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CopyrightAmericanSocietylor TestingandMaterials(ASTM)
100 Barr Harbor Orive, West Conshohocken,
Pennsylvania
19428-2959
Unitea
States
ot Amerlca
Kopia wykonana przez Polski Komilet NormalizacvJny
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Designation: D 5453
- ooe1
An AmericanNationalStandard
Motor
fi
1. Scope
1.1 This test method covers the determination of total suIfur
in liquid hydrocarbons, boiling in the range from approximaiely 25 to 400C, with viscosities bt:tween approximately
0.2 and 20 cSt (mm2/S) at room temperature.
1.2 Three separate inter-Iaboratory studies (ILS) on precision have determined that this test method is applicable to
naphthas, distillates, oils, and motor fuels: such as gasoline,
oxygen enriched gasoline (M-85, RFG), diesel, biodiesel and
jet fue!. SampIes containing 1.0 to 8000 mg/kg total suIfur can
be analyzed (Note l).
NOTE I-Estimates
of the pooled limit of quantification (PLOQ) for
each ofthe three precision studies were calculated. Values ranged between
less than 1.0 and less than 5.0 mg/kg (see Section 8 and 14.1).
1.3 This test method is applicable for total sulfur determination in liquid hydrocarbons containing less than 0.35 %
(mim) halogen(s).
lA The values stated in SI units are to be regarded as
standard.
~
.....
Copyright@ASTM. 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
5.1 Furnace-An
electric fumace held at a temperature
(1075 ::!: 25C) sufficient to pyrolyze all of the sample and
oxidize suIfur .to S02'
5.2 Combustion Tube-A
quartz combustion tube constructed to allow the direct injection of the sample into the
heated oxidation zone of the fumace or constructed so that the
inlet end of the tube is large enough to accommodate a quartz
4 Annuat Book or ASTM Standards, Vol 05.04.
5 Apparatus manufactured in several variations by Antek Instruments, Inc"
Houston, TX has been found suitable for this purpose.
~~~
D 5453
sample boat. The combustion tube must have sidc arms for the
introduction of oxygen and canier gas. The oxidation section
shall be large enough (see Fig. l and Fig. 2) to ensure complete
combustion of the sample. Fig. l and Fig. 2 depict convcntional combustion tubes. Other conflgurations are acceptable if
precision is not degraded.
5.3 Flow Control- The apparatus mus t be equipped with
flow controllers capable of maintaining a constant supply 01'
oxygen and carrier gas.
5.4 Drier Tube- The apparatus must be equipped with a
mechanism for the removal of water vapor. The oxidation
reaction produces water vapor which must be eliminated prior
to measurement by the detector. This can be accomplished with
a membrane drying tube, or a permeation d/J'er, that utilizes a
selective capillary action for water removal.
5.5 UV Fluoreseenee Detector-A qualitative and quantitative detector capable 01' measuring light emitted from the
fluorescence 01'sulfur dioxide by UV light.
5.6 Mierolitre S)Jringe-A microlitre syringe capable 01'
accurately de]ivering 5 to 20-)lL quantities. The needle shall be
50 mm (::!::5 mm) long.
5.7 Sample Inlet System-Either
01' two types of sample
inlet systems can be used.
5.7.1 Direet 1l1;jeetion-A direct injection inlet system must
be capable 01'allowing the quantitative delivery ofthc materia I
to be analyzed into an inlet carrier stream which directs the
sample into the oxidation zone at a controlled and repeatable
rate. A syringc drive mechanism which discharges the sample
from the microlitre syringe at a rate of approximately l )lLls is
required. See example, Fig. 3.
5.7.2 Boat Inlet System An extended combustion tube
provides a seal to the inlet ofthe oxidation area and is swept by
a canier gas. The system provides an area to position the
sample carrying mechanism (boat) at a retracted position
removed from the fumace. The boat drive mechanism will
fully insert the boat into the hottest section ofthe fumace inlet.
The sample boats and combustion tube are constructed of
quartz. The combustion tube provides a cooling jacket for the
area in which the retracted boat rests awaiting sample intro-
4S0mm
~- ":'"'"
,,""'-~
25mm
~
- 12m,n
1I
.~
l
77[~
~/
~,
100mm
6m:n , lmm ID
"
CAPILL~RY
\lJ
riO
isee
MUST FIT 12mm
~
Uf
..j
12mm
25mm
1 Direct
Inject
Quartz
Pyrolysis
Tube
90mm
IZmm.-/
~
~
S,PTUM
DETAILS,LOW
~m~
rI
D 5453
59?mm
,~
~
257mm
6mm
OD x 2mr~
ID
12r~m
35mm
~.~..
2.';rnm
5Dmrl --1
6rnm OD x 2rnm ID
5Dmm
I
r---.
Su
AJ\t (PuR
A(h
<cif
FURNACE
-INLET-CARRIER/OXYGEN
MIX
SYRINGE
PYRO OXYGEN
fUANACE
COOlANT OUT
INlET .cARRIfR
ANO OXYGfN ..X
PYRO
OXYGON
BOAT ORIVE
NOTE 2-A
correctiou
for chemical
impurity
cau be required.
~~~
D 5453
TABLE 2 Sulfur Standards
Curve III
Sulfur, ng/L
0.50
1.00
2.50
5.00
10.00
Injection Size
10-20 L
5.00
25.00
50.00
100.00
100.00
500.00
1000.00
Injection Size
5-1 O L
Injection Size
5 L
Num
6-Injection
would cstablish
or Apparatus
Curve II
Sulfur, ng/L
7, Hazards
9. Preparatioll
Curvel
Sulfur, ng/L
and Stalldardizatioll
1 ~L!s
140-160 mm/min
1075 :': 25C
450-500 mLirnin
10-30 mLimin
130-160 mLirnin
~~~
D 5453
Once the boat has reached its fully retracted position, allow at
least l min for cooling before the next sample injection (Note
9).
NOTE 9-S1owing
boat speed or briefly pausing the boat in the furnace
can be necessary to ensure complete sample combustion. Direct injection
can ease sample handling and improve sample combustion characteristics
for materiaIs containing very volatile sulfur compounds.
I'
/'"'
12. CalcuIation
12.l For analyzers caIibrated using a standard curve, ealculate thesulftlr content of the test specimen in parts per miJJion
(ppm) as follows:
(I - Y)
( l)
Sulfur.ppm (Ilg/g)= S x M x Kg
Ol',
(2)
where:
D
= density of test specimen solution, g/mL,
I
= average of integrated detector response tor test
specimen solution, counts,
= gravimetric dilution factor, mass of test specimen!
Kg
mass of test specimen and solvent, g/g,
Kv
11. Procedure
11.1 Obtain a test specimen using the procedure described
in Section 8. The sulfur concentration in the test specimen must
be less than the concentration of the highest standard and
greater than the concentration of the lowest standard used in
the calibration. If required, a dilution can be perfomled on
either a weight Ol' volume basis.
11.1.1 Gravimetrie Dilution (mass/mass) Record the mass
of the test specimen and the total mass of the test specimen and
solvenL.
11.1.2 Volumetrie Dilution (mass/volume)
Record the
mass of the test specimen and the total volume of the test
specimen and solvenL.
11.2 Measure the response for the test specimen solution
(4)
~~~
where:
D
Kg
lvI
v
G
D 5453
under constant operating conditions on identical test materia l
would, in the long run, in the nOffi1aland correct operation of
the test method, exceed the following values in only 1 case in
20, where x = the average of the two test results.
Less than 400 mg/kg
(6)
R =, 0.5797
X(O.7SJ
(7)
(8)
14. Precision
14.1 The test method was examined in three separate
inter-1aboratory studies.7 The precision of the test method, as
obtained by statistical analysis of test resuIts, is as follows
(Note II).
15. Keywords
15.1 analysis; diesel; ftuorescence; gasoline; jet fue!; kerosene; M-SS; RPG; sulfur; uItraviolet
(5)
0.1788 X(075)
TABLE 3 Repeatability
Concentration
(mg/kg S)
14.1.1 Repeatability The difference between two test resuIts obtained by the same operator with the same apparatus
1
5
10
50
100
400
(R)
R
0.2
0.6
1.0
3.4
5.7
16.0
0.6
1.9
3.3
10.9
18.3
51.9
APPENDIXES
(Nonmandatory lnformation)
Xl. QUALlTY CONTROL
Xl.I Confirm the performance of the instrument or the test
procedure by analyzing a quality control (QC) sample.
controllimits
MNL 7).8
, ASTM MN!' 7, Manual on Presentation ofData C,mlrol Chart Analysis, 6th ed.,
available from ASTM Headquarters.
6
~t
Method D 6299 and MNL 7). Any out-of-control data should
trigger investigation for root cause(s). The results of this
investigation may, but not necessarily. result in instrument
re-calibration.
X2. IMPORTANT
f'.
D 5453
10to 20 ~L
5 to 10~L
5 ~L
TABLEX2.1
TypicalGasFlows
Inlet carrier flowmeter settingsA
Inlet oxygen flowmeter setting
F urnace oxygen flowmeter setting
Ozone generator flowmeter settingB
Injection
FlowmeterBali
3.4-3.6
0.4-0.6
3.8-4.1
1.5-1.7
Analysis
MFC
140-160 mUmin
10-20 mUmin
450-500 mUmin
35-45 mUmin
~m~
D 5453
X2.l2 Calibration
Materials/Standard
Curve
Construction ..Prepare calibration standard s with solvent materials that have minimum or no sulful' contamination relative
to the concentration anticipated in the samp]e unknown.
Couect for sultur contribution trom solvent materia]s and
X3. IMPORTANT
0.
X3.9Membrane
Dryer Purge-Water produced during the
combustion of the sampIc is removed by the membrane dryer.
This water must then be purged. For an apparatus that utilizes
a desiccant scrubber (flow recycJe) to provide the membrane
dryer purge gas, replace the drying agent when color change
(blue to pink) indicates. When an auxiliary gas flow is used, set
membrane wyer purge flow at 200 to 250 mLlmin.
D-5453 (SUI_FUR)
~.
10 to 20 ~L
5 to 10 ~L
5 ~L
X3.ll Boat Blank/Baseline Stabilit;y-Prior to analysis, especially when analyzing low ]evels, advance the empty boat
into furnace to ensure that no contamination is present in the
boat ar on the inside areas of the pyrotube near the injection
area. Reat empty boat in the furnaee to ensure that boat is
dean, then rapidly move boat out to injection area.
NOTl" X3.l-..Ifthe
hot boa t being retumed to tbe injection area eauses
baseline upset, repeat the boat in and out cycle, until no sui fur is
--.-...
Inlet carrier ftowmeter settingsA
Inlet oxygen fiowmeter setting
Furnace oxygen fiowmeter setting
Ozone generator fiowmeter settingB
Inlet Analysis
Flowmeter Bali
3.4-3.6
0.4-0.6
3.8-4.1
1.5-1.7
MFC
130-160 mUmin
10-20 mUmin
450-500 mUmin
35-45 mUmin
~~J~
D 5453
X3.l2 Calibration
Materials/Standard
Curve
Construction Prepare calibration standards with solvent materials that have minimum or no sulfiIr contamination relative
to the concentration anticipated in the sample unknown.
Correct for sulfur contribution from solvent materials and
Sub-Committee D02.03 has identified the location of selected changes to this standard since thc last issue
(D 5453 93) that may impact the use of this standard.
(a) Updated and cxpanded applicable materials described in
Section ].
(h) Modified referenced documcnts in Section 2.
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with any item mentioned in this standard. Users of this standard are express/y advised that determination
of the validity of any such
patent rights, and the risk of infringement of such rights, are entire/y their own responsibility.
This standard is subject to revision at any time by the responsib/e technica/ committee and must be reviewed every five years and
if not revised. either reapproved or withdrawn. Your comments are invited either for revision ofthis standard or for additiona/ standards
and shou/d be addressed
to ASTM Headquarters.
Your comments
will receive careful consideration
at a meeting of the responsib/e
technical committee,
which you mayattend.
If you feel that your comments
have not received a fair hearing you shou/d make your
views known to the ASTM Committee
on Standards, at the address shown be/ow.
This standard is copynghted by ASTM. 100 Barr Harbor Dnve, PO Box C700, West Conshohocken, PA 19428-2959, United States.
Individua/ reprints (sing/e or multip/e copies) of this standard may be obtained by contacting ASTM at the above address or at
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