Asfaltenos IP143

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Ip v IP 143JOl {I/$ ASTM 06560-00 psg BS 2000-143 : 2001

Determination of asphaltenes (heptane insolublesl) incrude petroleum and petroleum products.___-_- -- _~--------- ------- ----- --

This standard does not purport to address all of the safety problerns associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability

of regulatory limitations prior to use.- --.

1 Scope

This standard specifies a procedure for the

determination of the heptane insoluble asphaltene

content of gas oil, diesel fuel, residual fuel oils,

lubricating oil, bitumen and crude petroleumwhich has been topped to an oil temperature of

260 “C (see A.2.1).

The prelcision is applicable to values between

0,50 ?h(M//;n) and 30,O %(m/m). Values outside

this range may stlill be valid, but may not give the

same precision values.

Oils containing additives may give erroneous

results.

2 Normative references

The following normative documents contain

provisions which, through reference in this text,

constitute provisions of this standard. For dated

references, subsequent amendments to, or

revisions of, anty of these publications do not

apply. However, p#arties to agreements based on

this standard are encouraged to investigate the

possibility of applyiing the most recent editions of

the normative documents indicated. For undated

referelnces, the latest edition of the normative

document referenced applies.

IS0 3 170, PetroJeum l iquids - Manual sampling.

IS0 3171, Petroleum l iquids - Autom atic

pipel ine samp, l ing.

IP 123, Petroleum products - Determinat ion of

dis illa iion character is t ics a t a tmospher ic

pressure. (E IS0 3405)

IP 160, Crude petroleum and l iquid petroleum

products - Laboratory determinat ion of densi ty

or re la t ive densi ty - Hydrometer method.

(= IS0 3675)

IP 365, Crude petroleum and l iquid petroleum

products - Determinat ion of den&y - QsciIJat ingU-tube meth od. (- IS0 12185)

3 Diefinitions

For the purposes of this standard, the following

definitions apply:

31asphalteneswax-free organic material insoluble in heptane,

but soluble in hot toluene.

NOTE. 1 l-lot benzene appeared in the original definitionasphaltenes, but for health reasons, this material is nolonger used. The precision of this method, when usingtoluene, has been found to be the same as when usingbenzene.

3.2crude petroleum residueresidue from distillation to an oil temperature of

260 “C carried out under the conditions of thespeciific plreparatory procedure described in annex A.

4Principle

A test portion of the sample is mixed with

heptane and the mixture heated under reflux, and

the precipitated asphaltenes, waxy substances

and inorganic material collected on a filter paper.The waxy substances are removed by washing

with hot heptane in an extractor.

After removal of the waxy substances, the

asphaltenes are separated from t,he inorga~nic

material by dissolution in hot toluene, the

143.1



ASPHALTENES (HEPTANE INSOLUBLES), IPI

extraction

asphaltenes

solvent

weighed.

is evaporated,, the

5 Reagents and materials

51 Methylbenzene (toluene) [C,H,CH,]

Analytical reagent grade, or nitration grade.

5.2 Heptane [C,H, 6l

Analytical reagent grade.

6 Apparatus

61 General

Ground-glass joints from different sources may

have one of two diameter to length ratios. For the

purposes off this standard , either is suitable, andfor some applications, the diameter itself can be

one of two. However, it is critical that the male

and female parts of each joint is from the same

series to avoid recession or protuberance.

-5-7 DIAHOLE

6.2, Condenser

With a coil or double surface,, fitted with a 34/45

or 34/35 ground-glass joinit at the bottoim to fit

the top of the extractor. Minimum length 300 mm.

6.3 Reflux extractor

Conforming to the dimensions given in Fiigure 1.

Tolerances are k 1 mm on the height and OD of

the extractor body, and t 0,5 mm on all other

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

bott:om shall match the female of the conical

flask.

6.4 Conical flasks

Of borosilicate glass of appropriate capacity (see

10.2 and Table I), with ground-glass joints to fit

the bottom of the extractor.

NOTE 2 Sizes 24/39, 24/29, 2 3/43 or 29/32 aresuitalble.

Figure 1 - Extractor Figure 2 - Filter paper

143.2



ASPHALTENES (HEPTANE INSOLUBLES), IP143

6.5 Stopper

Of borosilicate glass of a size to fit the conicalflask.

6.16 Mlixer

High-speeid, non-aerating.

6.6 Evaporating vessel

Of borosilicate glass. Either a hemispherical dish

of 90 mm t 5 mm diameter, or another suitable

vessel used in conjunction with a rotovapor.

NOTE 3 A rotovapor in conjunction with a nitrogenatmosphere reduces the hazard of toluene evaporation(see 10.7)L

6.7 Filter funinel

Of borosilicate glass, 100 mm t 5 mm diameter.

7 Sampling

Unless otherwise specified, samples shall be

taken by the procedures described in IS0 3170 oris0 3171 .

8 Test Portion Preparation

81 Test portions from the laboratory samples

shall be drawn after thorough mixing and

subdivision. Heat viscous samples of residual

fuels to a temperature which renders the sample

liquid, but not above 80 “C, anid Ihomogenize

using the mixer (6.16) as necessary.

6.8 Filter papers

Whatman grade 42, 110 mm or 125 mm

diameter.

8.2 Heat samples of penetration gradebitumens to a temperature not exceeding 120 “C,

and stir well before taking an aliquot.

6.9 Analytical balance

Capable of weighing with an accuracy of 0,l mg.

8.3 Samples of hard bitumens shall be ground

to a powder before an aliquot is takern.

6.10 Forceps

Stainless steel, spade ended.

8.4 Samples of crude petroleum shall be

prepared in accordance with the procedure

descriibed in annex A, unless it is known that thiecrude petroleum contains negligible quantities of

material boiling below 80 “C.

6.1 I Timing device 9

Electronic or manual, accurate to 1 ,O s.

6.12 Oven

Capable of maintaining a temperature of 100 OC

to 110 “C.

6.13 Graduated cylinders

91 Clean all glass flasks (6.:3) and dishes

(6.6) by a means that matches the cleanliness

obtained by the use of a strongly oxidizing agent

such as ammonium peroxydisulfate iin

concentrated sulfuric acid at approximately 8 g/I,

or sulfuric: acid itself, soaking for at least 12 h,

followed Iby rinses in tap water, distilled water

and then acetone, using forceps only for handling.

50 ml and 100 mil capacity.

6.14 Stirring rods

Made of glass or polytetrafluorethylene (PTFE),

150 mlm by 3 mm diameter.

9.2 For routine analysis, use a propriletary

laboratory detergent to clean the glassware,followed by the rinses described in 10.1. When

the dletergent cleaning no longer matches the

cleanlliness required based on visual appearance,

use a strong oxidizing agent.

6.15 Coolhg vessel

Consisting of either a desiccator without

desiccant, or another suitable tightly-stoppered

vessel.

9.3 After rinsing, place the glassware in the

oven (6.12) for 30 min, and cool in the cooling

vessel (6.15) for 30 min before weighing.

Apparatus Preparation

143.3



ASPHALTENES (HEPTANIE INSOLUBLES), IP”143

Table 1 - Test portion size, flask and heptane Volumes

Estimated asphaltene content

m/m)

Less than 0.5

0.5 to 2.0

Over 2.0 to 5.0

Over 5.0 to 10.0

Over 10.0 to 25.0

Over 25.0

Test portion sizer

c l

IO zt 2

8 t Zi

4tl

2tl

0.8 t 0.2

0.5 + 0.2

Heptane volume

ml

300 ~fr 60

240 + 60

120 I z 30

60 t 15

25 to 30

25 + 1

10 Procedure

10.1 Estimate the asphaltene content of the

sample, or residue obtained from the procedure inannex A, and weigh the quantity, to the nearest

1 mg for masses above 1 g, and to the nearest

0,l mg for masses of 1 g and below, indicated in

Table 1 into a flask (6.4) of appropriate capacity,,

also shown in Table I.

10.2 Add heptane (7.2) to the test portion

in the fllask at a ratio of 30 ml to each 1 g of

sample iif the expected asphaltene content is

below 25 %(m/m). For samples with anexpected asphaltene content of above25 %(Mm), a minimum heptane volume of 25 ml

shall be used. Table 1 also gives these values.

IO,.3 Boil the mixture under reflux for 60 min

rf: 5 min. Remove the flask and contents at theend of this period, cool, close with a stopper

(6.5), and store in a dark cupboard for 90 min to

150 min, calculated from the time of removal

f rolm ref Iux.

IO,.4 Place the filter paper, folded as shown in

Figure 2 ~(SO s to prevent loss of asphaltenes by

creeping), in the filter funnel using forceps, ,

Thereafter, handle the filter paper only with

forceps. Without agitation, decant the liquid into

the filter paper, and then transfer the residue in

the flask as completely as possible with

successive quantities of hot heptane, using the

stirring rod ( 6.14) as necessary. Give the flask a

final rinse with hot heptane and pour the rinsings

through the filter. Set the flask aside, withoutwashing, for use as specified in 11.6.

10.5 Remove the filter paper and contents from

the funnel and place in the reflux extractor (6.3).

Usiing a flask different from that used initially,

refllux with heptane (7.2) at a rate of 2 drops/s to

4 drops/s; from the end of the condenser for an

extraction period of not less than 60 min, or until

a fe w drops of heptane frorn the bottom of the

extractor leave no residue on evaporation on a

glasIs slide.

10.6 Replace the flask by the one used initially,

and to which has been added 30 ml to 6;O ml of

toluene ( 7.1), and continue refluxing until all theasphaltenes have been dissolved from the paper.

10.7 Transfer the contents of the flask to a

clealn and dry (see clause 9,) evaporating vessel

(6X), weighed to the nearest: 0,2 mg by tareagaiinst a similar dish. Wash out the fla:sk with

successive small quantities of ,toluene to a total

not exceeding 30 ml. Remove the toluene by

evaporation on a boiling water bath (see note 5),

or by evaporation in a rotovapor unider an

atmosphere of nitrogen

CAIJTION - Perform the evaporation in a fumecupboard.

10.8 Dry the dish and contents in the oven

(6.12) for 30 min. Cool in the cooling vessel

(6.15) for 30 min to 60 min and re-weigh by tare

against the dish used previously for this purpose,

and which has been subject,ed to the same

heating and cooling procedure as was the dish

containing asphaltenes.

NOTE 6 Asphaltenes are very susceptible to o:xidation,

and it is important. that the procedure specified in thefinal drying stage is adhered to exactly as regards totemperature and time.

11 Calculation

11.1 Calculate the asphaltene content, A, in %

(m/,m), of petroleum products using the equation:

A = 100 (M/G)

(1)




where:

M is the mass of asphaltenes, ingrams;

G is the mass of test portion, ingrams.

11.2 Calculate the asphaltene content, C, in

%(m/xn), of crude petroleum prepared in themanner described in annex A, using the equation:

c = 100 (MRIGD)

(2)

where:

M

R

G

5

is the mass of asphaltenes, ingrams;

is the mass of the residue fromdistillation, in grams;

is the mass of the residue aliquot,

in grams;

is the mass of crude petroleum

sample distil led, in grams.

12 Expression of results

12.1 Report the heptane insoluble asphaltene

content of valules less than I,00 % (m/m), to the

nearest 0,05 SJa m/m), by IP 143.

12.2 Report the heptane insoluble

asphaltene content of values of I,0 % (m/m)

and greater, to the nearest 0,l % (m/m), byIP 143.

13 Precision

13.1 General

The precision values were determined in an

interlaboratory programme using benzene as

solvent in 1956. A se ond interlaboratory

programme, using toluene as solvent, was carried

out in 1975 to confirm the precision. No data

from the 1956 evaluation programme can befound.

NOTE ‘7 A recent (1998) interlaboratory programme inFrance on four samples with asphaltene contents in therange of 0,50 %(~-&m) to 22,0 %(m/m) resulted inestimated precision values very similar to those given in13.2 and 13.3,, except for the reproducibility at verylow levels [C ,T,O 9-6 (m/m)] which was significantlyworse.

13.2 Repeatability, r

The difference between two successive test

results obtained by the same operat,lor with thesame apbparatus under constant operating

conditions on identical test material would, in the

normal and correct operation of the test method,

exceed the value below only in one case intwenty.

r := 0,l A

where A is the average result, in %(m/m).

13.3 Reproducibility,

The difference between two single and

independent results obtained by different

operaltors working in different laboratories on

nominally identical test material would, in the

normal and correct operation of the test method,

exceed the value below only in one case in

twenty.

R= 0,2 A

wherle A is the average result, in ?~(m/‘lm).

13.4# Bias

Since heptane insoluble asphalten es are defined

by thlis procedure, no bias can be asisigned. The

term ‘asphaltenes’ may be associateld with othersimilar procedures using alkanes as precipitating

agents other than heptane. In genieral, light,er

alkanes will give higher results, and heavier

alkanes will give lower results than1 heptane, but

no consistent ratio can be assigned.

14 Test report

The test report shall contain at least the following

infor~mation:

a)

b)

a reference to this standard;

all details necessary for complete

identification of the product testedl;

cl

d)

the result of the test (see clause 12);

any deviation, by agreemeint or otherwise,

from the procedure specified;

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.1 .I This annex describes a procedure for the

preparation of a crude petroleum residue (toppedto an oil temperature of 260 “C) suitable for the

determination of asphaltene content (see 9.4).

A.2 Principle

A Iweighed test portion of the crude petroleum

sample i:s distilled in specified glass apparatus

under specified conditions of heat input and rateof distillation The distillation is stopped at an oil

temperature of 260 “C and the mass of theresidue determined.

A.3 Apparatus

A.3.1 Residue distillation apparatus

The apparatus shall conform to the requirements;

of IP 123, with the exception of the temperature

sensor.

The temperature sensor shall be a liquid-in-glass

tlhermometer of total immersion type of total

length 300 m/m to 320 mm, with a temperature

range of -4 “C to 360 “C, and a maximum scale

error of 2 “C, or an alternative temperature

meiasurement device or system of at least

equivalenit accuracy. A transparent bath,

maintained at 15 “C zt 3 “C is mandatory for the

receiver.

NOTE 8 A witable thermometer is an IP 4C.

A.3.2 Drying distillation apparatus

The apparatus shall conform to A.3.1 with theexception of a 500 ml distillation flask instead of

the flask specified, and the receiver is substituted

by a 200 ml1 separating funnel immersed in broken

ice.

A.3.3 Drying apparatus

The drying apparatus shall conisist of one of thefollowing:

A3.3. I Centrifuge

A.3.3.2 Filter apparatus, operating alt inicreasedpressure.

A.3#.3.3 Steel container, capable of withstanding

1000 kPa pressure, and of lbeing heated to 200 “C.

A.3(.3.4 Cottrell-type electro:static separator

A.4 Sample Preparation

A.4,,1 If the crude petroleum c:ontains sufficient

water to cause difficulties in distillation (ex.cessive

foaming), dry the sample by a method that avoids

the loss of volatile components. The methods

given in A.4.1.1 to A.4.1 .5 are suitable.

A.4,,1 .I Separate the water by gravity or bycentrifuging in a closed container at the lowestpracticable temperature.

A.4.J .2 Filter the sample at the lowestpracticable temperature and applied pressure,

through anhydrous calcium chloride, sodium

sulfate, or other suitable drying agent, in a closed

vessel.

A.4.1.3 Heat the sample int a closed steel

container (A.3.3) fitted with a temperature sensor

and pressure sensor. Fill the container to

approximately 70 % capacity and heat it until theoil reaches a temperature Iof 200 “C, or until the

pressure reaches 700 kPa. Allow the container to

cool to ambient temperature iand then decant the

oil from the separated water.




A.4. II .4 Constwct a Cottrell-type separator from

a tall glass beaker with a brass gauze cylinder,lined with flannel that has been saturated with

water, and then squeezed out to leave it damp,

fitted tightly inside. A brass gauze cylindermounted on the glass spindle of a laboratory

stirrer rotated at approximately 30 rev/min forms

the central electrode. Pour the sample into thebeaker and apply a voltage to the electrodes.

Interrupt the water precipitation at intervals to

prevent the loss of volatile components and allow

the oil to cool. Separate the oil from the water

that has coalesced and run down the flannel

lining.

A.4.1.5 Distil off the water with the more volatile

hydrocarbons in the apparatus described in A.3.2.

Charge the flask with 300 ml of sample and place

the temperature sensor such that the sensing

point (bulb) is immersed in the sample. Heat the

flask gently so that the oil temperature rises

slowlly to ‘l5Q “C, vaporizing into the condenser

by means off a small gas flame, any drops of

water that collect on the walls of the flask. Stop

the distillation when no more water passes over

in the distillatle. Allow the residue to cool, run off

the water colllected in the separating funnel, and

add t,he oily distilllate back to the residue and mix

thoroughly. If visible water is still present, filter

by the method described in A.4.1.2.

A. 5 Procedure

A.5.l Determine the density at 15 “C of the

crude petroleum by IP 160 or IP 365.

A 52 Weigh the distillation flask to the nearest

0,l lg and charge it with a mass equivalent to

100 ml of sample at 15 “C to within 0,l g,

ensuring that no oil flows down the vapour tube

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 alternativetemperature seinsor to a position established to

give dentical temperature readings

NOTE 9 The position of the temperature sensor in theholder may be pre-marked before addition of the testportion to the flask.

A.5.3 Swab out the condenser tub/e iandassemble the apparatus, with the vapour tube of

the flask extending into the condlenser tube a

distance of between 25 mm and 50 mm. Makethe connection between flask and condenser tight

by means of a stopper or bung through which the

vapour tube passes.

A.5.4 Place a clean dry receiver at the outlet ofthe conldenser such that the condlenser tube or

adaptor extends into it at least .25 mm, lbut not

below the 100 ml mark. Immerse the receiver up

to the 100 ml mark in the transparent biath

(A.3.1). Cover the top of the receiver closely

durilng the distillation with a piece of paper

weighted to restrict volatile losses, and also to

overcome the buoyancy of the receiver in thewater bath. Circulate ice-cold (below 4 “C) water

through the condenser.

A.5.5 Apply heat to the flask and distil the

crude petroleum at a rate not exceeding23 mllmin until it ceases to foami, after which

keep the rate of distillation constant at 2,0 ml/min

to 3 5 ml/min (approximately 1 drop/s). Continue

the-bist:illation without interruption to 260 “C.

Remove the heat and allow thie condenser to

drailn into the receiver.

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

remove the temperature sensor, and weigh the

flas’k and residue. Record the mass of the residue

( R)’

AS.7 Use this residue to carry out the

proIcedwe (see clause 1 I) for the determination of

asphaltene content.

Asfaltenos IP143

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