D1319.PDF Aromaticos Turbosina
D1319.PDF Aromaticos Turbosina
D1319.PDF Aromaticos Turbosina
Designation: 156/97
This test method has been approved by the sponsoring committees and accepted by the cooperating societies in accordance with
established procedures.
This standard has been approved for use by agencies of the Department of Defense. This test method replaces Method 3703 of Federal
Test Method Standard No. 791b.
Copyright © ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
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D 1319
Gasoline by Gas Chromatography and Oxygen Selective length of an approximately 100-mm thread of mercury shall
Flame Ionization Detection5 not vary by more than 0.3 mm in any part of the analyzer
E 11 Specification for Wire-Cloth Sieves for Testing Pur- section. In glass-sealing the various sections to each other,
poses6 long-taper connections shall be made instead of shouldered
connections. Support the silica gel with a small piece of glass
3. Terminology wool located between the ball and socket of the 12/2 spherical
3.1 Definitions of Terms Specific to This Standard: joint and covering the analyzer outlet. The column tip attached
3.1.1 aromatics—the volume % of monocyclic and polycy- to the 12/2 socket shall have a 2-mm internal diameter. Clamp
clic aromatics, plus aromatic olefins, some dienes, compounds the ball and socket together and ensure that the tip does not
containing sulfur and nitrogen, or higher boiling oxygenated tend to slide from a position in a direct line with the analyzer
compounds (excluding those listed in 1.5). section during the packing and subsequent use of the column.
3.1.2 olefins—the volume % of alkenes, plus cycloalkenes, 7.1.2 For convenience, adsorption columns with standard
and some dienes. wall tubing, as shown on the left in Fig. 1, can be used. When
3.1.3 saturates—the volume % of alkanes, plus cycloal- using standard wall tubing for the analyzer section, it is
kanes. necessary to select tubing of uniform bore and to provide a
leakproof connection between the separator and the analyzer
4. Summary of Test Method sections. Calibrations of standard wall tubing would be im-
4.1 Approximately 0.75 mL of sample is introduced into a practical; however, any variations of 0.5 mm or greater, as
special glass adsorption column packed with activated silica measured by ordinary calipers, in the outside diameter along
gel. A small layer of the silica gel contains a mixture of the tube can be taken as an indication of irregularities in the
fluorescent dyes. When all the sample has been adsorbed on the inner diameter and such tubing should not be used. Draw out
gel, alcohol is added to desorb the sample down the column. one end of the tubing selected for the analyzer section to a fine
The hydrocarbons are separated in accordance with their capillary to retain the gel. Connect the other end of the analyzer
adsorption affinities into aromatics, olefins, and saturates. The section to the separator section with a 30-mm length of vinyl
fluorescent dyes are also separated selectively, with the hydro- tubing, making certain that the two glass sections touch. To
carbon types, and make the boundaries of the aromatic, olefin, ensure a leakproof glass-to-vinyl seal with the analyzer section,
and saturate zones visible under ultraviolet light. The volume it is necessary to heat the upper end of the analyzer section
percentage of each hydrocarbon type is calculated from the until it is just hot enough to melt the vinyl, then insert the upper
length of each zone in the column. end of the analyzer section into the vinyl sleeve. Alternatively,
this seal can be made by securing the vinyl sleeve to the
5. Significance and Use analyzer section by wrapping it tightly with soft wire.
5.1 The determination of the total volume % of saturates, 7.2 Zone-Measuring Device—The zones may be marked
olefins, and aromatics in petroleum fractions is important in with a glass-writing pencil and the distances measured with a
characterizing the quality of petroleum fractions as gasoline meter rule, with the analyzer section lying horizontally. Alter-
blending components and as feeds to catalytic reforming natively, the meter rule may be fastened adjacent to the
processes. This information is also important in characterizing column. In this case, it is convenient to have each rule fitted
petroleum fractions and products from catalytic reforming and with four movable metal index clips (Fig. 1) for marking zone
from thermal and catalytic cracking as blending components boundaries and measuring the length of each zone.
for motor and aviation fuels. This information is also important 7.3 Ultraviolet Light Source, with radiation predominantly
as a measure of the quality of fuels, such as specified in at 365 nm is required. A convenient arrangement consists of
Specification D 1655. one or two 915 or 1220-mm units mounted vertically along the
apparatus. Adjust to give the best fluorescence.
6. Interferences 7.4 Electric Vibrator, for vibrating individual columns or
6.1 Errors in the direction of high saturate values and low the frame supporting multiple columns.
aromatic and low olefin values can result if the sample 7.5 Hypodermic Syringe, 1 mL, graduated to 0.01 or 0.02
containing significant amounts of C5 and lighter hydrocarbons. mL, with needle 102 mm in length. Needles of No. 18, 20, or
Such samples are to be depentanized by Test Method D 2001. 22 gage are satisfactory.
7.6 Regulator, 2-stage, 0 to 103 kPa gage delivery range.
7. Apparatus
7.1 Adsorption Columns, with precision bore (“true bore” IP 8. Reagents and Materials
designation) tubing, as shown on the right in Fig. 1, made of 8.1 Silica Gel,7 manufactured to conform to the specifica-
glass and consisting of a charger section with a capillary neck, tions shown in Table 1. Determine the surface area of the gel
a separator section, and an analyzer section; or with standard by Test Method D 3663. Determine the pH of the silica gel as
wall tubing, as shown on the left in Fig. 1. follows: Calibrate a pH meter with standard pH 4 and pH 7
7.1.1 The inner diameter of the analyzer section for the buffer solutions. Place 5 g of the gel sample in a 250-mL
precision bore tubing shall be 1.60 to 1.65 mm. In addition the
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Available from W. R. Grace and Co., Davison Chemical Div., Baltimore, MD
6
Annual Book of ASTM Standards, Vol 14.02. 21203 by specifying Code 923.
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D 1319
FIG. 1 Adsorption Columns with Standard Wall (left) and Precision Bore (right) Tubing in Analyzer Section
TABLE 1 Silica Gel Specifications vessel at 175°C for 3 h. Transfer the dried gel to an air tight
2
Surface area, m /g 430 to 530 container while still hot, and protect it thereafter from atmo-
pH of 5 % water slurry 5.5 to 7.0 spheric moisture.
Loss on ignition at 955°C, mass-% 4.5 to 10.0
Iron as Fe2O3, dry basis, mass-ppm 50 max NOTE 2—Some batches of silica gel that otherwise meet specifications
Particle Size
have been found to produce olefin boundary fading. The exact reason for
Sieve NumberA µm Mass-%
this phenomenon is unknown but will affect accuracy and precision.
on 60 250 0.0 max
on 80 180 1.2 max 8.2 Fluorescent Indicator Dyed Gel— A standard dyed gel,8
on 100 150 5.0 max consisting of a mixture of recrystallized Petrol Red AB4 and
through 200 75 15.0 max
purified portions of the olefin and aromatic dyes obtained by
A
Detailed requirements for these sieves are given in Specification E 11, and chromatographic adsorption, following a definite, uniform
BS410: 1943.
beaker. Add 100 mL of water and a stirring bar. Stir the slurry 8
Available from UOP LLC, Finished Product Technologies Dept., 25 E.
on a magnetic stirrer for 20 min and then determine the pH Algonquin Rd., Des Plaines, IL 60017-5017, by requesting “FIA Standard Dyed
with the calibrated meter. Before use, dry the gel in a shallow Gel,” UOP LLC Product No. 80675.
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D 1319
procedure, and deposited on silica gel. The dyed gel shall be 12.3 Chill the sample and a hypodermic syringe to 2 to 4°C.
stored in a dark place under an atmosphere of nitrogen. When Draw 0.75 6 0.03 mL of sample into the syringe and inject the
stored under these conditions, the dyed gel can have a shelf life sample 30 mm below the surface of the gel in the charger
of at least five years. It is recommended that portions of the section.
dyed gel be transferred as required to a smaller working vial 12.4 Fill the charger section to the spherical joint with
from which the dyed gel is routinely taken for analyses. isopropyl alcohol. Connect the column to the gas manifold and
8.3 Isoamyl Alcohol, (3-methyl-1-butanol) 99 %. apply 14 kPa gas pressure for 2.5 min to move the liquid front
(Warning—Flammable. Health hazard.) down the column. Increase the pressure to 34 kPa gage for
8.4 Isopropyl Alcohol, (2-propanol) 99 %, conforming to another 2.5 min and then adjust the pressure required to give a
Specification D 770. (Warning—Flammable. Health hazard.) transit time of about 1 h. Usually a gas pressure of 28 to 69 kPa
8.5 Pressuring Gas—Air (or nitrogen) delivered to the top gage is needed for gasoline-type samples and 69 to 103 kPa
of the column at pressures controllable over the range from 0 gage for jet fuels. The pressure required will depend on the
to 103 kPa gage. (Warning—Compressed gas under high tightness of packing of the gel and the molecular weight of the
pressure.) sample. A transit time of 1 h is optimum; however, high-
8.6 Acetone, reagent grade, residue free. (Warning— molecular weight samples may require longer transit times.
Flammable. Health hazard.)
12.5 After the red, alcohol-aromatic boundary has advanced
8.7 Buffer Solutions, pH 4 and 7.
350 mm into the analyzer section, make a set of readings by
9. Sampling quickly marking the boundary of each hydrocarbon zone
observed in ultraviolet light (Warning—Direct exposure to
9.1 Obtain a representative sample in accordance with ultraviolet light can be harmful, and operators should avoid this
sampling procedures in Practice D 4057. Store the sample until as far as possible, particularly with regard to their eyes.) in the
ready for analysis at 2 to 4°C. (Warning—Flammable. Health following sequence. For the noninfluorescent saturate zone,
hazard.) mark the front of the charge and the point where the yellow
10. Preparation of Sample fluorescence first reaches its maximum intensity; for the upper
end of the second, or olefin zone, mark the point where the first
10.1 Samples containing any of the following: C 3 or lighter intense blue fluorescence occurs; finally, for the upper end of
hydrocarbons, more than 5% C4 hydrocarbons, or more than the third, or aromatic zone, mark the upper end of the first
10% C4 and C5 hydrocarbons can be depentanized in accor- reddish or brown zone. Refer to Fig. 2 as an aid in identifying
dance with Test Method D 2001. the boundaries. With colorless distillates, the alcohol-aromatic
boundary is clearly defined by a red ring of dye. However,
11. Preparation of Apparatus
impurities in cracked fuels often obscure this red ring and give
11.1 Mount the apparatus assembly in a darkened room or a brown coloration, which varies in length, but which shall be
area to facilitate observation of zone boundaries. For multiple counted as a part of the aromatic zone, except that when no
determinations, assemble an apparatus that includes the ultra- blue fluorescence is present, the brown or reddish ring shall be
violet light source, a rack to hold the columns, and a gas considered as part of the next distinguishable zone below it in
manifold system with spherical joints to connect to the desired the column. With some oxygenate blended fuel samples,
number of columns. another red band may appear several centimetres above the
reddish or brown alcohol-aromatic boundary (see Fig. 3) and
12. Procedure should be ignored. Avoid touching the column with the hands
12.1 Freely suspend the column from a loose-fitting clamp while marking the zones. If the boundaries have been marked
placed immediately below the spherical joint of the charger off with index clips, record the measurements. If the bound-
section. While vibrating the column along its entire length, add aries have been marked off with index clips, record the
small increments of silica gel through a glass funnel into the measurements.
charger section until the separator section is half full. Stop the 12.6 When the sample has advanced another 50 mm down
vibrator and add a 3 to 5-mm layer of dyed gel. Start the the column, make a second set of readings by marking the
vibrator and vibrate the column while adding additional silica zones in the reverse order as described in 12.5 so as to
gel. Continue to add silica gel until the tightly packed gel minimize errors due to the advancement of boundary positions
extends 75 mm into the charger section. Wipe the length of the during readings. If the marking has been made with a glass-
column with a damp cloth while vibrating the column. This writing pencil, two colors can be used to mark off each set of
aids in packing the column by removing static electricity. measurements and the distances measured at the end of the test
Vibrate the column after filling is completed for about 4 min. with the analyzer section lying horizontally on the bench top.
NOTE 3—More than one column can be prepared simultaneously by If the boundaries have been marked off with index clips, record
mounting several on a frame or rack to which an electric vibrator is the measurements.
attached. 12.7 Erroneous results can be caused by improper packing
12.2 Attach the filled column to the apparatus assembly in of the gel or incomplete elution of hydrocarbons by the
the darkened room or area, and when a permanently mounted alcohol. With precision bore columns, incomplete elution can
meter rule is used, fasten the lower end of the column to the be detected from the total length of the several zones, which
fixed rule with a rubber band. must be at least 500 mm for a satisfactory analysis. With
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FIG. 3 Pictorial Aid for Identification of Chromatographic Boundaries of Oxygenate Blended Fuel Samples
standard wall tubing, this criterion of total sample length is not attaching a rubber tube, connect to a water tap and flush with
strictly applicable because the inside diameter of the analyzer a rapid stream of water. Rinse with residue-free acetone and
section is not the same in all columns. dry by evacuation.
NOTE 4—For samples containing substantial amounts of material boil-
ing above 204°C, the use of isoamyl alcohol instead of isopropyl alcohol 13. Calculation
may improve elution.
13.1 For each set of observations calculate the hydrocarbon
12.8 Release the gas pressure and disconnect the column. To types to the nearest 0.1 volume % as follows:
remove used gel from the precision bore column, invert it
Aromatics, % volume 5 ~L a/L! 3 100 (1)
above a sink and insert through the wide end a long piece of
No. 19-gage hypodermic tubing with a 45° angle tip. By means Olefins, % volume 5 ~L o/L! 3 100 (2)
of 6-mm outside diameter copper tubing at the opposite end for Saturates, % volume 5 ~L s/L! 3 100 (3)
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D 1319
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16. Keywords
Data supporting the precision obtained from a round robin test for oxygenate
containing samples in Table 3 have been filed in a research report at ASTM 16.1 aromatics; fluorescent indicator absorption (FIA); hy-
headquarters. Request RR:D02-1361. drocarbon types; olefins; saturates
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D 1319
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