D 6560 - 00 - Rdy1nja
D 6560 - 00 - Rdy1nja
D 6560 - 00 - Rdy1nja
Designation: D 6560 – 00
Designation: IP 143/01
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D 6560 – 00
6. Apparatus TABLE 1 Test Portion Size, Flask, and Heptane Volumes
6.1 General—Ground-glass joints from different sources Estimated Asphaltene Test Portion Heptane Volume
Content Size Flask Volume
may have one of two diameter to length ratios. For the % m/m g mL mL
purposes of this test method, either is suitable, and for some Less than 0.5 10 6 2 1000 300 6 60
applications, the diameter itself can be one of two . However, 0.5 to 2.0 862 500 240 6 60
it is critical that the male and female parts of each joint are Over 2.0 to 5.0 461 250 120 6 30
Over 5.0 to 10.0 261 150 60 6 15
from the same series to avoid recession or protuberance. Over 10.0 to 25.0 0.8 6 0.2 100 25 to 30
6.2 Condenser, with a coil or double surface, fitted with a Over 25.0 0.5 6 0.2 100 25 6 1
34/45 or 34/35 ground-glass joint at the bottom to fit the top of
the extractor. Minimum length is 300 mm.
6.3 Reflux Extractor, conforming to the dimensions given in 6.8 Filter Papers, Whatman6 Grade 42, 110 or 125-mm
Fig. 1. Tolerances are 6 1 mm on the height and outer diameter diameter.
(OD) of the extractor body and 6 0.5 mm on all other 6.9 Analytical Balance, capable of weighing with an accu-
dimensions. The female ground-glass joint at the top shall racy of 0.1 mg.
match the male at the bottom of the condenser, and the male 6.10 Forceps, of stainless steel, spade ended.
ground-glass joint at the bottom shall match the female of the 6.11 Timing Device, electronic or manual, accurate to 1.0 s.
conical flask. 6.12 Oven, capable of maintaining a temperature from 100
6.4 Conical Flasks, of borosilicate glass of appropriate to 110°C.
capacity (see 11.2 and Table 1), with ground-glass joints to fit 6.13 Graduated Cylinders, of 50 and 100 mL capacity.
the bottom of the extractor. 6.14 Stirring Rods, of glass or polytetrafluoroethylene
NOTE 2—Sizes 24/39, 24/29, 29/43 or 29/32 are suitable.
(PTFE), 150 by 3-mm diameter.
6.15 Cooling Vessel, consisting of either a dessicator with-
6.5 Stopper, of borosilicate glass of a size to fit the conical out desiccant, or another suitable tightly-stoppered vessel.
flask. 6.16 Mixer, high-speed, nonaerating.
6.6 Evaporating Vessel, of borosilicate glass. Either a hemi-
spherical dish of approximately 90 mm diameter, or another 7. Reagents
suitable vessel used in conjunction with a rotovapor. 7.1 Toluene (methylbenzene) [C6H5CH3], analytical reagent
NOTE 3—A rotovapor in conjunction with a nitrogen atmosphere or nitration grade.
reduces the hazard of toluene evaporation (see 11.7). 7.2 Heptane [C7H16], analytical reagent grade.
6.7 Filter Funnel, of borosilicate glass, approximately 100 8. Sampling
mm diameter.
8.1 Unless otherwise specified, take samples by the proce-
dures described in Practice D 4057 or D 4177.
9. Test Portion Preparation
9.1 Test portions from the laboratory samples shall be
drawn after thorough mixing and subdivision. Heat viscous
samples of residual fuels to a temperature that renders the
sample liquid, but not above 80°C, and homogenize, using the
mixer (see 6.16) as necessary.
9.2 Heat samples of penetration grade bitumens to a tem-
perature not exceeding 120°C, and stir well before taking an
aliquot.
9.3 Samples of hard bitumens shall be ground to a powder
before an aliquot is taken.
9.4 Samples of crude petroleum shall be prepared in accor-
dance with the procedure described in the Annex A1, unless it
is known that the crude petroleum contains negligible quanti-
ties of material boiling below 80°C.
10. Apparatus Preparation
10.1 Clean all glass flasks (see 6.4) and dishes (see 6.6) by
a means that matches the cleanliness obtained by the use of a
strongly oxidizing agent, such as chromosulfuric acid, ammo-
nium peroxydisulfate in concentrated sulfuric acid at approxi-
mately 8 g/L, or sulfuric acid itself, soaking for at least 12 h,
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FIG. 1 Extractor Available from Whatman Int. Ltd., Maidstone, UK.
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D 6560 – 00
followed by rinses in tap water, distilled water, and then paper, and then transfer the the residue in the flask as
acetone, using forceps only for handling. (Warning— completely as possible with successive quantities of hot
Chromosulfuric acid is a health hazard. It is toxic, a recognized heptane, using the using the stirring rod (see 6.14) as necessary.
carcinogen as it contains Cr (VI) compounds, which are highly Give the flask a final rinse with hot heptane, and pour the
corrosive and potentially hazardous in contact with organic rinsings through the filter. Set the flask aside, without washing,
materials. When using chromosulfuric acid cleaning solution, for use as specified in 11.6.
eye protection and protective clothing are essential. Never 11.5 Remove the filter paper and contents from the funnel,
pipette the cleaning solution by mouth. After use, do not pour and place in the reflux extractor (see 6.3). Using a flask
cleaning solution down the drain, but neutralize it with great different from that used initially, reflux with heptane (see 7.2)
care, owing to the concentrated sulfuric acid present, and at a rate of 2 drops/s to 4 drops/s from the end of the condenser
dispose of it in accordance with standard procedures for toxic for an extraction period of not less than 60 min, or until a few
laboratory waste (chromium is highly dangerous to the envi- drops of heptane from the bottom of the extractor leave no
ronment). Nonchromium containing, strongly oxidizing acid residue on evaporation on a glass slide.
cleaning solutions are also highly corrosive and potentially 11.6 Replace the flask by the one used initially, and to which
hazardous in contact with organic materials, but do not contain has been added 30 to 60 mL of toluene (see 7.1), and continue
chromium, which has its own special disposal problems. refluxing until all the asphaltenes have been dissolved from the
10.2 For routine analysis, use a proprietary laboratory paper.
detergent to clean the glassware, followed by the rinses 11.7 Transfer the contents of the flask to a clean and dry (see
described in 10.1. When the detergent cleaning no longer Section 10) evaporating vessel (see 6.6), weighed to the nearest
matches the cleanliness required based on visual appearance, 0.2 mg by tare against a similar dish. Wash out the flask with
use a strong oxidizing agent. successive small quantities of toluene to a total not exceeding
10.3 After rinsing, place the glassware in the oven (see 30 mL. Remove the toluene by evaporation on a boiling water
6.12) for 30 min, and cool in the cooling vessel (see 6.15) for bath (Warning—Perform the evaporation in a fume hood.), or
30 min before weighing. by evaporation in a rotovapor under an atmosphere of nitrogen.
11.8 Dry the dish and contents in the oven (see 6.12) at 100
11. Procedure to 110°C for 30 min. Cool in the cooling vessel (see 6.15) for
11.1 Estimate the asphaltene content of the sample, or 30 to 60 min and reweigh by tare against the dish used
residue obtained from the procedure in the Annex A1, and previously for this purpose, and which has been subjected to
weigh the quantity, to the nearest 1 mg for masses above 1 g the same heating and cooling procedure as was the dish
and to the nearest 0.1 mg for masses of 1 g and below (see containing asphaltenes.
Table 1), into a flask (see 6.4) of appropriate capacity (see NOTE 4—Asphaltenes are very susceptible to oxidation, and it is
Table 1). important that the procedure specified in the final drying stage is adhered
11.2 Add heptane (see 7.2) to the test portion in the flask at to exactly as regards to temperature and time 6 1 min.
a ratio of 30 mL to each 1 g of sample if the expected
asphaltene content is below 25 % m/m. For samples with an 12. Calculation
expected asphaltene content of above 25 % m/m, a minimum 12.1 Calculate the asphaltene content, A, in % m/m, of
heptane volume of 25 mL shall be used (see Table 1). petroleum products as follows:
11.3 Boil the mixture under reflux for 60 6 5 min. Remove A 5 100 ~M/G! (1)
the flask and contents at the end of this period, cool, close with
a stopper (see 6.5), and store in a dark cupboard for 90 to 150 where:
min, calculated from the time of removal from reflux. M = is the mass of asphaltenes, in grams, and
11.4 Place the filter paper, folded as shown in Fig. 2 (so as G = is the mass of test portion, in grams.
to prevent loss of asphaltenes by creeping), in the filter funnel, 12.2 Calculate the asphaltene content, C, in % m/m, of
using forceps. Thereafter, handle the filter paper only with crude petroleum prepared in the manner described in the
forceps. Without agitation, decant the liquid into the filter Annex, as follows:
C 5 100 ~MR/GD! (2)
where:
M = is the mass of asphaltenes, in grams,
R = is the mass of the residue from distillation, in grams,
G = is the mass of the residue aliquot, in grams, and
D = is the mass of crude petroleum sample distilled, in
grams.
13. Report
13.1 Report the following information:
13.1.1 The heptane insoluble asphaltene content of values
less than 1.00 % m/m, to the nearest 0.05 % m/m, by Test
FIG. 2 Filter Paper Method D 6560.
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D 6560 – 00
13.1.2 The heptane insoluble asphaltene content of values where A is the average result, in % m/m.
of 1.0 % m/m and greater, to the nearest 0.1 % m/m, by Test 14.3 Reproducibility—The difference between two single
Method D 6560. and independent results obtained by different operators work-
ing in different laboratories on nominally identical test material
14. Precision and Bias
would, in the normal and correct operation of the test method,
14.1 Precision—The precision values were determined in exceed the value below in only one case in twenty.
an interlaboratory program, using benzene as solvent, in 1956.
R 5 0.2 A (4)
A second interlaboratory program, using toluene as solvent,
was carried out in 1975 to confirm the precision. No data from where A is the average result, in % m/m.
the 1956 evaluation program can be found. 14.4 Bias—Since heptane insoluble asphaltenes are defined
NOTE 5—A recent (1998) interlaboratory program in France on four
by this test method, no bias can be assigned. The term
samples with asphaltene contents in the range from 0.50 to 22.0 % m/m asphaltenes may be associated with other similar procedures
resulted in estimated precision values very similar to those given in 14.2 using alkanes as precipitating agents other than heptane. In
and 14.3, except for the reproducibility at very low levels (<2.0 % m/m), general, lighter alkanes will give higher results and heavier
which was significantly worse. alkanes will give lower results than heptane, but no consistent
14.2 Repeatability—The difference between two successive ratio can be assigned.
test results obtained by the same operator with the same
apparatus under constant operating conditions on identical test 15. Keywords
material would, in the normal and correct operation of the test 15.1 asphaltenes; bitumen; crude petroleum; diesel fuel; gas
method, exceed the value below in only one case in twenty. oil; heptane insoluble residues; lubricating oil; residual fuel
r 5 0.1 A (3) oils
ANNEX
(Mandatory Information)
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D 6560 – 00
A1.5.1.3 Heat the sample in a closed steel container (see A1.6.2 Weigh the distillation flask to the nearest 0.1 g, and
A1.4.2.3) fitted with a temperature sensor and pressure sensor. charge it with a mass equivalent to 100 mL of sample at 15°C
Fill the container to approximately 70 % capacity, and heat it to within 0.1 g, ensuring that no oil flows down the vapor tube
until the oil reaches a temperature of 200°C, or until the during this operation. Record the mass of oil (D). Place the
pressure reaches 700 kPa. Allow the container to cool to liquid-in-glass thermometer so that the bottom of the bulb is
ambient temperature, and then decant the oil from the sepa- 2.0 6 0.5 mm from the bottom of the flask, or the alternative
rated water. temperature sensor to a position established to give identical
A1.5.1.4 Construct a Cottrell-type separator from a tall temperature readings.
glass beaker with a brass gauze cylinder, lined with flannel that NOTE A1.2—The position of the temperature sensor in the holder may
has been saturated with water, and then squeezed out to leave be premarked before addition of the test portion to the flask.
it damp, fitted tightly inside. A brass gauze cylinder mounted A1.6.3 Swab out the condenser tube, and assemble the
on the glass spindle of a laboratory stirrer, rotated at approxi- apparatus with the vapor tube of the flask extending into the
mately 30 rev/min, forms the central electrode. Pour the sample condenser tube a distance of between 25 and 50 mm. Make the
into the beaker, and apply a voltage to the electrodes. Interrupt connection between flask and condenser tight by means of a
the water precipitation at intervals to prevent the loss of stopper or bung through which the vapor tube passes.
volatile components, and allow the oil to cool. Separate the oil A1.6.4 Place a clean dry receiver at the outlet of the
from the water that has coalesced and run down the flannel condenser such that the condenser tube or adaptor extends into
lining. it at least 25 mm, but not below the 100-mL mark. Immerse the
A1.5.1.5 Distil off the water with the more volatile hydro- receiver up to the 100-mL mark in the transparent bath (see
carbons in the apparatus described in A1.4.1.2. Charge the flask A1.4.1.1). Cover the top of the receiver closely during the
with 300 mL of sample, and place the temperature sensor such distillation with a piece of paper weighted to restrict volatile
that the sensing point (bulb) is immersed in the sample. Heat losses and also to overcome the buoyancy of the receiver in the
the flask gently so that the oil temperature rises slowly to water bath. Circulate ice-cold (below 4°C) water through the
150°C, vaporizing into the condenser by means of a small gas condenser.
flame any drops of water that collect on the walls of the flask. A1.6.5 Apply heat to the flask, and distil the crude petro-
Stop the distillation when no more water passes over in the leum at a rate not exceeding 2.5 mL/min until it ceases to foam,
distillate. Allow the residue to cool, run off the water collected after which keep the rate of distillation constant at 2.0 to 2.5
mL/min (approximately 1 drop/s). Continue the distillation
in the separating funnel, and add the oily distillate back to the
without interruption to 260°C. Remove the heat, and allow the
residue and mix thoroughly. If visible water is still present,
condenser to drain into the receiver.
filter by the method described in A1.5.1.2.
A1.6.6 Allow the residue in the flask to cool, remove the
temperature sensor, and weigh the flask and residue. Record
A1.6 Procedure
the mass of the residue (R).
A1.6.1 Determine the density at 15°C of the crude petro- A1.6.7 Use this residue to carry out the procedure (see
leum by Test Method D 1298 or D 4052. Section 11) for the determination of asphaltene content.
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