed in annex A, unless it is known that thie
crude petroleum contains negligible quantities of
Stainless steel, spade ended. material boiling below 80 “C.

6.1 I Timing device 9 Apparatus Preparation

Electronic or manual, accurate to 1 ,O s. 91 Clean all glass flasks (6.:3) and dishes
(6.6) by a means that matches the cleanliness
6.12 Oven obtained by the use of a strongly oxidizing agent
such as ammonium peroxydisulfate iin
Capable of maintaining a temperature of 100 OC concentrated sulfuric acid at approximately 8 g/I,
to 110 “C. or sulfuric: acid itself, soaking for at least 12 h,
followed Iby rinses in tap water, distilled water
6.13 Graduated cylinders and then acetone, using forceps only for handling.

50 ml and 100 mil capacity. 9.2 For routine analysis, use a propriletary
laboratory detergent to clean the glassware,
6.14 Stirring. rods followed by the rinses described in 10.1. When
the dletergent cleaning no longer matches the
Made of glass or polytetrafluorethylene (PTFE), cleanlliness required based on visual appearance,
150 mlm by 3 mm diameter. use a strong oxidizing agent.

6.15 Coolhg vessel 9.3 After rinsing, place the glassware in the
oven (6.12) for 30 min, and cool in the cooling
Consisting of either a desiccator without vessel (6.15) for 30 min before weighing.
desiccant, or another suitable tightly-stoppered
vessel.

143.3
 ASPHALTENES (HEPTANIE INSOLUBLES), IP”143

Table 1 - Test portion size, flask and heptane Volumes

Estimated asphaltene content Test portion sizer Heptane volume

% (m/m) cl ml
Less than 0.5 IO zt 2 300 ~fr60
0.5 to 2.0 8 t Zi! 240 + 60
Over 2.0 to 5.0 4tl 120 I!z 30
Over 5.0 to 10.0 2tl 60 t 15
Over 10.0 to 25.0 0.8 t 0.2 25 to 30
Over 25.0 0.5 + 0.2 25 + 1

10 Procedure extraction period of not less than 60 min, or until

a fe!w drops of heptane frorn the bottom of the
10.1 Estimate the asphaltene content of the extractor leave no residue on evaporation on a
sample, or residue obtained from the procedure in glasIs slide.
annex A, and weigh the quantity, to the nearest
1 mg for masses above 1 g, and to the nearest 10.6 Replace the flask by the one used initially,
0,l mg for masses of 1 g and below, indicated in and to which has been added 30 ml to 6;O ml of
Table 1 into a flask (6.4) of appropriate capacity,, toluene ( 7.1), and continue refluxing until all the
also shown in Table I. asphaltenes have been dissolved from the paper.

10.2 Add heptane (7.2) to the test portion 10.7 Transfer the contents of the flask to a
in the fllask at a ratio of 30 ml to each 1 g of clealn and dry (see clause 9,) evaporating vessel
sample iif the expected asphaltene content is (6X), weighed to the nearest: 0,2 mg by tare
below 25 %(m/m). For samples with an agaiinst a similar dish. Wash out the fla:sk with
expected asphaltene content of above successive small quantities of ,toluene to a total
25 %(Mm), a minimum heptane volume of 25 ml not exceeding 30 ml. Remove the toluene by
shall be used. Table 1 also gives these values. evaporation on a boiling water bath (see note 5),
or by evaporation in a rotovapor unider an
IO,.3 Boil the mixture under reflux for 60 min atmosphere of nitrogen
rf: 5 min. Remove the flask and contents at the
end of this period, cool, close with a stopper CAIJTION - Perform the evaporation in a fume
(6.5), and store in a dark cupboard for 90 min to cupboard.
150 min, calculated from the time of removal
f rolm ref Iux. 10.8 Dry the dish and contents in the oven
(6.12) for 30 min. Cool in the cooling vessel
IO,.4 Place the filter paper, folded as shown in (6.15) for 30 min to 60 min and re-weigh by tare
Figure 2 ~(SOas to prevent loss of asphaltenes by against the dish used previously for this purpose,
creeping), in the filter funnel using forceps,, and which has been subject,ed to the same
Thereafter, handle the filter paper only with heating and cooling procedure as was the dish
forceps. Without agitation, decant the liquid into containing asphaltenes.
the filter paper, and then transfer the residue in
the flask as completely as possible with NOTE 6 Asphaltenes are very susceptible to o:xidation,
and it is important. that the procedure specified in the
successive quantities of hot heptane, using the
final drying stage is adhered to exactly as regards to
stirring rod ( 6.14) as necessary. Give the flask a
temperature and time.
final rinse with hot heptane and pour the rinsings
through the filter. Set the flask aside, without
11 Calculation
washing, for use as specified in 11.6.

11.1 Calculate the asphaltene content, A, in %

10.5 Remove the filter paper and contents from
(m/,m), of petroleum products using the equation:
the funnel and place in the reflux extractor (6.3).
Usiing a flask different from that used initially,
A= 100 (M/G)
refllux with heptane (7.2) at a rate of 2 drops/s to
(1)
4 drops/s; from the end of the condenser for an
 ASPHALTENES (HEPTANE INSOLUBLES), IP143

where: 13.2 Repeatability, r

M is the mass of asphaltenes, in
grams; The difference between two successive test
G is the mass of test portion, in results obtained by the same operat,lor with the
grams. same apbparatus under constant operating
conditions on identical test material would, in the
11.2 Calculate the asphaltene content, C, in normal and correct operation of the test method,
%(m/xn), of crude petroleum prepared in the exceed the value below only in one case in
manner described in annex A, using the equation: twenty.

c = 100 (MRIGD) r := 0,l A

(2)
where A is the average result, in %(m/m).
where:
13.3 Reproducibility, R
M is the mass of asphaltenes, in
grams; The difference between two single and
R is the mass of the residue from independent results obtained by different
distillation, in grams; operaltors working in different laboratories on
G is the mass of the residue aliquot, nominally identical test material would, in the
in grams; normal and correct operation of the test method,
5 is the mass of crude petroleum exceed the value below only in one case in
sample distilled, in grams. twenty.

12 Expression of results R= 0,2 A

12.1 Report the heptane insoluble asphaltene wherle A is the average result, in ?~(m/‘lm).
content of valules less than I,00 % (m/m), to the
nearest 0,05 SJa(m/m), by IP 143. 13.4# Bias

12.2 Report the heptane insoluble Since heptane insoluble asphalten!es are defined
asphaltene content of values of I,0 % (m/m) by thlis procedure, no bias can be asisigned. The
and greater, to the nearest 0,l % (m/m), by term ‘asphaltenes’ may be associateld with other
IP 143. similar procedures using alkanes as precipitating
agents other than heptane. In genieral, light,er
13 Precision alkanes will give higher results, and heavier
alkanes will give lower results than1 heptane, but
13.1 General no consistent ratio can be assigned.

The precision values were determined in an 14 Test report

interlaboratory programme using benzene as
solvent in 1956. A second interlaboratory The test report shall contain at least the following
programme, using toluene as solvent, was carried infor~mation:
out in 1975 to confirm the precision. No data
from the 1956 evaluation programme can be a) a reference to this standard;
found.
b) all details necessary for complete
NOTE ‘7 A recent (1998) interlaboratory programme in identification of the product testedl;
France on four samples with asphaltene contents in the
range of 0,50 %(~-&m) to 22,0 %(m/m) resulted in cl the result of the test (see clause 12);
estimated precision values very similar to those given in
13.2 and 13.3,, except for the reproducibility at very any deviation, by agreemeint or otherwise,
d)
low levels [C ,T,O 9-6 (m/m)] which was significantly
from the procedure specified;
worse.

e) the date of the test.

143.5
 ASPHALTENES (HEP’TANE INSOLUBLES), IP143

Annex A,
(normative)

Preparation of crude petroleum residue by distillation

A.1 Scope A.3.3 Drying apparatus

A.1 .I This annex describes a procedure for the The drying apparatus shall conisist of one of the
preparation of a crude petroleum residue (topped following:
to an oil temperature of 260 “C) suitable for the
determination of asphaltene content (see 9.4). A3.3. I Centrifuge

A.2 Principle A.3.3.2 Filter apparatus, operating alt inicreased

pressure.
A Iweighed test portion of the crude petroleum
sample i:s distilled in specified glass apparatus A.3#.3.3 Steel container, capable of withstanding
under specified conditions of heat input and rate 1000 kPa pressure, and of lbeing heated to 200 “C.
of distillation The distillation is stopped at an oil
temperature of 260 “C and the mass of the A.3(.3.4 Cottrell-type electro:static separator
residue determined.
A.4 Sample Preparation
A.3 Apparatus
A.4,,1 If the crude petroleum c:ontains sufficient
water to cause difficulties in distillation (ex.cessive
A.3.1 Residue distillation apparatus
foaming), dry the sample by a method that avoids
the loss of volatile components. The methods
The apparatus shall conform to the requirements;
given in A.4.1.1 to A.4.1 .5 are suitable.
of IP 123, with the exception of the temperature
sensor.
A.4,,1 .I Separate the water by gravity or by
centrifuging in a closed container at the lowest
The temperature sensor shall be a liquid-in-glass
practicable temperature.
tlhermometer of total immersion type of total
length 300 m/m to 320 mm, with a temperature
A.4.J .2 Filter the sample at the lowest
range of -4 “C to 360 “C, and a maximum scale
practicable temperature and applied pressure,
error of 2 “C, or an alternative temperature
through anhydrous calcium chloride, sodium
meiasurement device or system of at least
sulfate, or other suitable drying agent, in a closed
equivalenit accuracy. A transparent bath,
vessel.
maintained at 15 “C zt 3 “C is mandatory for the
receiver.
A.4.1.3 Heat the sample int a closed steel
container (A.3.3) fitted with a temperature sensor
NOTE 8 A witable thermometer is an IP 4C.
and pressure sensor. Fill the container to
approximately 70 % capacity and heat it until the
A.3.2 Drying distillation apparatus
oil reaches a temperature Iof 200 “C, or until the
pressure reaches 700 kPa. Allow the container to
The apparatus shall conform to A.3.1 with the
cool to ambient temperature iand then decant the
exception of a 500 ml distillation flask instead of
oil from the separated water.
the flask specified, and the receiver is substituted
by a 200 ml1 separating funnel immersed in broken
ice.
 ASPHALTENES (HEPTANE INSOLUBLES), IP143

A.4. II .4 Constwct a Cottrell-type separator from NOTE 9 The position of the temperature sensor in the
a tall glass beaker with a brass gauze cylinder, holder may be pre-marked before addition of the test
lined with flannel that has been saturated with portion to the flask.
water, and then squeezed out to leave it damp,
fitted tightly inside. A brass gauze cylinder A.5.3 Swab out the condenser tub/e iand
mounted on the glass spindle of a laboratory assemble the apparatus, with the vapour tube of
stirrer rotated at approximately 30 rev/min forms the flask extending into the condlenser tube a
the central electrode. Pour the sample into the distance of between 25 mm and 50 mm. Make
beaker and apply a voltage to the electrodes. the connection between flask and condenser tight
Interrupt the water precipitation at intervals to by means of a stopper or bung through which the
prevent the loss of volatile components and allow vapour tube passes.
the oil to cool. Separate the oil from the water
that has coalesced and run down the flannel A.5.4 Place a clean dry receiver at the outlet of
lining. the conldenser such that the condlenser tube or
adaptor extends into it at least .25 mm, lbut not
A.4.1.5 Distil off the water with the more volatile below the 100 ml mark. Immerse the receiver up
hydrocarbons in the apparatus described in A.3.2. to the 100 ml mark in the transparent biath
Charge the flask with 300 ml of sample and place (A.3.1). Cover the top of the receiver closely
the temperature sensor such that the sensing durilng the distillation with a piece of paper
point (bulb) is immersed in the sample. Heat the weighted to restrict volatile losses, and also to
flask gently so that the oil temperature rises overcome the buoyancy of the receiver in the
slowlly to ‘l5Q “C, vaporizing into the condenser water bath. Circulate ice-cold (below 4 “C) water
by means off a small gas flame, any drops of through the condenser.
water that collect on the walls of the flask. Stop
the distillation when no more water passes over A.5.5 Apply heat to the flask and distil the
in the distillatle. Allow the residue to cool, run off crude petroleum at a rate not exceeding
the water colllected in the separating funnel, and 23 mllmin until it ceases to foami, after which
add t,he oily distilllate back to the residue and mix keep the rate of distillation constant at 2,0 ml/min
thoroughly. If visible water is still present, filter to 3 5 ml/min (approximately 1 drop/s). Continue
by the method described in A.4.1.2. the-bist:illation without interruption to 260 “C.
Remove the heat and allow thie condenser to
drailn into the receiver.
A. 5 Procedure

A.56 Allow the residue in the ,flask to cool,

A.5.l Determine the density at 15 “C of the
remove the temperature sensor, and weigh the
crude petroleum by IP 160 or IP 365.
flas’k and residue. Record the mass of the residue
( R)’.
A.52 Weigh the distillation flask to the nearest
0,l lg and charge it with a mass equivalent to
AS.7 Use this residue to carry out the
100 ml of sample at 15 “C to within 0,l g,
proIcedwe (see clause 1 I) for the determination of
ensuring that no oil flows down the vapour tube
asphaltene content.
during this operation. Record the mass of oil (D).
Place the liquid-in-glass thermometer so that the
bottom of the bulb is 2,0 mm t 0,5 mm from
the bottom of the flask, or the alternative
temperature seinsor to a position established to
give dentical temperature readings