1、 STD.API/PETRO TR 997-ENGL 2000 111 0?3224!l 0626376 273 m Comprehensive Report of API Crude Oil Characterization Measurements API TECHNICAL REPORT 997 FIRST EDITION, AUGUST 2000 American Petroleum Institute Helping You Get The Job Done Right? Comprehensive Report of API Crude Oil Characterization M
2、easurements Downstream Segment API TECHNICAL REPORT 997 FIRST EDITION, AUGUST 2000 Work Performed For American Petroleum Institute 1220 L. Street, Northwest Washington, DC 20005 Gene P. Sturm, Jr. Johanna Y. Shay American Petroleum Institute TRW Inc. TRW Petroleum Technologies P.O. Box 2543 Bartlesv
3、ille, OK 74005 (9 1 8) 338-4400 STD*API/PETRO TR 797-ENGL 2000 m 0732290 ObZbL98 04b m SPECIAL NOTES API publications necessarily address problems of a general nature. With respect to partic- ular circumstances, local, state, and federal laws and regulations should be reviewed. API is not undertakin
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13、uirements of that standard. API does not represent, warrant, or guarantee that such prod- ucts do in fact conform to the applicable API standard. All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic, mechanical, photocopyi
14、ng, recording, or otherwise, without prior written permission from the publishel: Contact the Publishel; API Publishing Services, 1220 L Street, N. W, Washington, D. C. 20005. Copyright 0 2000 American Petroleum Institute ABSTRACT A consortium of American Petroleum Institute member companies has spo
15、nsored a research program consisting of a series of projects on the characterization of crude oils. The goal of this program was to obtain complete sets of assay and thermophysical property data on a few widely varying crude oils to test the basic correlations and models typically used in the design
16、 of crude oil refining and related facilities. The crude oils chosen were Alaskan North Slope, Utah Altamont, and San Joaquin Valley. This report provides descriptions of the test procedures, discussions of their accuracy, and a comprehensive compilation of the data for the three crude oils measured
17、 under this program. The scope of this report is limited to discussion of the characterization tests and compilation of the data. Although the data were generated to allow for the evaluation of various correlations used for design purposes, such evaluation has beedwill be done by APIs Technical Data
18、 Committee and may be published later. It is important to note, however, that a number of these data have been utilized in the development of correlations that are included in the three most recent revisions of the API Technical Data Book, most notably Chapter 2 (Characterization) and Chapter 3 (Dis
19、tillation Interconversions). 111 . ACKNOWLEDGEMENT The authors acknowledge and express appreciation to Cheryl Dickson for preparation of the manuscript, Dr. William V. Steele, Oak Ridge National Lab, for material and discussions on vapor pressure by ebulliometry, and to Dr. Calvin F. Spencer, Kellog
20、g Brown and Root, for review of the draft manuscript. Also, the authors and TRW Petroleum Technologies would like to express deep appreciation to the American Petroleum Institute Technical Data Committee member companies who sponsored the API crude oil characterization program conducted by TRW Petro
21、leum Technologies and its predecessors. The sponsor companies and their years of sponsorship are listed below. , SDonsor Commny Amom Oil Company Chevron Research and Technology Fluor Daniel M. W. Kellogg Mobil Research for 50-90% off, r is 1.8 F; and for FBP, r is 5.8“ F. Results are presented in Ta
22、ble 11. 2.2.4 Boiling Range DistribGion of High Boiling Fractions and Resids by ASTM D 5307 and High Temperature Simulated Distillation Three methods were used to determine boiling range distributions for the high boiling fiactions and resids fom the three crudes. The first, AST“ D 5307, has been di
23、scussed earlier. The second is a variation of the ASTM proposed high temperature method “Boiling Range Distribution of Heavy Petroleum Fractions by Gas Chromatography“ that is analogous to ASTM D 2887. This method uses a high temperature GC and column to elute material boiling below 6 STD*API/PETRO
24、TR 777-ENGL 2000 I 0732290 Ob2b2LL 30T H 1350“ F. An internal standard is not used, and complete sample elution by 1350“ F is assumed. The third is the AST“ proposed high temperature method in a variation that uses an internal standard. This method is applicable to materials with an initial boiling
25、point of at least 60OoF, since elution of the internal standard (typically C, and C, n-paraffins) must be complete before the sample elution begins. Reproducibility and repeatability data on the two proposed methods are not available and bias has not been determined due to lack of an accepted refere
26、nce material. Data for the fractions and resids from the three crudes are listed in Table 12. Most samples were run by the proposed high temperature method using an internal standard. Samples run by the proposed method without an internal standard and one sample run by ASTM D 5307 are indicated by f
27、ootnotes. 3. GENERAL PHYSICAL PROPERTY CHARACTERIZATION DATA 3.1 Cloud Point Cloud points were determined for all fractions distilling between 320 and 550“ F by ASTM D 2500, Cloud Point of Petroleum Products. This method is applicable to petroleum products that are transparent in layers of 40 mm thi
28、ckness, and with cloud points below 120“ F. The cloud point is the temperature at which a cloud of wax crystals frst appears in a liquid that is cooled at a specified rate. The repeatability for this test is 3.6“ F. Reproducibility is 7.2“ F. The procedure has no bias as the value of cloud point can
29、 be defined only in terms of a test method. Results are listed in Table 13. 3.2 Pour Point Pour points on the whole crude and all distillate fractions above 450“ F were determined by ASTM D 97, Pour Point for Petroleum Products. This method is applicable to any petroleum product. The pour point is t
30、he lowest temperature at which the sample shows movement after first being heated and then ccioled at a Specified rate and examined at 5“ F intervals. Repeatability for this method is 5“ F. Reproducibility is 10“ F. No bias statement can be made since there are no criteria for measuring bias for the
31、 test-product combinations in the method. Results are provided in Table 13. Pour point determinations on samples of the 850-950“ F distillates from ANS and ALT crude oils that were submitted with sample numbers without specific sample information (blind) were identical with the original sample deter
32、minations. A later repeat determination on the 1 150-1250“ F distillate from ANS crude deviated by 10“ F from the original determination. This deviation is within the reproducibility limits of the method. 7 STD-APIIPETRO TR 997-ENGL 2000 II 0732270 0626212 246 S 3.3 Freeze Point Freeze points were d
33、etermined for fractions distilling between 320 and 550“ F by ASTM D 2386, Freezing Point of Aviation Fuels. This method is applicable to aviation turbine fiels and aviation gasolines, although the precision data were determined using only aviation turbine fuels. The method involves cooling the fuel
34、until solid hydrocarbon crystals appear, and then noting the temperature at which the crystals disappear as the temperature is allowed to rise. The repeatability of the method is 1.4“ F. Reproducibility is 4.1 o F. Bias could not be established since no liquid hydrocarbon mixtures of known freezing
35、point that simulate aviation fuels could be found. Results are listed in Table 13. 3.4 Rei-active Index Refiactive indexes for the distillates boiling below 650“ F were measured by ASTM D 121 8, Rehtive Index and Reliactive Dispersion of Hydrocarbon Liquids using the sodium D line and at 20“ C. Meas
36、urements for the higher boiling distillates (%50“ F) were made by ASTM D 1747, Refiactive Index of Viscous Materials. These measurements were also made with the sodium D line but at 80“ C. ASTM D 1218 is applicable to transparent and light-colored hydrocarbon liquids that have refkactive indexes in
37、the range from 1.33 to 1 SO, and at temperatures liom 20 to 30“ C. The method involves measuring the refkactive index by the critical angle method with a Bausch all others are ignored. Other factors that can produce erroneous results are large amounts of a single compound, any other unusual distribu
38、tion of compounds, or thermally unstable components. The mass spectral resolution required for the method is 5,000 (10% valley definition). The main advantage over the standard ASTM methods that apply to fractions in the same boiling range is the absence of need for prior separation of the samples.
39、Another advantage for the Teeter method over ASTM Method D 2425 for middle distillates (or diesel fuels) is the determination of more compound types (up to 22 compared to 1 1 for ASTM D 2425). In particular, the dhmination of thiophenic types by the Teeter method could be a very important advantage
40、for some samples in view of the forthcoming more stringent control of the level of sulfur species in gasoline and other petroleum products (the ASTM method determines only hydrocarbon types). For higher boiling samples in the gas-oil range, the combination of ASTM D 2786 (7 saturate and 1 aromatic t
41、ypes) and ASTM D 3239 (18 aromatic hydrocarbon and 3 aromatic sulfur-containing types) does determine more compound types than the Teeter method, but requires the prior separation and analysis of two samples. Overall, the precision and accuracy of the Teeter and various ASTM methods are comparable.
42、A summary of 12 STD-APIIPETRO TR 997-ENGL 2000 II 0732290 062b217 828 m the analytical results for a sample used for QNQC purposes in our laboratory and in a clients laboratory (using a different mass spectrometric method modified Robinson method similar to ASTM D 24251 and instrument CEC 21-1031) a
43、re shown below: Compound TYPe PdhS Naphthenes Aromatics Teeter Method on OW MS-50 16.01 0.29 14.55 i 0.47 69.40 2 0.56 Clients 21-103 data 16.91 i 0.43 16.06 i 0.46 67.03 & 0.55 The emor limits listed are plus or minus one standard deviation. The agreement between the results from the two methods is
44、 quite good, especially considering that the data were acquired by different operators using different methods and different instruments located in diffrent laboratories. Results for the Teeter analysis are provided in Table 15. 4.3 Aromatic Carbon by Nuclear Magnetic Resonance Spectroscopy Aromatic
45、 carbon contents of three fiactions and one composite were determined using carbon-13 nuclear magnetic resonance (NMR) spectrometry. Results are listed in Table 16. The aromaticity, fa, is defined as the mole fraction of aromatic carbons in the sample, and is obtained by fnding the ratio of the arom
46、atic carbon signal integral to the total carbon signal integral fiom the NMR spectrum. The fastest procedure is to obtain the proton NMR spectrum of the sample, which is inherently quantitative. However, the underlying carbon structure of the sample must be iderred fiom the proton spectrum using som
47、e assumptions based on the nature of the sample, so the resulting aromaticity is subject to some uncertainty. Because of the variable interaction of the carbon-13 nuclear spin with those of the attached protons during proton decoupling (nuclear Overhauser effect, NOE) and the long spin-lattice relax
48、ation times of non-protonated carbons, care must be exercised to obtain quantitative carbon- 13 NMR spectra. Gated decoupling is used where the proton decoupling field is applied only during signal acquisition and not during the longer delay between successive pulses to avoid the variable NOE. A lon
49、g delay between successive pulses is used to allow complete relaxation of the different carbon types in the sample between pulses to achieve quantitative results. Because of the low isotopic ratio of carbon-1 3 in the sample, many successive signals must be added to achieve adequate signallnoise ratios, leading to long experiment times. The experiment can be 13 shortened by adding a relaxation agent, such as chromium acetylacetonate, to the sample solution. This can shorten the time by a factor of four or more. From the quantitative carbon-13 NMR spectnun, the integ
