ASTM D4006-81(2005)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
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An American National Standard
Designation:D4006–81(Reapproved 2005)
Designation: Manual of Petroleum Measurement Standards (MPMS), Chapter 10.2
Designation: IP 358/97
Standard Test Method for
Water in Crude Oil by Distillation
This standard is issued under the fixed designation D4006; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
This standard has been approved for use by agencies of the Department of Defense.
1. Scope D1796 TestMethodforWaterandSedimentinFuelOilsby
the Centrifuge Method (Laboratory Procedure) (API
1.1 This test method covers the determination of water in
MPMS Chapter 10.6)
crude oil by distillation.
D4057 Practice for Manual Sampling of Petroleum and
1.2 This standard does not purport to address all of the
Petroleum Products (API MPMS Chapter 8.1)
safety concerns, if any, associated with its use. It is the
D4177 Practice for Automatic Sampling of Petroleum and
responsibility of the user of this standard to establish appro-
Petroleum Products (API MPMS Chapter 8.2)
priate safety and health practices and determine the applica-
E123 Specification for Apparatus for Determination of
bility of regulatory limitations prior to use. For specific
Water by Distillation
warning statements, see 6.1 and A1.1.
2.2 API Standards:
2. Referenced Documents
MPMS Chapter 8.1 Manual Sampling of Petroleum and
Petroleum Products (ASTM Practice D4057 (API MPMS
2.1 ASTM Standards:
Chapter 8.1))
D95 Test Method for Water in Petroleum Products and
MPMS Chapter 8.2 Automatic Sampling of Petroleum and
Bituminous Materials by Distillation (API MPMS Chapter
Petroleum Products (ASTM Practice D4177)
10.5)
MPMS Chapter 10.1 Test Method for Sediment in Crude
D96 TestMethodsforWaterandSedimentinCrudeOilby
Oils and Fuel Oils by the Extraction Method (ASTMTest
CentrifugeMethod(FieldProcedure)(API MPMSChapter
Method D473)
10.4)
MPMS Chapter 10.4 Determination of Water and/or Sedi-
D473 Test Method for Sediment in Crude Oils and Fuel
ment in Crude Oil by the Centrifuge Method (Field
Oils by the Extraction Method (API MPMS Chapter 10.1)
Procedure) (ASTM Test MethodD96)
D665 Test Method for Rust-Preventing Characteristics of
MPMS Chapter 10.5 Test Method for Water in Petroleum
Inhibited Mineral Oil in the Presence of Water
Products and Bituminous Materials by Distillation
(ASTM Test MethodD95)
This test method is under the jurisdiction of ASTM Committee D02 on
MPMSChapter10.6 TestMethodforWaterandSedimentin
Petroleum Products and Lubricants and theAPI Committee on Petroleum Measure-
Fuel Oils by the Centrifuge Method (Laboratory Proce-
ment, and is the direct responsibility of Subcommittee D02.02/COMQ the joint
dure) (ASTM Test Method D1796)
ASTM–API committee on Static Petroleum Measurement. This test method has
been approved by the sponsoring committees and accepted by the Cooperating
3. Summary of Test Method
Societiesinaccordancewithestablishedprocedures.Thistestmethodwasissuedas
a joint ASTM-API-IP standard in 1981.
3.1 The sample is heated under reflux conditions with a
Current edition approved June 1, 2005. Published September 2005. Originally
e1
waterimmisciblesolventwhichco-distillswiththewaterinthe
approved in 1981. Last previous edition approved in 2000 as D4006–81(2000) .
For referenced ASTM standards, visit the ASTM website, www.astm.org, or sample. Condensed solvent and water are continuously sepa-
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ratedinatrap—thewatersettlesinthegraduatedsectionofthe
Standards volume information, refer to the standard’s Document Summary page on
trap, and the solvent returns to the distillation flask.
the ASTM website.
ASTM standard withdrawn.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D4006–81 (2005)
5.1.3 The apparatus used in this test will be accepted when
satisfactory results are obtained by the calibration technique
described in Section 8.
6. Solvent
6.1 Xylene—reagent grade (Warning—Extremely flam-
mable.Vapor harmful. SeeAnnexA1.)Asolvent blank will be
established by placing 400 mL of solvent in the distillation
apparatus and testing as outlined in Section 9. The blank will
be determined to the nearest 0.025 mLand used to correct the
volume of water in the trap as in Section 10.
6.2 Thexyleneusedinthisprocedureisgenerallyamixture
of ortho, meta, and para isomers and may contain some ethyl
benzene. The typical characteristics for this reagent are:
Color (APHA) not more than 10
Boiling range 137–144°C
Residue after evaporation 0.002 %
Sulfur compounds (as S) 0.003 %
Substances darkened by H SO Color pass test
2 4
Water (H O) 0.02 %
Heavy metals (as Pb) 0.1 ppm
Copper (Cu) 0.1 ppm
Iron (Fe) 0.1 ppm
Nickel (Ni) 0.1 ppm
Silver (Ag) 0.1 ppm
7. Sampling, Test Samples, and Test Units
7.1 Sampling is defined as all steps required to obtain an
aliquotofthecontentsofanypipe,tank,orothersystemandto
place the sample into the laboratory test container.
FIG. 1 Distillation Apparatus
7.1.1 Laboratory Sample—Only representative samples ob-
tained as specified in Practice D4057 (API MPMS Chapter
8.1) and Practice D4177 (API MPMS Chapter 8.2) shall be
4. Significance and Use
used for this test method.
4.1 A knowledge of the water content of crude oil is
7.1.2 Preparation of Test Samples—The following sample
important in the refining, purchase, sale, or transfer of crude
handling procedure shall apply in addition to those covered in
oils.
7.1.1.
7.1.2.1 Thesamplesizeshallbeselectedasindicatedbelow
5. Apparatus
based on the expected water content of the sample:
5.1 The preferred apparatus, shown in Fig. 1, consists of a
Expected Water Content, Approximate Sample Size,
weight or volume % gormL
glassdistillationflask,acondenser,agraduatedglasstrap, and
50.1–100.0 5
a heater. Other types of distillation apparatus are specified in
25.1– 50.0 10
Specification E123.Any of these apparatus will be acceptable
10.1– 25.0 20
5.1– 10.0 50
for this test method provided it can be demonstrated that they
1.1– 5.0 100
operate within the precision established with the preferred
0.5– 1.0 200
apparatus.
less than 0.5 200
5.1.1 Distillation Flask—A 1000-mL round-bottom, glass,
7.1.2.2 If there is any doubt about the uniformity of the
distillation flask fitted with a 24/40 female taper joint shall be
mixedsample,determinationsshouldbemadeonatleastthree
used. This flask receives a 5-mL Specification E123 Type E
test portions and the average result reported as the water
calibrated,graduatedwatertrapwith0.05-mLgraduations.The
content.
trap will be fitted with a 400-mm Liebig condenser. A drying
7.1.2.3 To determine water on a volume basis, measure
tube filled with desiccant (to prevent entrance of atmospheric
mobile liquids in a 5, 10, 20, 50, 100, or 200-mL calibrated,
moisture) is placed on top of the condenser.
graduated cylinder (NBS Class A) depending on the sample
5.1.2 Heater—Any suitable gas or electric heater that can
size indicated in 7.1.2.1. Take care to pour the sample slowly
uniformly distribute heat to the entire lower half of the flask
into the graduated cylinder to avoid entrapment of air and to
may be used.An electric heating mantle is preferred for safety
adjust the level as closely as possible to the appropriate
reasons.
graduation. Carefully pour the contents of the cylinder into the
distillation flask and rinse the cylinder with at least 200 mLof
xylene in five steps of 40 mLand add the rinsings to the flask.
Drain the cylinder thoroughly to ensure complete sample
AvailableonspecialorderfromScientificGlassApparatusCo.,Bloomfield,NJ
07003. transfer.
D4006–81 (2005)
7.1.2.4 To determine water on a mass basis, weigh a test 9.4 Apply heat to the flask. The type of crude oil being
portion of sample in accordance with 7.1.2.1, pouring the evaluated can significantly alter the boiling characteristics of
sample directly into the distillation flask. If a transfer vessel the crude-solvent mixture. Heat should be applied slowly
(beaker or cylinder) must be used, rinse it with at least five during the initial stages of the distillation (approximately ⁄2 to
portions of xylene and add the rinsings to the flask. 1 h) to prevent bumping and possible loss of water from the
system. (Condensate shall not proceed higher than three
8. Calibration
quartersofthedistanceupthecondenserinnertube(Point Ain
Fig. 1).) To facilitate condenser wash-down, the condensate
8.1 Calibrate both the trap and the entire assembly prior to
should be held as close as possible to the condenser outlet.
use as indicated in 8.1.1-8.1.3.
After the initial heating, adjust the rate of boiling so that the
8.1.1 Verify the accuracy of the graduation marks on the
condensate proceeds no more than three quarters of the
trap by adding 0.05-mLincrements of distilled water, at 20°C,
distance up the condenser inner tube. Distillate should dis-
from a 5-mLmicroburet or a precision micro-pipet readable to
chargeintothetrapattherateofapproximately2to5dropsper
the nearest 0.01 mL. If there is a deviation of more than
second. Continue distillation until no water is visible in any
0.050mL between the water added and water observed, reject
part of the apparatus, except in the trap, and the volume of
the trap or recalibrate.
water in the trap remains constant for at least 5 min. If there is
8.1.2 Also calibrate the entire apparatus. Put 400 mLof dry
a persistent accumulation of water droplets in the condenser
(0.02% water maximum) xylene in the apparatus and test in
inner tube, flush with xylene. (A jet spray washing tube, see
accordance with Section 9. When complete, discard the con-
Fig. 2, or equivalent device is recommended.) The addition of
tentsofthetrapandadd1.00 60.01mLofdistilledwaterfrom
anoil-solubleemulsionbreakerataconcentrationof1000ppm
the buret or micro-pipet, at 20°C, directly to the distillation
to the xylene wash helps dislodge the clinging water drops.
flask and test in accordance with Section 9. Repeat 8.1.2 and
Afterflushing,redistillforatleast5min(theheatmustbeshut
add 4.50 6 0.01 mLdirectly to the flask. The assembly of the
off at least 15 min prior to wash-down to prevent bumping).
apparatus is satisfactory only if trap readings are within the
After wash-down, apply heat slowly to prevent bumping.
tolerances specified here:
Repeatthisprocedureuntilnowaterisvisibleinthecondenser
Limits Capacity Volume of Water Permissible for
andthevolumeofwaterinthetrapremainsconstantforatleast
of Trap at 20°C, Added at 20°C, Recovered Water
mL mL at 20°C, mL
5 min. If this procedure does not dislodge the water, use the
5.00 1.00 1.006 0.025
TFE-fluorocarbon scraper, pick shown in Fig. 2, or equivalent
5.00 4.50 4.50 6 0.025
device to cause the water to run into the trap.
8.1.3 A reading outside the limits suggests malfunctioning
9.5 When the carryover of water is complete, allow the trap
due to vapor leaks, too rapid boiling, inaccuracies in gradua-
and contents to cool to 20°C. Dislodge any drops of water
tions of the trap, or ingress of extraneous moisture. These
adhering to the sides of the trap with the TFE-fluorocarbon
malfunctions must be eliminated before repeating 8.1.2.
scraper or pick and transfer them to the water layer. Read the
volume of the water in the trap. The trap is graduated in
9. Procedure
0.05-mLincrements,butthevolumeisestimatedtothenearest
9.1 The precision of this test method can be affected by
0.025 mL.
water droplets adhering to surfaces in the apparatus and
10. Calculation
therefore not settling into the water trap to be measured. To
minimize the problem, all apparatus must be chemically
10.1 Calculate the water in the sample as follows:
cleanedatleastdailytoremovesurfacefilmsanddebriswhich
A– B
~ !
hinder free drainage of water in the test apparatus. More Volume% 5 3100 (1)
C
frequent cleaning is recommended if the nature of the samples
~A– B!
being run causes persistent contamination.
Volume% 5 3100 (2)
~M/D!
9.2 To determine water on a volume basis, proceed as
~A– B!
indicated in 7.1.2.3.Add sufficient xylene to the flask to make
Mass% 5 3100 (3)
M
the total xylene volume 400 mL.
9.2.1 To determine water on a mass basis, proceed as
where:
indicated in 7.1.2.4.Add sufficient xylene to the flask to make
A = mL of water in trap,
the total xylene volume 400 mL.
B = mL of solvent blank,
9.2.2 A magnetic stirrer is the most effective device to
C = mL of test sample,
reduce bumping. Glass beads or other boiling aids, although
M = g of test sample, and
less effective, have been found to be useful. D = density of sample, g/mL.
9.3 AssembletheapparatusasshowninFig.1,makingsure
Volatile water-soluble material, if present, may be
all connections are vapor and liquid-tight. It is recommended measured as water.
that glass joints not be greased. Insert a drying tube containing
11. Report
anindicatingdesiccantintotheendofthecondensertoprevent
condensation of atmospheric moisture inside the condenser. 11.1 Report the result as the water content to the nearest
Circulate water, between 20 and 25°C, through the condenser 0.025% and reference this Test Method D4006 (API MPMS
jacket. Chapter 10.2) as the procedure used.
D4006–81 (2005)
FIG. 2 Pick, Scraper, and Jet Spray Tube for Distillation Apparatus
Greater than 0.1 % water, repeatability is constant at 0.08.
12. Precision and Bias
12.1.2 Reproducibility—The difference between the two
12.1 The precision of this test method, as obtained by
single and independent test results obtained by different
statistical examination of interlaboratory test results in the
operators working in different laboratories on identical test
range from 0.01 to 1.0%, is described in 12.1.1 and 12.1.2.
material, would, in the long run, in the normal and correct
12.1.1 Repeatability—The difference between successive
operation of the test method, exceed the following value in
test results, obtained by the same operator with the same
only one case in twenty:
apparatus under constant operating conditions on identical test
From 0.0 % to 0.1 % water, see Fig. 3
material, would, in the long run, in the normal and correct
Greater than 0.1 % water, reproducibility is constant at 0.11.
operation of the test method, exceed the following value in
only one case in twenty:
13. Keywords
From 0.0 % to 0.1 % water, see Fig. 3.
13.1 crude oil; distillation; water
D4006–81 (2005)
FIG. 3 Basic Sediment and Water Precision
...