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Documents - Pub - Simdis Simulated Distillation PDF
Documents - Pub - Simdis Simulated Distillation PDF
To develop an accurate and rapid evaluation of distillation yield curves of heavy crude oils,
simulated distillation by gas chromatography (SIMDIS GC) curves were performed for the first
time in Mexican Istmo and Maya crude oil samples. In this study, we found large uncertainties
using ASTM D-5307, and some improvements to the technique were applied as alternatives to
measure the assay distillation. These results were compared with the curves obtained from the
physical distillation method outlined in ASTM Method D-2892, showing good agreement. The
statistical analysis of the SIMDIS data is addressed as a good alternative for measuring these
heavy crude oils.
GC-vacuum thermogravimetry,15 or high-performance °C and the injector was programmed to operate from 100 °C
liquid chromatography (HPLC)-evaporative light scat- to 430 °C, at a rate of 15 °C/min, and the detector was
tering detector.16 The method of high temperature for programmed to operate from 50 °C to 430 °C, a rate of 10 °C
simulated distillation (HT SIMDIS), as described in /min. The chromatogram was integrated over a period of 44
min, and the final temperature of the oven continued for 10
ASTM Method D-5307, have not been extensively
min to clean the system. The injector temperature was
proven by the oil industry, because of the existence of maintained for 2 min.
many problems in the preparation and nonhomogeni-
Preparation of the Sample. The samples were previously
zation of the sample. These problems must be solved, stored at a temperature of 0-5 °C for at least 4 h before
because, to obtain reliable results, a quantitative method exposing them to the environment. To ensure homogeneity,
requires a rigorous and exact mass balance. In this the heavy and viscous crude may require warming, as well as
paper, we wish to describe a strategy for developing and stirring. The samples should be dried with anhydrous calcium
optimizing an appropriate methodology for the rapid chloride or sodium sulfate by shaking the mixture of sample
evaluation of distillation yield curves in Mexican crude and drying agent vigorously. According to ASTM Method
oils using GC SIMDIS described in ASTM Method D-5307, the low-viscosity liquid samples can be analyzed
D-5307. In addition, an expeditious and improved directly. The dried sample is removed from the desiccant using
methodology for preparing heavy oil samples is de- a pipet and accurately weighted (0.15-0.20 g) in a 25 mL
volumetric flask and dissolved with 10 g of carbon disulfide.
scribed. Also, a comparison with the results of physical
The solution was weighed, and it had a concentration of ∼2%.
distillation (ASTM Method D2892) tests was per- Two milliliters of this solution was withdrawn and poured into
formed.5 a vial that had been weighed; this sample should be considered
as the sample without internal standard. The remainder of
Experimental Section the solution was weighed after this process and then a weighed
quantity of internal standard (20 µL, measured in a tared 100
The samples of Istmo and Maya crude oil were supplied from µL syringe) was added to the remaining solution and mixed
Pemex. Carbon disulfide (99.00%) was purchased from Aldrich by shaking. As done previously, 2 mL of this solution was
Chemical Company. A mixture of n-alkanes C5 through C98 poured into a vial and should be considered as the sample with
(Polywax 655) was purchased from Analytical Control U.S.A. internal standard.
A mixture of n-alkanes C14, C15, C16, and C17, which were Physical Distillation. This procedure was performed
used as internal standards traceable to the National Institute according to ASTM Method D-2892. The water-free crude was
for Standards and Technology (NIST), was purchased from tested using columns of 15 theoretical plates under a relation-
Hewlett-Packard. A mixture of n-alkanes C5 through C44 was ship of reflux of 5:1; this method is known as the true boiling
used as a reference in the SIMDIS analysis, for comparison point (tBP) assay. The distillation started under barometric
and validation of the test. pressure (760 mm Hg) and is continued later under vacuum
The analyses were performed with a Hewlett-Packard model conditions (5-100 mm Hg) at 370 °C. The boiling points are
HP 6890-II gas chromatograph that was equipped with a flame converted to their equivalent value at 1 atm (AEBP). At this
ionization detector (FID) with an outlet diameter of 0.30 mm, point, the method was changed to the corresponding ASTM
a liquid nitrogen cryogenic system, automatic injection for Method D-5236 procedure, in which the distillation continued
eight vials, and software for calculation of the SIMDIS at a pressure of 0.5 mm Hg until reaching a limit near the
methods. The column used was 5-6 m long, comprised of AEBP (538 °C). Conversion charts for the conditions of AEBP
stainless-steel capillary columns 0.53 mm in diameter, and are included in the method.
filled with methyl silicon, and the film thickness was 0.09-
0.15 µm, respectively. The carrier gas was helium (99.999%
purity), with a flow of 20 mL/min and an inlet pressure of 80 Results and Discussion
psi. The injector and detector temperatures were each 430 °C.
The combustible gas for feeding the detector was hydrogen For the purposes of this study, four analyses were
(99.999% purity), with an inlet pressure of 60 psi and a flow performed with two different crude oils from the two
rate of 35 mL/min and air (99.999%, chromatographic grade) following categories: Istmo crude (20-30 °API, 0.8932
with an inlet pressure of 80 psi and a flow rate of 350 mL/ g/cm3) and Maya crude (<20 °API, 0.9238 g/cm3). In
min. The FID is highly sensitive (5 pg C/s) to hydrocarbons, addition, two repeatability experiments and two repro-
which allows for detection of the high-boiling-point compo- ducibility experiments for each operator were per-
nents, such as heavy crude oil and their fractions. The detector formed, according to the procedure described for ASTM
has a low sensitivity to carbon disulfide, which allows injection Method D-5307. The comparison between the two
of the dissolved crude oils into the chromatograph. Although
analyses allows the percentage of the eluted sample to
the FID is a mass-dependent detector, the analytic results are
comparable to the results of a physical distillation expressed
be calculated, up to a temperature of 538 °C. Basically,
in terms of a volume percentage. ASTM Method D-5307 is an extension of ASTM Method
Conditioning of the Column. The column was condi- D-2887, but the addition of a standard is not required.
tioned without being connected to the detector, by purging with By considering this stipulation, the strategy consisted
helium at low temperature. The column outlet was covered of performing an initial analysis for a calibration
immediately with an appropriate seal. The flow of helium was mixture of C5 to C44 linear paraffins, under the same
continued for 2-3 h at 430 °C. The oven was cooled at 100 °C, conditions of the sample analysis under which all the
and the seal was removed, to re-establish the helium flow in assignments were performed, by comparison with this
the column. The equipment was programmed 2-3 times at curve. Figure 1 shows a chromatogram with a boiling-
the operation conditions and the column was connected to the point (BP) distribution of the C5-C44 paraffin mixture,
detector. The equipment was stabilized at the required condi- as well as a plot of the calibration curve. At high
tions. The oven was programmed to operate from 40 °C to 430
temperature, the samples should be eluted up to 430
°C, which is equivalent to atmospheric conditions.
(15) Southern, T. G.; Iacchelli, A.; Cuthiell, D.; Selucky, M. L. Anal.
Chem. 1985, 57, 303-308. Therefore, elution of the C44 paraffin, which has a BP
(16) Padlo, D. M.; Kugler, E. L. Energy Fuels 1996, 10, 1031-1035. >538 °C, is conducted at 430 °C. Under these conditions,
1834 Energy & Fuels, Vol. 18, No. 6, 2004 Espinosa-Peña et al.
Figure 1. Chromatogram (top) and calibration curve (bottom) for the mixture C5-C44.
no evidence of cracking has been visualized. In the the corresponding peaks is good, which avoids satura-
selected chromatographic conditions, the separation of tion of the column. For the heavy crude oil, the sample
Distillation Yield Curves in Heavy Crude Oils Energy & Fuels, Vol. 18, No. 6, 2004 1835
internal standard, 0.0000 g; elution at start, 0.00; elution at end, <24.43; found recovery, 102.0%; and used recovery, 100.0%. b Initial
boiling point. c Final boiling point.
is not eluting completely in the chromatographic col- standard allows calculation of the relationship that
umn, and, thus, area normalization cannot be applied. exists between the area of the second segment and the
The sample then must be analyzed in duplicate. In the sum of the areas of the first and third segments. For
first run, the sample without an internal standard is practical purposes, the response factor in each inte-
analyzed, whereas in a second run, the sample with an grated segment is considered to be 1.17 The response of
internal standard is analyzed. The comparison between the detector is proportional to the distilled quantity for
two analyses allows calculation of the percentages of each BP interval, and it is equivalent to the percentage
sample that were eluted up to 538 °C. With these values, of this response, with respect to the total response of
these percentages are re-normalized from interval- the components in the analyzed mixture. Because of the
calculated BPs on the corresponding normalized curve regularity of elution order, the retention times can be
of distillation for the analysis of the sample without correlated with BP temperatures, the graphic represen-
internal standard. tation of which is a straight line (see Figure 1). The
For quality assurance, the reference gas oil that was empiric correlation between retention time and BP
analyzed by physical distillation was also analyzed by temperature is established using a mixture of n-paraffin
SIMDIS after and before each sequence of samples. that covers the expected BP interval. Although these
Results are reported in terms of mass percentage in calculations can be performed automatically by the
Table 1 and as the SIMDIS curve in Figure 2. SIMDIS software, they can be calculated empirically by
The BP distribution in Maya crude is described for a integrating the areas of each segment in both chromato-
mass fraction of 59.4 mass %, in which the initial boiling grams.12
point (IBP) was 36 °C and the final boiling point (FBP) The usefulness of any method, in regard to its ability
was 545 °C (see Table 2). The residue fraction is to determine the tBP curves, is greatly dependent on
estimated to be 40.6 mass %. In the Istmo crude, the its ability to provide repeatable data. Therefore, it is a
BP distribution is given for 80 mass % crude and 20 fundamental requirement to obtain tBP curves with the
mass % residue. The corresponding chromatograms of maximum level of repeatability possible. According to
Maya crude with and without internal standard are ASTM Method D 5307-97, the established repeatability
showed in Figure 3. In these chromatograms, the and reproducibility values in Maya and Istmo samples
quantitative calculations are illustrated and were per- are compared to the corresponding obtained values in
formed using the re-normalization area method: the tBP. Table 3 presents this data as a temperature
chromatogram of the eluted sample is divided in three fluctuation (twice the standard deviation), in terms of
segments, each of which represents the percentage of degrees centigrade, observed for different intervals of
total area and the total volume of the sample whose BP weight percent. Taking into account an average of four
interval corresponds to the assigned temperature and determinations for two different operators, these values
the respective retention time. The first segment (de- are very satisfactory, in regard to mass percent and even
noted as A or B) corresponds to the total area of the volume percent.
sample (crude with or without internal standard) that To describe the improvements of the SIMDIS method
is eluting up to 538 °C, and the second segment (denoted in heavy Mexican crude oils over the physical distillation
as AIS or BIS) is the total area of the internal standard method, a comparison of both methods was performed;
in the chromatogram either with or without the internal
standard. The third segment (denoted as AI or BI) (17) Villanti, D. C.; Maynard, J. B.; Aryan, J. C.; Frayed, A. A. Yield
Correlation between Crude Assay Distillation and High-Temperature
describes the area of the noneluted sample after 538 Simulated Distillation (HTSD). Presented at the 1997 AIChE Spring
°C. The chromatogram of the sample without internal National Meeting Houston, TX, March 9-13, 1997.
1836 Energy & Fuels, Vol. 18, No. 6, 2004 Espinosa-Peña et al.
Figure 2. Boiling-point distribution plot showing the simulated distillation (SIMDIS) curve for reference gas oil.
0.0100 g; elution at start, 0.04; elution at end, <24.46; found recovery, 59.4%; and used recovery, 59.4%. b Initial boiling point.
this comparison showed good agreement, in terms of percentage values from the SIMDIS method. Before
either mass percent or volume percent (see Figures 4 these values are correlated to determine the corre-
and 5). These comparisons were evaluated by the sponding values for volume percentage in the SIMDIS
standard deviation parameter (σn-1). The value of this method (see Table 5), the standard deviation indicates
feature, in terms of mass percent, for IBP to FBP of that the values are in good agreement. The best values
Maya crude was in the range of 0.0-9.60 for physical of σn-1 are observed for the SIMDIS method, in com-
distillation and 0.0-6.71 for SIMDIS; for Istmo crude, parison to physical distillation. For Maya crude oil, in
the σn-1 value was 0.0-6.92 for physical distillation and terms of volume percentage, the σn-1 value from IBP to
0.0-0.25 for SIMDIS (see Table 4). FBP is 0.0 to 0.00 using the SIMDIS method, which
Determination of the volume percentage using the shows slight differences from IBP to FBP (σn-1 is 0.069
SIMDIS method is highly desirable, because the major- to 1.7). For Istmo crude oil, the σn-1 value for physical
ity of refinery operations are based on volume percent- distillation from IBP to FBP is 2.6 to 0.00, and the
age rather than mass percentage. A plot of mass SIMDIS method exhibits a σn-1 value of 1.8 to 1.8.
percentage versus volume percentage is constructed for The SIMDIS results are dependent on the baseline
the physical distillation results. The obtained curve and the required correction for compensating the con-
allowed interpolation between the mass and volume tinuous partial loss of the stationary liquid phase,
Distillation Yield Curves in Heavy Crude Oils Energy & Fuels, Vol. 18, No. 6, 2004 1837
Figure 3. Chromatograms of Maya crude with internal standard (top) and without an internal standard (bottom).
1838 Energy & Fuels, Vol. 18, No. 6, 2004 Espinosa-Peña et al.
Figure 4. Comparison between physical distillation and SIMDIS mass curves (top) and volume curves (bottom) in Maya crude.
Legend for mass curve: ([) physical distillation, (0) SIMDIS 1, and (4) SIMDIS 2. Legend for volume curve: ([) physical distillation
and (4) SIMDIS.
because of the high operation temperatures of the manipulation: the previous registration of the weights
chromatograph. The chromatograph has a specific de- during the sample preparation for each vial diminishes
vice in place to subtract the baseline in each chromato- the systematic error.
gram electronically. The reproducibility and precision The differences of statistical error, or the confidence
of the results is achieved with automatic injection. Note interval, between both physical and simulated distilla-
the possible evaporation of the solvent during the tion curves are reported in Table 6. The values for the
Distillation Yield Curves in Heavy Crude Oils Energy & Fuels, Vol. 18, No. 6, 2004 1839
Figure 5. Comparison between physical distillation and SIMDIS mass curves (top) and volume curves (bottom) in Istmo crude.
Legend for mass curve: (9) physical distillation, (*) SIMDIS 1, and (b) SIMDIS 2. Legend for volume curve: ([) physical distillation
and (9) SIMDIS.
Table 4. Comparison between Physical Distillation and SIMDIS, on the Basis of Mass Percentage, for Maya and Istmo
Crude Oils
Maya Crude Istmo Crude
Physical Distillation SIMDIS Physical Distillation SIMDIS
boiling point, boiling point, BP (°C) boiling point, boiling point, BP (°C)
mass % BP (°C)a σb mass % (1)c (2)d σb mass % BP (°C)a σb mass % (1)c (2)d σb
0.5 37.5 0.00 0.5 36.0 36.0 0.00 0 0.0 0.00 0.5 36.0 36.0 0.00
5.0 115.0 3.60 5.0 100.5 100.5 0.00 5 80.0 2.94 5.0 89.0 89.0 0.00
10.0 160.0 3.05 10.0 155.0 157.0 1.76 10 114.5 2.49 10.0 123.5 126.0 1.25
20.0 250.0 4.04 20.0 249.0 254.0 3.53 20 173.5 3.29 20.0 180.0 184.0 2.00
30.0 320.0 3.21 30.0 329.0 334.5 3.88 30 235.5 2.64 30.0 238.0 242.5 2.25
40.0 400.0 4.16 40.0 405.0 412.5 5.30 40 287.5 3.39 40.0 293.5 297.5 2.00
50.0 476.0 5.03 50.0 479.0 488.5 6.71 50 341.5 4.10 50.0 349.0 351.5 2.00
55.0 516.0 4.04 55.0 514.0 523.0 6.36 60 401.5 3.29 60.0 405.0 409.0 2.00
58.0 538.5 9.60 58.0 533.0 542.5 6.71 70 473.5 5.43 70.0 468.5 470.5 1.00
77 534.0 6.97 80.0 542.0 541.5 0.25
a Average of four determinations. b Standard deviation. c Results for operator 1 in SIMDIS. d Results for operator 2 in SIMDIS.
SIMDIS method are less than the corresponding values in comparison to Istmo crude. Heavy or very heavy
for physical distillation. In SIMDIS, the confidence crude oils can be analyzed by following the improved
intervals after 430-538 °C are greater for Maya crude, methodology described here.
1840 Energy & Fuels, Vol. 18, No. 6, 2004 Espinosa-Peña et al.
Table 5. Comparison between Physical Distillation and SIMDIS, on the Basis of Volume Percentage, for Maya and
Istmo Crude Oils
Maya Crude Istmo Crude
Physical Distillation SIMDIS Physical Distillation SIMDIS
boiling point, boiling point, boiling point, boiling point,
vol % BP (°C)a σb vol % BP (°C)a σb vol % BP (°C)a σb vol % BP (°C)a σb
0.5 37.7 0.000 0.5 36.0 0.691 0.5 25.7 2.625 0.5 0.5 1.871
10.0 138.0 1.750 10.0 126.5 1.312 10.0 80.0 2.494 10.0 110.0 1.027
20.0 210.0 1.732 20.0 216.5 1.080 20.0 104.3 1.700 20.0 151.0 1.650
30.0 280.0 5.011 30.0 287.5 2.248 30.0 153.0 3.682 30.0 209.0 1.650
40.0 348.0 5.563 40.0 358.0 1.700 40.0 204.3 2.161 40.0 264.5 2.494
50.0 420.7 3.857 50.0 435.0 1.841 50.0 256.0 3.742 50.0 308.0 1.312
60.0 497.3 2.142 60.0 510.0 1.027 60.0 309.0 5.312 60.0 363.0 1.871
64.9 538.0 0.000 64.5 542.0 1.700 70.0 428.7 3.682 70.0 427.0 0.850
80.0 506.7 5.793 80.0 498.0 3.082
84.5 538.0 0.000 84.5 542.0 1.841
a Average of four determinations. b Standard deviation.
Table 6. Comparison of Physical Distillation (ASTM D-2892) and SIMDIS (ASTM D-5307) in Maya and Istmo Crude Oils
Maya Crude Istmo Crude
Physical Distillation SIMDIS GC Physical Distillation SIMDIS GC
avg BP confidence avg BP confidence avg BP confidence avg BP confidence
mass % (°C)a rangea mass % (°C)a rangea mass % (°C)a rangea mass % (°C)a rangea
Operator 1 Operator 2
0 37.67 (16.1 1 46.5 (10.5 0.5 25.66 (2.62 0.5 36 (0.00
10.7 166.66 (6.6 10 159.00 (8.5 10.7 144.66 (2.94 10 123.50 (1.25
20.8 254.33 (5.25 20 249.50 (5.5 20.8 173.66 (3.30 20 180.00 (0.50
31.5 334.67 (2.49 30 328 (1.0 31.5 235.33 (2.62 30 239.50 (2.25
41.0 406.67 (5.73 40 403 (1.75 41.0 287.66 (3.40 40 295.00 (2.0
58.3 538.00 (0.00 50 477 (4.0 58.3 341.00 (4.11 50 349.25 (2.0
58.4 538.5 (4.0 60.5 401.66 (3.30 60 407.25 (1.00
70.9 473.66 (5.43 70 469.50 (0.25
80.0 538.00 (0.00 80 545.00 (0.00
Operator 2 Operator 2
1 43.5 (7.5 0.5 36 (0.00
10 164.25 (9.25 10 122.25 (2.25
20 252.5 (3.5 20 180.0 (0.50
30 328.75 (0.25 30 239.25 (1.25
40 402 (3.0 40 295.50 (1.75
50 473.75 (5.25 50 349.00 (1.75
58.4 539.75 (5.25 60 407.25 (1.25
70 469.50 (0.25
80 545.00 (0.00
a Average of four determinations.