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1. Scope
1.1 This provisional specification2 covers low sulfur biodiesel (B100) for use as a blend component with diesel fuel oils
defined by Specification D 975 Grades 1-D, 2-D, and low
sulfur 1-D and 2-D.3
1.2 This specification, unless otherwise provided by agreement between the purchaser and the supplier, prescribes the
required properties of biodiesel fuel at the time and place of
delivery.
1.3 Nothing in this specification shall preclude observance
of federal, state, or local regulations which may be more
restrictive.
2. Referenced Documents
2.1 ASTM Standards:
D 93 Test Methods for Flash Point by Pensky-Martens
Closed Cup Tester4
D 130 Test Method for Detection of Copper Corrosion from
Petroleum Products by the Copper Strip Tarnish Test4
D 189 Test Method for Conradson Carbon Residue of
Petroleum Products4
D 445 Test Method for Kinematic Viscosity of Transparent
and Opaque Liquids (and the Calculation of Dynamic
Viscosity)4
D 524 Test Method for Ramsbottom Carbon Residue of
Petroleum Products4
D 613 Test Method for Cetane Number of Diesel Fuel Oil5
D 664 Test Method for Acid Number of Petroleum Products
by Potentiometric Titration4
D 874 Test Method for Sulfated Ash from Lubricating Oils
and Additives4
D 974 Test Method for Acid and Base Number by ColorIndicator Titration4
D 975 Specification for Diesel Fuel Oils4
3. Terminology
3.1 Definitions of Terms Specific to This Standard:
3.1.1 biodiesel, na fuel comprised of mono-alkyl esters of
long chain fatty acids derived from vegetable oils or animal
fats, designated B100.
1
This provisional specification is under the jurisdiction of ASTM Committee
D-2 on Petroleum Products and Lubricants and is the direct responsibility of
Subcommittee D02.E on Burner, Diesel, and Gas Turbine Fuels.
Current edition approved July 27, 1999. Published September 1999.
2
Provisional standards exist for two years subsequent to the approval date.
3
This fuel complies with 40 CFR Part 79.
4
Annual Book of ASTM Standards, Vol 05.01.
5
Annual Book of ASTM Standards, Vol 05.04.
Copyright ASTM, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959, United States.
PS 121
TABLE 1 Detailed Requirements for Biodiesel (B100)A
3.1.1.1 DiscussionBiodiesel, as defined above, is registered with the US EPA as a fuel and a fuel additive under
Section 211(b) of the Clean Air Act. There is, however, other
usage of the term biodiesel in the market place. Due to its EPA
registration and the wide spread commercial use of the term
biodiesel in the US market place, the term biodiesel will be
maintained for this specification.
3.1.1.2 DiscussionBiodiesel is typically produced by a
reaction of a vegetable oil or animal fat with an alcohol such as
methanol or ethanol in the presence of a catalyst to yield
mono-alkyl esters and glycerin. The finished biodiesel derives
approximately 10 % of its mass from the reacted alcohol. The
alcohol used in the reaction may or may not come from
renewable resources.
3.1.2 biodiesel blend, na blend of biodiesel fuel with
petroleum-based diesel fuel designated BXX, where XX is the
volume % of biodiesel.
3.1.3 biodiesel fuel, nsynonymn for biodiesel.
3.1.4 diesel fuel, na light or middle petroleum distillate
fuel.
3.1.5 free glycerin, na measure of the amount of unbonded glycerin remaining in the fuel.
3.1.6 total glycerin, nthe sum of the free glycerin and the
glycerin portion of any unreacted or partially reacted oil or fat.
Test MethodB
Property
Flash point (closed cup)
Water and sediment
Kinematic viscosity, 40C
Sulfated ash
SulfurD
Copper strip corrosion
Cetane number
Cloud point
Carbon residue
Acid number
Free glycerin
Total glycerin
D 93
D 2709
D 445
D 874
D 2622
D 130
D 613
D 2500
D 4530
D 664
F
F
Limits
100.0 min
0.050 max
1.9-6.0C
0.020 max
0.05 max
No. 3 max
40 min
Report to
customer
0.050 max
0.80 max
0.020G
0.240G
Units
C
% volume
mm2/s
% mass
% mass
C
% mass
mg KOH/g
% mass
% mass
4. Requirements
4.1 The biodiesel specified shall be mono-alkyl esters of
long chain fatty acids derived from vegetable oils and animal
fats.
4.2 A representative sample obtained using such techniques
as Practice D 4057 or D 4177 shall be used for all analysis.
4.3 The biodiesel specified shall conform to the detailed
requirements shown in Table 1.
NOTE 2A considerable amount of experience exists in the US with a
20 % blend of biodiesel, primarily produced from soybean oil, with 80 %
diesel fuel (B20). Experience with biodiesel produced from animal fat and
other oils is similar. Although biodiesel (B100) can be used, blends of over
20 % biodiesel with diesel fuel (B20) should be evaluated on a case by
case basis until further experience is available.
NOTE 3In certain items of fuel injection equipment in compression
ignition engines, such as rotary/distributor fuel pumps and injectors, the
fuel functions as a lubricant as well as a source for combustion. Blending
biodiesel fuel with diesel fuel typically adds lubricity.
5. Test Methods
5.1 The ASTM test methods identified in the specification
are based on those for diesel fuel. These testing methods appear
applicable for biodiesel testing. However precision and bias of
these methods with biodiesel is unknown and is under evaluation.
5.2 The requirements enumerated in this specification shall
be determined in accordance with the following methods.
5.2.1 Flash PointTest Methods D 93, except where other
methods are prescribed by law. Test Method D 3828 can also
be used. Test Method D 93 shall be the referee method.
6. Workmanship
6.1 The biodiesel fuel shall be visually free of undissolved
water, sediment, and suspended matter.
7. Keywords
7.1 alternative fuel; biodiesel fuel; diesel fuel oil; fuel oil;
renewable resource; specification
PS 121
ANNEX
(Mandatory Information)
A1. TEST METHOD FOR DETERMINATION OF FREE AND TOTAL GLYCERINE IN B 100 BIODIESEL METHYL ESTERS
BY GAS CHROMATOGRAPHY
A1.1 Scope
A1.1.1 This test method provides for the quantitative determination of free and total glycerin in B100 methyl esters by gas
chromatography. The range of detection for free glycerin is
0.005 to 0.05 mass %, and total glycerin from 0.05 to 0.5 mass
%. This procedure is not applicable to vegetable oil methyl
esters obtained from lauric oils, such as coconut oil and
palmkernel oil.
A1.1.2 The values stated in SI units are to be regarded as the
standard.
A1.1.3 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
A1.6 Apparatus
A1.6.1 Chromatographic SystemSee Practice D 355 for
specific designations and definitions.
A1.6.1.1 Gas Chromatograph (GC)the system must be
capable of operating at the conditions given in Table A1.1.
A1.6.1.2 Column, open tubular column with a 5 % phenylpolydimethylsiloxane bonded and cross linked phase internal coating. The column should have an upper temperature
limit of at least 400C. Columns, either 10 m or 15 m in length,
with a 0.32 mm internal diameter, and a 0.1 m film thickness
have been found satisfactory. Any column with better or
equivalent chromatographic efficiency and selectivity can be
used. It is recommended that a 2 to 5 metre 0.53 mm high
temperature guard column be installed from the injector to the
analytical column. This allows the use of autoinjectors and also
increases column life.
A1.6.2 Electronic Data Acquisition System::
A1.6.2.1 Integrator or Computer, capable of providing real
time graphic and digital presentation of the chromatographic
data is recommended for use. Peak areas and retention times
shall be measured by computer or electronic integration.
A1.6.2.2 This device must be capable of performing multilevel internal-standard-type calibrations and be able to calculate the correlation coefficient (r2) and internal standard calculations for each data set.
1 l
Column Temperature Program
50C
15C / min to 180C
7C / min to 230C
30C / min 380C
Flame ionization
380C
Carrier Gas
Hydrogen or helium
3 mL/min
hold 1 min
hold 10 min
measured at 50C
PS 121
TABLE A1.3 Standard Solutions
10
30
50
70
20
50 100 150
10
20
40
70
10
20
40
70
100 100 100 100
100 100 100 100
100
200
100
100
100
100
(A1.1)
where:
Ai = area of reference substance, and
As = area of internal standard.
amti 5 ~Wi /Ws!
(A1.2)
where:
Wi = mass of reference substance, and
Ws = mass of internal standard.
Prepare a calibration curve for each reference component by
plotting the response ratios (rspi), as the y-axis, versus the
amount ratios (amti), as the x-axis.
A1.9.6 Calculate the correlation coefficient r2 value for each
reference component in the calibration set using Eq A1.3. The
r2 value should be at least 0.99 or greater. If the above criteria
for r2 are not met, rerun the calibration or check instrument
parameters and hardware.
r2 5
@ ( xy2#
@ ( x2 # @ ( y2 #
(A1.3)
where:
9
Glycrein
1-Mono [cis-9-octadecenoyl]-racglycerol (monoolein)
1,3-Di [cis-octadecenoyl]glycerol
(diolein)
1,2,3-Tri [cis-octadecenoy]glycerol
(triolein)
(S) - (-) -1,2,4-Butanetriol
1,2,3-Tridecanolylglycerol (tricaprin)
(A1.4)
y 5 Yi 2 y
(A1.5)
56-81-5
111-03-5
25
50
50
10
and:
Xi = amti ratio data point,
x = average values for all amti data points
Yi = corresponding rspi data points,
y = average values for all rspi data points.
A1.9.7 Calibration FunctionsFor each reference calibration functions are calculated in the form:
2465-32-9
50
10
Wx/Wis 5 bx 3 ~Ax/Ais! 1 ax
122-32-7
50
10
42890-76-6
321-71-6
25
80
25
10
x 5 Xi 2 x
CAS No.
Approximate Volumetric
Weight (mg) Flask Size
(mL)
where:
Wx = weight of reference substance, mg,
Wis = weight of internal standard, mg,
Ax = peak area of reference substance,
4
(A1.6)
PS 121
Ais
bx
ax
A1.10 Procedure
A1.10.1 Set the instrument operating variables to the values
specified in Table A1.1. Weigh to the nearest 0.1 mg approximately 100 mg of sample directly into a 10 mL septa vial.
Using microlitre syringes, add exactly 100 L of each internal
standard and MSTFA. Shake the vials, and allow to set for 15
to 20 min at room temperature. Add approximately 8 mL of
n-Heptane to the vial and shake.
A1.10.2 Inject 1 L of the reaction mixture into the cool
on-column injection port and start the analysis. Obtain a
chromatogram and peak integration report.
A1.10.3 Peak IdentificationIdentify peaks by comparison
of retention times to the standards. For identification of
additional peaks, use the relative retention times given in Table
A1.4 and the reference chromatograms given in Fig. A1.1. The
mono-, di, and triglycerides are separated according to carbon
numbers (CN).
A1.10.4 Monoglycerides consist of the four overlapping
peaks with relative retention times (RRT) of 0.76 and 0.83 to
0.86 with respect to the internal standard tricaprin. A pair of
peaks, methyl esters with a carbon number of 24, may appear
with RRT of 0.80 to 0.82, and should not be included in the
calculation of monoglycerides.
A1.10.5 Diglycerides are also primarily separated according
to carbon number, but due to varying double bonds in the
molecules, baseline resolution of the peaks does not occur. The
grouping of 3 to 4 peaks with RRT of 1.05 to 1.09 (CN 34, 36,
and 38) shall be attributed to diglycerides. Carbon number also
separates triglycerides. Peaks with RRT of 1.16 to 1.31 (CN 52,
54, 56, and 58) should be included in the calculation.
where:
G
= mass percentage of glycerin in sample,
Ag
= peak area of glycerin,
Ais1 = peak area of Internal Standard 1,
Wis1 = weight of Internal Standard 1 in mg,
W
= weight of sample in mg,
bg
= slope of the calibration function,
= intercept of the calibration function.
ag
A1.11.1.2 Individual Glycerides:
Gli 5 ~bo 3 Agli/Ais2 1 ao1! 3 Wis2 3 100/W
where:
GlM = 0.2591 3 ( monoglyceride, mass % determined in
Eq A1.8,
GlD = 0.1488 3 ( diglyceride, mass % determined in Eq
A1.8, and
GlT = 0.1044 3 ( triglyceride, mass % determined in Eq
A1.8.
A1.11.2 Report the free and total glycerin to the nearest
0.001 mass %.
0.85
1.00
2
2
0.76
0.83-0.86
1.00
2
2
(A1.9)
where:
free glycerin
= glycerin determined in Eq A1.7,
bound glycerin = ( (GlM, GlD, GlT)
Glycerin
1,2,4 Butanetriol
Internal Standard 1
Monopalmitin
Monoolein, monolinolein
monolinolenin, and monostearin
Tricaprin
Internal Standard 2
Diglycerides
Triglycerides
(A1.8)
where:
=
Gli
Agli =
Ais2 =
Wis2 =
W
=
=
bol
Component
(A1.7)
A1.13 Keywords
A1.13.1 biodiesel; free glycerin; Gas Chromatography 4;
methyl esters; total glycerin
1.05-1.09
1.16-1.31
PS 121
APPENDIXES
(Nonmandatory Information)
X1. SIGNIFICANT OF PROPERTIES SPECIFIED FOR BIODIESEL FUEL
X1.1 Introduction
X1.1.1 The properties of commercial biodiesel fuel depends
upon the refining practices employed and the nature of the
PS 121
with biodiesel or its blends. There is no substantiating data to
support the calculation of cetane index with biodiesel or
biodiesel blends.
X1.3 Viscosity
X1.3.1 For some engines it may be advantageous to specify
a minimum viscosity because of power loss due to injection
pump and injector leakage. Maximum allowable viscosity, on
the other hand, is limited by considerations involved in engine
design and size, and the characteristics of the injection system.
The upper limit for the viscosity of biodiesel (6.0 mm2/s at
40C) is higher than the maximum allowable viscosity in
Specification D 975 Grade 2-D and 2-D low sulfur (4.1 mm/s
at 40C). Blending biodiesel with diesel fuel close to its upper
limit could result in a biodiesel blend with viscosity above the
upper limits contained in Specification D 975.
X1.5 Sulfur
X1.5.1 The effect of sulfur content on engine wear and
deposits appears to vary considerably in importance and
depends largely on operating conditions. Fuel sulfur can also
affect emissions control systems performance and various
limits on sulfur have been imposed for environmental reasons.
PS 121
X2. STORAGE STABILITY
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