Designation: D7112 – 09

Standard Test Method for

Determining Stability and Compatibility of Heavy Fuel Oils
and Crude Oils by Heavy Fuel Oil Stability Analyzer (Optical
Detection)1
This standard is issued under the fixed designation D7112; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.

1. Scope* D2880 Specification for Gas Turbine Fuel Oils

1.1 This test method covers an automated procedure involv- D4057 Practice for Manual Sampling of Petroleum and
ing titration and optical detection of precipitated asphaltenes Petroleum Products
for determining the stability and compatibility parameters of D4175 Terminology Relating to Petroleum, Petroleum
refinery residual streams, residual fuel oils, and crude oils. Products, and Lubricants
Stability in this context is the ability to maintain asphaltenes in D4177 Practice for Automatic Sampling of Petroleum and
a peptized or dissolved state and not undergo flocculation or Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance
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precipitation. Similarly, compatibility relates to the property of

mixing two or more oils without precipitation or flocculation of and Control Charting Techniques to Evaluate Analytical
asphaltenes. Measurement System Performance
1.2 This test method is applicable to residual products from D6560 Test Method for Determination of Asphaltenes
atmospheric and vacuum distillation, from thermal, catalytic, (Heptane Insolubles) in Crude Petroleum and Petroleum
and hydrocracking processes, to products typical of Specifica- Products
tions D396, Grades No. 5L, 5H, and 6, and D2880, Grades No. 3. Terminology
3-GT and 4-GT, and to crude oils, providing these products
contain 0.05 mass % or greater concentration of asphaltenes. 3.1 Definitions:
1.3 This test method is not relevant to oils that contain less 3.1.1 For definitions of some terms used in this test method,
than 0.05 % asphaltenes, and would be pointless to apply to such as crude oil, repeatability, reproducibility, and residual
unstable oils that already contain flocculated asphaltenes. fuel oil, refer to Terminology D4175.
1.4 The values stated in SI units are to be regarded as 3.1.2 asphaltenes, n—in petroleum technology, molecules
standard. No other units of measurement are included in this of high molecular mass, high carbon/hydrogen ratio, and
standard. containing hetero-atoms.
1.5 This standard does not purport to address all of the 3.1.2.1 Discussion—Asphaltenes are generally found in
safety concerns, if any, associated with its use. It is the crude oils and in heavy fuel oils containing residual fractions.
responsibility of the user of this standard to establish appro- Their presence is determined by their insolubility in alkanes
priate safety and health practices and determine the applica- such as n-heptane and solubility in aromatics such as xylene.
bility of regulatory limitations prior to use. 3.1.3 compatibility, n—of crude oils and of heavy fuel oils,
the ability of two or more crude oils or fuel oils to be blended
2. Referenced Documents together within specified ratios without evidence of separation,
2.1 ASTM Standards:2 such as flocculation or separation of asphaltenes.
D396 Specification for Fuel Oils 3.1.4 flocculation, n—of asphaltenes in crude oils or heavy
fuel oils, the aggregation of colloidally dispersed asphaltenes
into larger, visible masses that may or may not settle.
1
This test method is under the jurisdiction of ASTM Committee D02 on 3.1.5 stability reserve, n—of crude oils, heavy fuel oils, and
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee residual streams containing asphaltenes, the property of an oil
D02.14 on Stability and Cleanliness of Liquid Fuels.
Current edition approved Dec. 1, 2009. Published February 2010. Originally to maintain asphaltenes in a peptized (colloidally dispersed)
approved in 2005. Last previous edition approved in 2005 as D7112–05a. DOI: state and prevent their flocculation when stored or when
10.1520/D7112-09.
2
blended with other oils.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3.1.5.1 Discussion—An oil with a high stability reserve can
Standards volume information, refer to the standard’s Document Summary page on be stored for a long period of time or blended with a range of
the ASTM website. other oils without flocculation of asphaltenes.

*A Summary of Changes section appears at the end of this standard.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.

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 D7112 – 09
3.2 Definitions of Terms Specific to This Standard: indicates that an oil is more stable with respect to flocculation
3.2.1 aromatic solvent equivalent (xylene equivalent), SE, of asphaltenes. P-value by this test method relates specifically
n—the lowest aromatic solvent (xylene) content, expressed as to xylene and n-heptane as the aromatic and paraffinic solvents,
a volume %, in a mixture containing aromatic and paraffinic respectively.
solvents (xylene and n-heptane) which, when mixed with oil, 3.2.9 Pa, n—the P-value of an asphaltene, which is the
will not result in flocculation of asphaltenes. See flocculation peptizability or ability of an asphaltene to remain colloidally
ratio. dispersed.
3.2.1.1 Discussion—SE is defined as FR5/1 multiplied by 3.2.10 Po, n—the P-value of an oil matrix. See oil matrix.
100 %, as shown in Eq 2. 3.2.11 peptize, v—of an oil or cutter stock, to dissolve an
3.2.2 evaporation correction coeffıcient, n—the rate of asphaltene or to maintain an asphaltene in colloidal dispersion.
evaporation of aromatic solvent (xylene) from the sample cup, 3.2.12 solubility blending number, SBN, n—a crude oil
measured in grams per hour. blending model parameter which can be used to determine if
3.2.3 flocculation ratio (FR), n—the lowest aromatic sol- blends of oils are incompatible or compatible. See insolubility
vent (xylene) concentration, expressed as a proportion of number.
xylene to xylene plus n-heptane which, when mixed with an 3.2.12.1 Discussion—Solubility blending numbers for indi-
oil, will not result in flocculation of asphaltenes. See 15.1, Eq vidual oils are determined and calculated from the density of
1. the oil, aromatic solvent equivalent value, and volume of
3.2.4 FR5/1, n—the flocculation ratio at a dilution of 5 mL of paraffinic solvent that can be added to 5 mL of oil without
xylene and n-heptane solvent mixture to 1 g of oil. asphaltene precipitation. The equations are given under Calcu-
3.2.4.1 Discussion—The ratio 5 to 1 is used internally by a lation of Results (see 15.2).
number of oil companies involved with the stability and 3.2.13 step size, n—the volume in mL of each portion of
compatibility of heavy fuel oils and crude oils. This ratio is n-heptane added to the stock solution in the course of the test
chosen so that a P-value of six represents an FR5/1 of zero. procedure.
3.2.5 insolubility number, IN, n—a crude oil blending model 3.2.14 stock solution, n—a solution of a sample dissolved in
parameter which can be used to determine if blends of oils are a specific amount of xylene.
compatible or incompatible. See solubility blending number. 3.3 Symbols:
FR = flocculation ratio
3.2.5.1 Discussion—Insolubility numbers for individual oils
FR5/1 = flocculation ratio at a dilution of 5 mL solution
are determined and calculated from the density of the oil,
(xylene plus n-heptane) to 1 g of oil
aromatic solvent equivalent value and volume of paraffinic
FRmax = maximum flocculation ratio
solvent (n-heptane) that can be added to 5 mL of oil without
IN = insolubility number
asphaltene precipitation. The equations are given under Calcu-
P = the P-value of an oil
lation of Results (see 15.2).
Pa = the P-value of an asphaltene
3.2.6 maximum flocculation ratio, FRmax, n—of asphaltenes
Po = the P-value or peptizing power of an oil matrix
in residual fuel oils and crude oils, the minimum required
SBN = solubility blending number
solvency power of a solvent mixture, expressed as a ratio by
SE = xylene equivalent, volume %
volume of aromatic solvent (xylene) to aromatic solvent plus
Xmin = n-heptane consumption of undiluted oil, in mL/g of
paraffinic solvent (n-heptane) to keep the asphaltenes in an oil
oil
colloidally dispersed.
3.2.6.1 Discussion—FRmax is determined from a plot of 4. Summary of Test Method
flocculation ratios versus the oil concentration in solvent, 4.1 Stability and compatibility parameters are determined
extrapolated to infinite dilution of the sample at the y-axis by titration and optical detection of precipitated asphaltenes. A
(where (1/X) = 0. See Eq 3). stock solution is prepared and three different mixtures of the
3.2.7 oil matrix, n—that portion of a sample of heavy fuel sample oil plus xylene are titrated with n-heptane to cause
oil or crude oil that surrounds and colloidally disperses the precipitation of asphaltenes. The titrated mixture is continu-
asphaltenes. ously circulated through an optical detector which detects
3.2.7.1 Discussion—For purposes of this test method, an oil precipitated asphaltenes by back-scattering of visible light. The
sample is considered to be composed of an oil matrix (some- amounts of oil, xylene, and n-heptane are used to calculate
times called an oil medium) and asphaltenes. stability parameters: solvent equivalent, P-value, and FR5/1. If
3.2.8 P-value, n—of refinery residual steams, residual fuel the density of a crude oil sample is known, then the compat-
oils and crude oils, an indication of the stability or available ibility parameters (SBN and IN) of the crude oil may also be
solvency power of an oil with respect to precipitation of calculated.
asphaltenes.
3.2.8.1 Discussion—Since the equation defining P-value is 5. Significance and Use
P = (1 + Xmin), where Xmin is the minimum volume of paraffinic 5.1 Automatic determination of stability parameters using a
solvent, n-heptane, (in mL) needed to be added to 1 g of oil to light back-scattering technique improves accuracy and re-
result in flocculation of asphaltenes, the smallest P-value is 1, moves human errors. In manual testing, operators have to
which means the oil is unstable and can precipitate asphaltenes visually compare oil stains on pieces of filter paper to deter-
without addition of any paraffinic solvent. A higher P-value mine if asphaltenes have been precipitated.
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 D7112 – 09
5.2 Refinery thermal and hydrocracking processes can be for n-heptane and xylene addition, the circulation line for
run closer to their severity limits if stability parameters can be passing the sample through the detector and the exhaust line,
calculated more accurately. This gives increased yield and which empties the sample cup after analysis.
profitability. 7.1.1.4 Aromatic Solvent Pump, accurate and adjustable
5.3 Results from the test method could be used to set a ceramic piston pump, capable of delivering xylene at a rate of
standard specification for stability parameters for fuel oils. 0.01 to 0.5 mL/s.
5.4 The compatibility parameters of crude oils can be used 7.1.1.5 Paraffınic Solvent Pump, accurate and adjustable
in crude oil blending in refineries to determine, in advance, ceramic piston pump, capable of delivering n-heptane at a rate
which crude oil blends will be compatible and thus can be used of 0.01 to 0.5 mL/s.
to minimize plugging problems, unit shut downs, and mainte- 7.1.1.6 Circulation Pump, accurate and adjustable ceramic
nance costs. Determination of crude oil compatibility param- piston pump used to circulate the sample under test through the
eters also enables refineries to select crude oil mixtures more detector system.
economically. 7.1.1.7 Exhaust Pump, accurate and adjustable ceramic
5.5 This test method can measure stability and compatibility piston pump used to empty the sample cup at the end of the
parameters, and determine stability reserve on different blends measurement.
for particular applications to optimize the blending, storage, 7.1.1.8 Detector System, (see Fig. 3) optical detector
and use of heavy fuel oils through which the sample solution is continuously circulated.
NOTE 1—Users of this test method would normally use stability and The detector is composed of a visible light source and a
compatibility parameters to determine stability reserve of residual prod- photodiode for recording the light reflecting from asphaltene
ucts, fuel blends and crude oils. However, the interpretation of stability, particles in the test sample.
stability reserve and compatibility is heavily ‘use dependent,’ and is
beyond the scope of this test method.
7.1.1.9 Hot Plate, a temperature controlled heating system
may be located below the sample cups, which will warm up the
6. Interferences sample so that the titration may be performed at an elevated
6.1 Free water present in the oil can cause difficulties with temperature. The temperature of the hot plate should be
the optical detector and should be removed by centrifuging adjustable between 20 and 100°C.
prior to testing. 7.1.2 Computer, controls the measurement and calibration
6.2 Solid particles, such as coke or wax particles, mud, programs and is an interface between the operator and the
sand, or catalyst fines, in the oil will not affect the optical analyzer.
detector or interfere with the results. 7.1.3 PORLA Step Measurement Screen, computer display,
allowing data about the sample and operator to be input as well
7. Apparatus as showing the results of each titration (see Fig. 4).
7.1 PORLA Heavy and Crude Oil Stability and Compatibil- 7.1.4 Parameter Screen, computer display, allows all of the
ity Analyzer3,4—See Figs. 1 and 2. measurement cycle parameters to be adjusted from the default
7.1.1 A portion of the apparatus is shown diagrammatically values and also allows the pump calibration procedure to be
in Fig. 2 and is comprised of the following parts: run (see Fig. 5).
7.1.1.1 Sample Cup, light weight, inert cups designed to fit
the sample carousel, with a smooth, flat bottom, volume 8. Reagents and Materials
approximately 100 mL. Typically, aluminum cups have been 8.1 Purity of Reagents—Reagent grade chemicals shall be
used. used in all tests. Unless otherwise indicated, all reagents shall
7.1.1.2 Sample Carousel, typically a four-position sample conform to the specifications of the Committee on Analytical
cup holder delivering the sample cups sequentially to the Reagents of the American Chemical Society where such
measurement position. specifications are available.5 Other grades may be used, pro-
7.1.1.3 Mixer Lift System, vertically moving lift system, vided it is first determined that the reagents are of sufficiently
forming a seal with the sample cup in the measurement high purity to permit their use without lessening the accuracy
position and incorporating a mechanical stirrer which starts to of the determination.
rotate when the seal is made. It also incorporates delivery lines 8.2 Xylene (C8H10)—The xylene used is generally a mixture
of ortho, meta, and para isomers and may contain some ethyl
benzene. (Warning—Flammable, health hazard.)
3
The PORLA Heavy and Crude Oil Stability and Compatibility Analyzer is 8.3 n-heptane (C7H16)—(Warning—Flammable, health
covered by Euro patent EP 0737309 and U.S. patent US5715046. Interested parties
hazard.)
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are invited to submit information regarding the identification of an alternative(s) to

this patented item to the ASTM International Headquarters. Your comments will
receive careful consideration at a meeting of the responsible technical committee,1
which you may attend.
4 5
The sole source of supply of the PORLA Heavy and Crude Oil Stability and Reagent Chemicals, American Chemical Society Specifications, American
Compatibility Analyzer known to the committee at this time is Finnish Measurement Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Systems Limited, Outilantie 3, Fin-83750 Sotkuma, Finland. If you are aware of listed by the American Chemical Society, see Analar Standards for Laboratory
alternative suppliers, please provide this information to ASTM International Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
Headquarters. Your comments will receive careful consideration at a meeting of the and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
responsible technical committee,1 which you may attend. MD.

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 D7112 – 09
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FIG. 1 PORLA Heavy and Crude Oil Stability and Compatibility Analyzer

9. Hazards 10.3 Ensure that the sample is homogeneous before with-

9.1 Place the analyzer in a fume hood or similar well drawing an aliquot or test specimen for testing.
ventilated area to minimize exposure of operators to harmful 10.4 To avoid changes or degradation of oil samples,
vapors. minimize exposure to air, temperatures above 25°C, and light.
9.2 Operators should use proper protective laboratory cloth- Store samples in sealed, opaque containers such as metal cans
ing and gloves to avoid skin exposure to oil samples and or dark glass bottles.
solvents. In addition, operators should be careful when han- 11. Preparation of Apparatus
dling hot oil containers when preparing the stock solutions
from very viscous oils as oil spills on exposed skin will cause 11.1 Review the operations manual for the apparatus,6 and
burns. follow all recommended steps. The following actions summa-
rize the preparation of the apparatus:
10. Sampling and Test Specimens 11.1.1 Place the apparatus on a level surface, in a well-
ventilated area such as a fume hood.
10.1 Obtain samples in accordance with procedures de-
11.1.2 Connect the analyzer and the computer to a suitable
scribed in Practices D4057 or D4177. Ensure that samples are
ac power source, and connect the analyzer, keyboard, monitor,
representative of the whole batch of oil.
and mouse to the computer with the cables supplied.
10.2 A minimum sample size of 40 g is required for a single
test. It is preferable to collect a larger sample such as 200 to
500 g to allow for multiple testing, if necessary. 6
Obtain the operator’s manual from the supplier of the apparatus.

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 D7112 – 09

FIG. 2 Schematic Diagram of PORLA Heavy and Crude Oil Stability and Compatibility Analyzer

is empty. Connect the three plastic bottles, labeled aromatic

solvent, paraffinic solvent and waste, to the appropriate lines
from the analyzer.
11.1.4 Switch the analyzer on using the rocker switch on the
back panel. A green lamp will illuminate on the upper right of
the front panel.
11.1.5 Switch on the computer and allow it to boot up.
11.1.6 Select either PORLA Step or PORLA Test by double
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clicking the mouse on the appropriate icon to bring up the

PORLA Step measurement screen (see Fig. 4) or the system
test screen.

12. Calibration and Standardization

12.1 Pump Calibration—Perform the pump calibration at
the initial set-up and whenever the instrument has been
serviced. When in continuous service, perform pump calibra-
tions monthly to verify the pumping rates.
12.1.1 On the PORLA Step measurement screen (Fig. 4)
select the Parameter screen (see Fig. 5). Calibrate the xylene
and n-heptane pumps by starting the automatic procedure
FIG. 3 Schematic Diagram of PORLA Heavy and Crude Oil under Pump Calibration.
Stability and Compatibility Analyzer Detector 12.1.2 Identify two clean sample cups as ‘xylene’ and
‘n-heptane,’ and accurately weigh to two decimal places. These
are the tare weights of the cups.
NOTE 2—All of the controls for the instrument except for the main 12.1.3 The instrument automatically pumps solvent over a
power switch are accessed by means of the keyboard and mouse of the constant period of time (60 s) into a tared sample cup.
computer.
12.1.4 Weigh the collected solvent and sample cup and
11.1.3 Fill the aromatic and paraffinic solvent bottles with subtract the tare weight of the sample cup to give the weight of
xylene and n-heptane, respectively, and ensure the waste bottle solvent pumped in the set time period (60 s).

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FIG. 4 PORLA Step Measurement Screen

12.1.5 Enter the weight of solvent collected in the appro- in the instrument. However, evaporation of xylene does occur when
priate screen. several sample cups sit in the sample carousel during the fully automatic
12.1.5.1 For the xylene pump rate, the instrument calculates mode of operation.
the updated pump rate in g/s and displays it in the appropriate
13. Quality Control Monitoring
field in the parameter screen.
12.1.5.2 For the n-heptane pump rate, the instrument calcu- 13.1 Confirm the performance of the instrument and test
lates the updated pump rate and displays it in mL/s in the procedure by analyzing quality control (QC) samples.
appropriate field in the parameter screen. 13.1.1 The QC sample(s) should be a stable and homoge-
12.2 Evaporation Correction Coeffıcient—Determine the neous residual fuel oil or crude oil similar in composition and
evaporation correction coefficient for the xylene by weighing viscosity to the type of samples routinely tested, and containing
(accurate to two decimal places) a sample cup containing a from 1 to 10 mass % asphaltene. Asphaltene content may be
stock solution after 0.5, 1.0, and 1.5 h of standing in the sample measured by Test Method D6560.
carousel and calculate the average solvent loss by evaporation 13.2 Prior to monitoring the measurement process, deter-
in g/h. Input this information into the PORLA parameter mine the average value and control limits for the QC sample
screen, which is accessed by means of the Parameter button in (see Practice D6299 and Section 3 of Manual 77).
the PORLA Step measurement screen.
12.2.1 Verify the evaporation correction coefficient quar- 13.3 Record QC results and analyze by control charts or
terly when the instrument is in continuous service. other statistically equivalent techniques to ascertain the statis-
12.2.2 If a specific sample contains volatile components, tical control status of the total test process.7,8 Investigate any
such as a whole crude oil, use the semi-automatic Light Ends
mode of operation. In this mode of operation, evaporation is
minimized by loading the stock solution cups one at a time into 7
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis , 6th
the carousel. See 14.9. edition, Section 3: Control Chart for Individuals. Available from ASTM Interna-
tional Headquarters.
NOTE 3—No significant evaporation of solvent or sample occurs during 8
In the absence of explicit requirements given in the test method, this clause
the titration procedure because the sample cup is sealed in the test position provides guidance on QC testing frequency.

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 D7112 – 09

FIG. 5 PORLA Parameter Screen

out-of-control data for root cause(s). The results of this high, warm up the oil in an oven before shaking. A temperature
investigation may, but not necessarily, result in instrument of 80°C is normally sufficient.
recalibration. 14.1.3 Weigh out 20 g of the xylene into the sealable
13.4 The frequency of QC testing is dependent on the container (bottle), accurate to two decimal places, and then add
criticality of the quality being measured, the demonstrated 40 g of the oil, also weighed to two decimal places.
stability of the testing process and customer requirements.8 14.1.4 Shake the stock solution container until the oil has
Generally, a QC sample should be analyzed each testing day dissolved in the xylene. Ensure that the oil has completely
for routine samples. The QC frequency should be increased if dissolved before proceeding. A visually homogeneous stock
a large number of samples are routinely analyzed. However, solution mixture usually indicates complete dissolution of oil
when it is demonstrated that the testing is under statistical in the xylene.
control, the QC testing frequency may be reduced. The QC 14.1.5 In the case of oil samples that are very difficult to
sample testing precision should be periodically checked against dissolve, use a refluxing device instead of shaking the bottle.
the ASTM method precision to ensure data quality.7 When using the refluxing device, let the stock solution cool
13.5 It is recommended that, if possible, the type of QC down before pouring it into the sealable container.
sample that is regularly tested be representative of the samples
14.2 Test Information and Instrument Settings:
routinely analyzed. An ample supply of QC sample material
14.2.1 Open the PORLA Step measurement screen and type
should be available for the intended period of use, and shall be
in the operator’s name and sample name in the appropriate
homogeneous and stable under the anticipated storage condi-
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fields.
tions.
13.6 See Practice D6299 and Manual 77 for further guid- 14.2.2 Type in the oil and xylene weights, accurate to two
ance on test method QC and control charting techniques. decimal places, used in the preparation of the stock solution, in
the appropriate fields.
14. Procedure 14.2.3 Type in the density of a crude oil sample, in g/mL at
14.1 Sample Preparation: 15°C, in the appropriate field, if compatibility parameters are
14.1.1 Stock Solution—Prepare a stock solution in a seal- desired. Determine density by a method appropriate to the
able container such as a screw cap glass bottle (volume about sample type, if required.
100 mL) from 40 g of the oil under test and 20 g of xylene, as 14.2.4 Select xylene from the drop down list of aromatic
described below. solvents displayed under Aromatic.
14.1.2 Thoroughly mix the oil by vigorously shaking the 14.2.5 Before each test, ensure that there is an adequate
sample container for at least 2 min. If the viscosity of the oil is volume of solvent in the aromatic (xylene) and paraffinic

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 D7112 – 09
(n-heptane) solvent bottles, and the waste bottle has capacity to 14.8 Select the specific titration method to determine the
accept the volume of waste from the test. xylene dilution rates applied by the analyzer and the amount of
stock solution to be placed in each sample cup.
NOTE 4—If the n-heptane bottle is empty, or runs empty during a test,
the instrument will continue pumping air until the total pumped volume 14.9 The analyzer can be run in fully automatic mode or
equals the volume set for the cup (typically set at 55 mL), at which point semi-automatic mode. Select the mode from a drop down list
the instrument will shut down and display the message Sample cup full. directly above the method list (see Fig. 4). Normal Operation
14.3 The test method is normally performed at laboratory is the fully automatic mode and Light Ends is the semi-
ambient temperature. If particular properties of a sample, such automatic mode.
as high viscosity, require testing at an elevated temperature, set 14.9.1 Use the Light Ends mode only when the oil contains
a suitable temperature using the hot plate control and record the a significant amount of volatile components which could be
temperature of the test with the results. lost by evaporation if several sample cups were stored in the
carousel for an extended period of time (see 12.2). In the Light
NOTE 5—The temperature of the test is normally slightly above ambient
due to heat generated in the apparatus. Testing and results during
Ends (semi-automatic) mode, place one sample cup in the
development of the test method have not indicated any affect of such slight carousel at a time. When the analyzer stops after each titration,
temperature variations. place the next sample cup in the carousel.
14.4 If the sample is totally unknown, determine the order 14.10 Fill three sample cups with the amounts of stock
of magnitude of the n-heptane consumption using the follow- solution indicated in the three fields directly below the Test
ing fast screening procedure. Run field, weighed to an accuracy of two decimal places, and
14.4.1 Weigh out about 15 g of stock solution, accurate to place the sample cups in the sample carousel. Modify the
two decimal places, into a sample cup and place the cup in weights in these fields to reflect the actual weights of the stock
position No. 1 in the sample carousel. solution used and type in the carousel positions in the fields
directly to the right of these weights.
14.4.2 Enter the sample weight, accurate to two decimal
places, into the Test Run field and enter 0 in the adjacent 14.11 Set the measurement parameters that are displayed in
Paraffin mL field. the Parameter screen to the expected optimal values for each
14.4.3 Start the measurement with the Start button. The type of sample.
analyzer will continuously add paraffinic solvent until the 14.11.1 Cleanse Cycles—Determines the number of wash-
asphaltenes precipitate as indicated by the Intensity bar and ing cycles (using xylene) the program performs after the
Intensity screen, which will read full scale and 10.00 respec- complete analytical procedure. Use a minimum of two washing
tively. cycles, but three cycles is recommended. The analyzer per-
14.4.4 Read the amount of n-heptane consumed from the forms one washing cycle after the analysis of each sample.
Paraffin mL field directly below the Intensity field. 14.11.2 Circulation Time—Determines how long the sample
14.5 After performing the fast screening procedure, or from is circulated through the detector after the mixing period,
previous testing, divide the total n-heptane consumption by 20 followed by the xylene addition before the intensity measure-
to obtain the approximate correct step size for the main ments are started. Set 60 to 70 s, which is normally sufficient
measurement. Type this calculated step size into the appropri- circulation time to give a consistent result.
ate field in the parameter screen. 14.11.3 Suction Line Empty Time—Determines how long
14.6 Enter the total expected n-heptane consumption for the the circulation pump operates to empty the detector after each
test sample, determined in 14.4.4 or known from prior expe- measurement. Set 30 s, which is normally sufficient.
rience, into the Paraffin mL field to the right of the Test Run 14.11.4 Mixing Time—Determines how long the sample is
field. mixed after the aromatic solvent addition, before starting the
14.7 Select the titration method to be used from a drop circulation of the sample solution to the detector. 60 s is usually
down list to the right of the Start button (Fig. 4). sufficient.
14.7.1 Select Low Floc. Rate, which is the normal opera- 14.11.5 Paraffın Pump Rate—Determines the pumping rate
tion, for high stability products such as crude oils, straight run of the n-heptane pump. The pumping rate is adjustable. Set the
residues, and residues from visbreaking and lower severity pumping rate at 0.05 mL/s.
hydrocracking processes. 14.11.6 Aromatic Pump Rate—Determines the pumping
14.7.2 Select High Floc. Rate for low stability oils such as rate of the xylene pump. Set the pumping rate at 0.07 g/s.
residual products from very severe cracking processes. Low
14.11.7 Exhaust Pump Rate—Determines the pumping rate
stability oils typically have an FR5/1 above 0.7.
of the exhaust pump, which will empty the sample cups after
NOTE 6—For Low Floc. Rate the PORLA instrument selects dilution the analyses and washing cycle. Set the rate at 0.4 g/s.
ratios of xylene to oil of 1 : 2, 1 : 1, and 2 : 1. For High Floc. Rate the 14.11.8 Aromatic Dose Time—Determines how long the
PORLA instrument selects dilution ratios of xylene to oil of 2 : 1, 3 : 1,
xylene is pumped for each washing cycle. Set the dose time at
and 4 : 1.
45 s.
NOTE 7—A third mode allows the operator to edit the method and select
custom dilution rates. Use of this mode may be useful for research 14.11.9 Cleanse Time(s)—Determines the length of the
purposes but would be a deviation from the standard method. washing time of the detector. Set the washing time at 60 s.
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 D7112 – 09
14.11.10 Cup Capacity—Determines how much solution is 14.11.14 Aromatic Evaporation Rate (g/h)—Determines the
allowed to be pumped into a sample cup before the measure- rate at which the aromatic solvent is evaporating from open
ment program will be interrupted with Sample cup full mes- sample cups while they are standing on the warm plate of the
sage. Spillage of solution from the cups onto the analyzer due sample carousel prior to the analyses. The method for calcu-
to overflow is prevented by the cup capacity limit. While the lating this is described under 12.2.
cup has a nominal capacity of 100 mL, the highest cup capacity 14.12 Press the start button to start the analysis.
value recommended is 55 mL. 14.13 As soon as the analysis has started, an interrupt button
NOTE 8—Samples containing less than 0.05 % asphaltenes will reach will appear to the right of the start button. This allows the
the sample cup full point, and the titration will be terminated automati- analysis to be interrupted immediately, should it be necessary.
cally. 14.14 The analyzer will complete the three titrations that
14.11.11 Paraffınic Step Size—Determines the size (vol- make up the analysis and report the results in numerical and
ume) of n-heptane addition in each step. When analyzing graphical form in the bottom half of the measurement screen.
samples with low stability, use a small step size of 0.3 to 0.5 See Fig. 4 and Fig. 6.
mL. Use a larger step size of 0.5 to 1 mL for normal visbreaker 14.14.1 The computer program plots the flocculation ratio
products and, for high stability products such as crude oil against the ratio of the oil sample to solvent volume. This
residues from atmospheric or vacuum distillation units, use 1 to concentration ratio is used because it gives a straight line
3 mL. relationship.
14.11.12 Step Wait Time—Determines the waiting time 14.15 Values for the solvent ratio and oil-to-solvent ratio for
between n-heptane addition steps. Use 60 to 120 s. each titration are given in the FR field and 1/X field respec-
14.11.13 Paraffınic Start Feed Factor—Determines the per- tively.
centage, shown as a decimal figure (0.4 means 40 %, for
14.15.1 A straight-line graph is shown using a least squares
example) of the expected total n-heptane consumption that will
sum procedure where the intercept on the y-axis is given in the
be added as a first portion to the sample cup. This allows the
FRmax field.
total measurement time to be decreased. If the operator wants
to carry out all of the paraffinic solvent addition in small steps 14.15.2 The extrapolated n-heptane consumption, of the
without the initial larger portion, enter 0 into the Paraffin start undiluted oil, is given in the Xmin field.
feed factor field. An initial portion larger than 0.4 can be used 14.15.3 The slope of the graph is given in the slope field.
for research purposes but shall not be used for this standard 14.15.4 The peptizability or P-value of the asphaltene is
procedure. given in the Pa field.
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NOTE—1/X is the oil to solution ratio, where the solution is the sum of the volumes of the aromatic and paraffinic solvents (xylene and n-heptane).
FIG. 6 Typical Analyzer Plot of Stability Results

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 D7112 – 09
14.15.5 The peptizing power of the oil matrix is given in the where:
Po field. IN = insolubility number,
14.15.6 The correlation factor indicating the significance SBN = solubility blending number,
level of the fitting of the straight line is given in the r2 field. D = density of oil, g/mL,
14.16 The stability parameters, P-value and flocculation SE = aromatic solvent equivalent, volume %, and
ratio at a dilution of 5 mL solution to 1 g of oil, are given under VH = volume of paraffinic solvent that can be added to 5
the P-value and FR5/1 fields, respectively. mL of oil without asphaltene precipitation.
14.17 If the crude oil compatibility option software is
installed and the density of the oil under test has been entered 16. Report
into the D (g/mL) field at the start of the measurement, the 16.1 Report the following information:
crude oil blending model parameters of insolubility number 16.1.1 The identity of the sample,
(IN) and solubility blending number (SBN) will be displayed in 16.1.2 The stability parameters: SE, P-value, and FR5/1,
the IN and SBN fields, respectively. 16.1.3 The compatibility parameters: IN and SBN, if deter-
mined,
15. Calculation of Results 16.1.4 Reference to this test method, and
15.1 The instrument automatically calculates the stability 16.1.5 If an elevated temperature above ambient room
parameters by linear regression and by extrapolation (see Fig. temperature was used, report the temperature of the test.
4), using the following equations:
Varom 17. Precision and Bias 9
FR 5 (1)
~Varom 1 Vpara! 17.1 Precision—The precision statements for P, Pa, Po, and
SE 5 ~FR5/1!~100 %! (2) FR5/1 are based on results from an interlaboratory study that
1 Moil
involved 11 samples (heavy fuel oils, atmospheric and visbro-
X 5 ~Varom 1 Vpara! (3) ken residues and crude oils) that contained from 0.7 to 22.5 %
by mass asphaltenes as measured using Test Method D6560.
P 5 1 1 Xmin (4)
Five operators used three instruments at one location to
Pa 5 1 2 FRmax (5) develop the repeatability precision. The recommended ranges
Po 5 ~FRmax!P or Po 5 ~FRmax!~1 1 Xmin! (6) for applicability of the precision follow. The recommended
precision range is determined by:
where: Parameter r Recommended
FR = flocculation ratio, Precision Range
FR5/1 = flocculation ratio at a dilution of 5 mL solution to P 0.103*X 1.28 – 4.54
1 g of oil, Pa 0.03 0.33 – 0.83
FRmax = maximum flocculation ratio (at 1/X = 0), Po 0.2 0.43 – 1.31
SE = aromatic solvent equivalent, expressed as a per- FR5/1 0.03 0.05 – 0.62
where: X is the average of the measured results.
cent value,
1/X = oil to solution ratio, g/mL, NOTE 9—The precision of this test method may not apply to samples
Xmin = paraffinic solvent consumption of undiluted oil, outside the range of materials examined in the research report.
mL/g of oil (at FR = 0), 17.1.1 Repeatability—The difference between successive
Moil = mass of oil, g, results obtained by the same operator with the same apparatus,
Varom = volume of aromatic solvent in the mixture, mL, under constant operating conditions, on identical test materials
Vpara = volume of paraffinic solvent in the mixture, mL, would, in the long run, in the normal and correct operation of
P = P-value of an oil, this test method, exceed the values in 17.1 only in one case in
Pa = peptizability of an asphaltene, and twenty.
Po = peptizing power of the oil matrix.
The recommended precision range is determined by:
15.2 The instrument uses the following equations to deter-
(min. sample mean – repeatability) to (max. sample mean +
mine compatibility parameters of crude oil samples, if re-
repeatability).
quired:
SE
IN 5 (7)
~1 2 VH/25D! 9
Supporting data have been filed at ASTM International Headquarters and may
SBN 5 IN~1 1 VH/5! (8) be obtained by requesting Research Report RR: RR:D02-1675.

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 D7112 – 09
17.1.2 Reproducibility—Reproducibility has not been 18. Keywords
evaluated because it is not relevant to the intended application
18.1 asphaltene precipitation; asphaltenes; compatibility;
of this test method, and typical samples are sufficiently
crude oil; heavy fuel oil; insolubility number; P-value; residual
unstable that results from different laboratories, performed at
oil; solubility blending number; solvent equivalent; stability;
different times on samples that have been exposed to varying
storage conditions, will be suspect. stability reserve
17.2 This test method has no bias because the results of the
test are defined only in terms of this test method.

SUMMARY OF CHANGES

Subcommittee D02.14 has identified the location of selected changes to this standard since the last issue
(D7112–05a) that may impact the use of this standard.

(1) Updated precision in Section 17. (2) Deleted Appendix X1.

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