The Distillation Group, Inc.

P.O. Box 10105, College Station, TX 77842-0105 USA Phone 409-764-3975

[email protected] Fax 409-764-1449
Yield Correlations Between Crude Assay Distillation
And High Temperature Simulated Distillation (HTSD)
Reprint distributed with permission from the copyright holders.
Copyright D.C. Villalanti, J.B. Maynard, J.C. Raia, and A.A. Arias (1997)
All rights reserved.
Not to be uploaded to any other site without
written permission from the copyright
holders.
Distributed by
The Distillation Group, Inc.
P.O. Box 10105
College Station, TX 77842-0105
USA
[1]-(409)-764-3975
[1]-(409)-764-1449 fax
[email protected]
www.distillationgroup.com
Paper 51b
Yield Correlations between Crude Assay Distillation
And
High Temperature Simulated Distillation (HTSD)
Dan Villalanti, Triton Analytics Corp., 16840 Barker Springs #302, Houston, TX 77084
Jim Maynard, Shell Development Co., P.O. Box 1380, Houston, TX 77001
Joe Raia, Triton Analytics Corp., 16840 Barker Springs #302, Houston, TX 77084
Aaron Arias, Shell Development Co., P.O. Box 1380, Houston, TX 77001
Prepared for Presentation at
The AIChE 1997 Spring National Meeting, Houston, TX
March 9-13, 1997
Distillation Symposium, Distillation Design and Operation: Troubleshooting,
Operation, and Optimization, Paper 51b
Copyright1997 D.C. Villalanti, J.B. Maynard, J.C. Raia, A.A. Arias.
March 1997
"UNPUBLISHED"
"AIChE shall not be responsible for statements or opinions contained in papers or printed
in its' publications"
1
Yield Correlations between Crude Assay Distillation and
High Temperature Simulated Distillation (HTSD)
Dan Villalanti, Triton Analytics Corp., 16840 Barker Springs #302, Houston, TX 77084
Jim Maynard, Shell Development Co., P.O. Box 1380, Houston, TX 77001
Joe Raia, Triton Analytics Corp., 16840 Barker Springs #302, Houston, TX 77084
Aaron Arias, Shell Development Co., P.O. Box 1380, Houston, TX 77001
Prepared for Presentation at the AIChE 1997 Spring National Meeting, Houston, TX.
March 9-13, 1997, Distillation Symposium, Distillation Design and Operation:
Troubleshooting, Operation, and Optimization, Paper 51b
Copyright1997 D.C. Villalanti, J.B. Maynard, J.C. Raia, A.A. Arias.
March 1997
Summary
The ability to rapidly and accurately evaluate the variability of distillation yield curves of
opportunistic crudes and crudes from currently producing fields has increasingly important
economic considerations in refining margins. Recent advances in the analytical laboratory
using gas chromatography techniques have allowed the method of High Temperature
Simulated Distillation (HTSD) to be successfully used in place of the laboratory method
of Crude Assay Distillation (ASTM D2892 and D5236). This paper presents a brief
description of the HTSD analysis (including detailed precision data) and the HTSD yield
curve correlations to Crude Assay distillations for a variety of crudes. By knowing the
statistical significance of the HTSD data generated and the correlation to existing crude
assay, marginal values of various crudes can be derived and the economics evaluated.
In this study, approximately 100 crudes were analyzed by Crude Assay Distillation and
HTSD. To allow a meaningful comparison of the yield curves obtained by Crude Assay
Distillation and HTSD, the crudes were grouped into light, intermediate, and heavy
categories by API gravity. The yield curves are compared at 10 distillation cutpoints. At
each cutpoint, the average percent weight (%weight) differences between Crude Assay
Distillation and HTSD are summarized for each API Gravity grouping. In addition, the
estimated precision of the correlation between Crude Assay Distillation and HTSD at each
distillation cutpoint is presented.
2
Crude Assay Distillation
ASTM Standard Test Method D2892 for the Distillation of Crude Petroleum defines the
methodology for Crude Assay Distillation. The method uses a 15 plate column operating
under a reflux ratio of 5:1. This is known as TBP or True Boiling Point. The distillation
is usually started at ambient pressure (760mm Hg) and then switched to vacuum
conditions (from 100 and then to 5 mm Hg) to extend the method to about 650F
Atmospheric Equivalent Boiling Point (AEBP). At this point the remaining charge is
transferred to a vacuum potstill method (ASTM D5236) where the distillation continues at
0.5mm Hg, thus allowing an AEBP limit of about 1000-1050F. Conversion tables for the
vacuum conditions to AEBP are included in the method.
Although the Crude Assay Distillation (D2892 and D5236) method provides only an
estimate of the yields of the fractions of various boiling ranges, the results (when properly
and skillfully obtained) are of great importance for the characterization and commercial
trading of crudes.
Several areas that contribute to the variance of the D2892 method include:
1.) Column hold up
2.) Conversion to AEBP from various vacuum settings
3.) Cracking Limits on the maximum distilling temperature are different for different types
of crudes.
4.) Pressure drops across the column.
HTSD Methodology
High Temperature Simulated Distillation
1
(HTSD) is basically an extension of ASTM
method D2887 for the boiling range distribution of hydrocarbons by gas chromatography
(GC). (Figure1). The analysis is calibrated by correlating the C5 to C120 n-paraffins
elution time to their Atmospheric Equivalent Boiling Point (AEBP) as described in API
Project 44. (Figure 2).
A key difference however between HTSD and D2887 is the ability of HTSD to handle
residue containing samples. (i.e. 1000F+) The range of applications
2
for HTSD includes:
Crude Oil Characterization, Cat Crack feed and product, CFH feed and product,
Hydrotreater feed and products, Atmospheric Residue, Vacuum Gas Oils
3
, Deasphalted
Oils, and Vacuum Tower Bottoms (pitch).
3
Under the special conditions of HTSD, elution of materials from the GC column occurs at
up to 500-600F below their AEBP. For instance, the elution of C
110
(AEBP of 1351F)
occurs at about 800F column temperature. Also under these conditions, little or no
evidence of cracking is normally seen in HTSD.
HTSD Precision
The Quality Control (QC) and Quality Assurance (QA) procedures in the lab to assure the
integrity of HTSD must be followed rigorously to ensure statistically meaningful results.
1
The initial QC involved the analysis of a reference oil (Figure 3) that has been physically
distilled by ASTM D2892 (TBP). This material (with FBP<1000F) is used to calibrate
the HTSD system as an external standard for all % recovery calculations. In addition, the
HTSD analysis results are compared to the physical weight distribution data from the true
boiling point (TBP) distillation. The statistical error of the difference between HTSD data
versus TBP is then reported. (Table 1).
For HTSD analysis of crudes, a full, wide boiling range (naphtha and residue containing)
petroleum sample is routinely analyzed for QA. The typical HTSD report for a full range
petroleum sample is shown in Table 2. The HTSD cutpoint statistics for this full range
hydrocarbon are summarized below for 500+ determinations:
HTSD Cutpoint %Weight Std. Dev.
360F 12.7 0.3
480F 19.6 0.3
650F 28.9 0.3
1000F 73.0 0.5
1351F 98.4 0.9
Grouping of Crudes by API Gravity
For the purpose of this study approximately 100 Crudes were analyzed by Crude Assay
Distillation and HTSD and grouped into the following three categories based on API
Gravity (density).
Crude Type API Gravity # of Crudes API Range
Light >30 49 30.1-52.3
Intermediate 20-30 27 20.5-30.0
Heavy <20 8 9.7-19.5
4
The crudes included in this study have a widely varying content of pitch of Pitch, Sulfur,
Nickel, Vanadium, Conradison Carbon or Microcarbon Residue, and Asphaltene.
Comparison of Crude Assay and HTSD
The comparisons of the yield curves (expressed in %weight) of Crude Assay (ASTM
D2892) to HTSD are presented for five typical crudes spanning the range of light,
intermediate, and heavy API gravities. (Figures 4, 5, 6, 7, & 8). Each crude is compared
at the following ten distillation cutpoints:
Cutpoint Number Cutpoint Temperature F
1 68
2 155
3 265
4 350
5 400
6 500
7 600
8 750
9 900
10 1000
In the next series of comparisons, the % weight at each of the ten cutpoints as determined
by HTSD was subtracted from the % weight from Crude Assay Distillation. The average
differences for all the crudes in each of the three API categories are shown in Figures 9,
10, & 11. In addition, these figures also show the estimated standard deviation of the
differences in the yields of Assay (D2298) minus HTSD.
Conclusions
About one hundred crudes ranging in API gravity from light to intermediate to heavy were
analyzed. The comparison of the distillation yield curves (% weight) as determined by
Crude Assay Distillation (ASTM D2892 and D5236) and by HTSD shows good overall
agreement. In general, the difference observed at each cutpoint is < +/-2 % weight
(Figure 12). However, an exception is the cutpoint region from 750F for light and
intermediate crudes and the region from 750-900F for heavy crudes. The 750F cutpoint
is the first cutpoint following the crossover from ASTM D2892 (TBP-15 plate) to D5236
(Vacuum Potstill, 1 plate) conditions. This change in distillation conditions is thought to
5
contribute most of the difference when compared to HTSD, which has no pressure-related
crossover effects.
The precision of HTSD cutpoints up to 1000F is better than 0.5%wt. The estimated
precision of the correlation between Crude Assay Distillation and HTSD yield at each
cutpoint result in a standard deviations of <2% weight except at the crossover point at
750F (Figure 13).
The future opportunities of Crude Characterization by HTSD include:
1.) Tighter precision than conventional lab distillation.
2.) Faster turnaround and less expense than laboratory physical distillation.
3.) Valuable business tool for evaluating new crudes and confirming crude quality before
purchase.
4.) Ensuring crude product integrity during transportation and delivery.
References:
1.) D.C. Villalanti, D. Janson, P. Colle, Hydrocarbon Characterization by High
Temperature Simulated Distillation (HTSD), Session 4b , AIChE Spring Meeting,
Houston, TX., March 19-23, 1995.
2.) S.W. Golden, D.C. Villalanti, G.R. Martin, Feed Characterization and Deepcut
Vacuum Columns: Simulation and Design, Impact of High Temperature Simulated
Distillation, Session 47a, AIChE Spring Meeting, Atlanta, GA., April 18-20, 1994
3.) S.W. Golden, S. Craft, D.C. Villalanti, Refinery analytical techniques optimize unit
performance, Hydrocarbon Processing, November 1995.
Figure 1 Summary of ASTM Physical and Simulated Distillation
HT 750
D2887E
D2887
D3710
BP
D86
D1160
D2892
D5236
C 60
C 44
C 15
125 C 250 C 375 C 500 C 625 C 750 C
257 F 482 F 707 F 932 F 1157 F 1382 F
C 120
C 14
C 25
C 26
C 44
FIGURE 4
11
ASSAY AND HTSD YIELDS
LIGHT CRUDE - API GRAVITY = 50.4
0
20
40
60
80
100
68 155 265 350 400 500 600 650 750 900 1000
BOILING POINT, DEG F
Y
E
I
L
D
,

W
T
%
ASSAY HTSD
FIGURE 5
12
ASSAY AND HTSD YIELDS
LIGHT CRUDE - API GRAVITY = 34.2
0
20
40
60
80
100
68 155 265 350 400 500 600 650 750 900 1000
BOILING POINT, DEG F
Y
E
I
L
D
,

W
T
%
ASSAY HTSD
FIGURE 6
13
ASSAY AND HTSD YIELDS
INTERMEDIATE CRUDE - API GRAV = 24.2
0
20
40
60
80
100
68 155 265 350 400 500 600 650 750 900 1000
BOILING POINT, DEG F
Y
E
I
L
D
,

W
T
%
ASSAY HTSD
FIGURE 7
14
ASSAY AND HTSD YIELDS
HEAVY CRUDE - API GRAVITY = 16.8
0
20
40
60
80
100
68 155 265 350 400 500 600 650 750 900 1000
BOILING POINT, DEG F
Y
E
I
L
D
,

W
T
%
ASSAY HTSD
FIGURE 8
15
ASSAY AND HTSD YIELDS
HEAVY CRUDE - API GRAVITY = 9.7
0
20
40
60
80
100
68 155 265 350 400 500 600 650 750 900 1000
BOILING POINT, DEG F
Y
E
I
L
D
,

W
T
%
ASSAY HTSD
FIGURE 9
CRUDES GROUPED BY API GRAVITIES
16
ASSAY -HTSD
AVG DIFF AND STD DEV AT EACH CUT POINT
-8
-6
-4
-2
0
2
4
68 155 265 350 400 500 600 650 750 900 1000
CUT BP DEG F

W
T
%
API >20 AVG DIFF API >20 STD DEV
FIGURE 10
CRUDES GROUPED BY API GRAVITIES
17
ASSAY- HTSD
AVG DIFF AND STD DEV AT EACH CUT POINT
-8
-6
-4
-2
0
2
4
68 155 265 350 400 500 600 650 750 900 1000
CUT BP DEG F

W
T
%
API 20-30 AVG DIFF API 20-30 STD DEV
FIGURE 11
CRUDES GROUPED BY API GRAVITIES
18
ASSAY -HTSD
AVG DIFF AND STD DEV AT EACH CUT POINT
-8
-6
-4
-2
0
2
4
68 155 265 350 400 500 600 650 750 900 1000
CUT BP DEG F

W
T
%
API <20 AVG DIFF API <20 STD DEV
FIGURE 12
CRUDES GROUPED BY API GRAVITIES
19
ASSAY -HTSD
WT% DIFF AT EACH CUT POINT
-8
-6
-4
-2
0
2
4
68 155 265 350 400 500 600 650 750 900 1000
CUT BP DEG F

W
T
%
API >30 AVG DIFF API 20-30 AVG DIFF API <20 AVG DIFF
FIGURE 13
CRUDES GROUPED BY API GRAVITIES
20
ASSAY -HTSD
WT% DIFF AT EACH CUT POINT
0
1
2
3
68 155 265 350 400 500 600 650 750 900 1000
CUT BP DEG F

W
T
%
API >30 STD DEV API 20-30 STD DEV API <20 STD DEV