1、Designation: D8003 15D8003 15aStandard Test Method forDetermination of Light Hydrocarbons and Cut PointIntervals in Live Crude Oils and Condensates by GasChromatography1This standard is issued under the fixed designation D8003; the number immediately following the designation indicates the year ofor
2、iginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope Scope*1.1 This test method covers the determination of light hyd
3、rocarbons and cut point intervals by gas chromatography in live crudeoils and condensates with VPCR4 (see Note 1) up to 500 kPa at 37.8 C.NOTE 1As described in Test Method D6377.1.2 Methane (C1) to hexane (nC6) and benzene are speciated and quantitated. Samples containing mass fractions of up to 0.5
4、% methane, 2.0 % ethane, 10 % propane, or 15 % isobutane may be analyzed.Amass fraction with a lower limit of 0.001 % existsfor these compounds.1.3 This test method may be used for the determination of cut point carbon fraction intervals (see 3.1.2) of live crude oils andcondensates from initial boi
5、ling point (IBP) to 391 C (nC24). The nC24 plus fraction is reported.1.4 Dead oils or condensates sampled in accordance with 12.1 may also be analyzed.1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.5.1 ExceptionWhere th
6、ere is no direct SI equivalent such as tubing size.1.6 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of r
7、egulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1265 Practice for Sampling Liquefied Petroleum (LP) Gases, Manual MethodD3700 Practice for Obtaining LPG Samples Using a Floating Piston CylinderD4307 Practice for Preparation of Liquid Blends for Use as Analytical Standar
8、dsD5002 Test Method for Density and Relative Density of Crude Oils by Digital Density AnalyzerD6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-ment System PerformanceD6377 Test Method for Determination of Vapor Pressure of Crude
9、 Oil: VPCRx (Expansion Method)D6792 Practice for Quality System in Petroleum Products and Lubricants Testing LaboratoriesE1510 Practice for Installing Fused Silica Open Tubular Capillary Columns in Gas Chromatographs2.2 Other Regulations:CAN/CGSB-3.0 No. 14.3-99 Standard Test Method for the Identifi
10、cation of Hydrocarbon Components in Automotive Gasolineusing Gas Chromatography33. Terminology3.1 Definitions:1 This test method is under the jurisdiction ofASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of SubcommitteeD02.04.0L on Gas Chromat
11、ography Methods.Current edition approved June 1, 2015Dec. 1, 2015. Published July 2015February 2016. Originally approved in 2015. Last previous edition approved in 2015 asD8003 15. DOI: 10.1520/D8003-15.10.1520/D8003-15A.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contact
12、ASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 Available from Standards Council of Canada (SCC), 60055 Metcalfe St., Ottowa, ON K1P 6L5, http:/www.scc.ca.This document is not an ASTM st
13、andard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all ca
14、ses only the current versionof the standard as published by ASTM is to be considered the official document.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.1 D1265 cy
15、linder, na container used for storage and transportation of a sample obtained at pressures above atmosphericpressure as described in Practice D1265.3.1.2 cut point carbon fraction interval, nthe percent mass obtained between two selected n-paraffins of the interval. The cutpoint carbon fraction inte
16、rval as used in this test method is defined as the percent mass obtained between the end of one n-paraffinpeak to the end of the next n-paraffin peak, thus a temperature interval is not used to determine the cut points but rather the endpoints sequential of a n-paraffin peak pair.3.1.3 dead crude oi
17、l, na term usually employed for crude oils that, when exposed to normal atmospheric pressure at roomtemperature, will not result in actual boiling of the sample.3.1.3.1 DiscussionThese crudes will have vapor pressures below atmospheric pressure at room temperature.3.1.4 floating piston cylinder, na
18、high pressure sample container, with a free floating internal piston that effectively dividesthe container into two separate compartments, as described in Practice D3700.3.1.5 live crude oil, ncrude oil with sufficiently high vapor pressure that it would boil if exposed to normal atmosphericpressure
19、 at room temperature.3.1.5.1 DiscussionSampling and handling of live crude oils requires a pressurized sample system and pressurized sample containers to ensure sampleintegrity and prevent loss of volatile components.3.1.6 residue, nthe percent mass of the sample that either does not elute from the
20、column or elutes after the end of the nC24peak.3.1.7 vapor pressure of crude oil (VPCRx), nthe pressure exerted in an evacuated chamber at a vapor-liquid ratio of X:1 byconditioned or unconditioned crude oil, which may contain gas, air, or water, or a combination thereof, where X may vary from4 to 0
21、.02.4. Summary of Test Method4.1 This is a gas chromatographic method using a Heated Pressurized Liquid Injection System (HPLIS) (trademarked)4,split/splitless inlet, capillary column, and flame ionization detector. A calibration mixture which fully elutes from the capillarycolumn, consisting of a f
22、ull range of hydrocarbons including methane, ethane, and normal paraffins up to C24 is used to ensuresystem performance (Section 7). This calibration mixture serves as an external response standard to determine sample recovery.Samples are introduced to the GC system by loading the HPLIS valve under
23、pressure followed by the pneumatic piston action ofthe HPLIS injection system introducing the sample into the gas chromatographic injection port.5. Significance and Use5.1 This test method determines methane (nC1) to hexane (nC6), cut point carbon fraction intervals to nC24 and recovery(nC24+) of li
24、ve crude oils and condensates without depressurizing, thereby avoiding the loss of highly volatile components andmaintaining sample integrity. This test method provides a highly resolved light end profile which can aid in determining andimproving appropriate safety measures and product custody trans
25、port procedures. Decisions in regards to marketing, schedulingand processing of crude oils may rely on light end compositional results.5.2 Equation of state calculations can be applied to variables provided by this method to allow for additional samplecharacterization.6. Apparatus6.1 Gas Chromatogra
26、phThe recommended conditions of the gas chromatograph are listed in Table 1. The gas chromatographshall be equipped with an electronic pressure control (EPC) or manual split/splitless inlet system.A4-way 24 VDC solenoid valvecontrolled from the gas chromatograph keyboard for actuator air pressure co
27、ntrol to accommodate the HPLIS is also required.Important features of instrument components are listed in section 6.2 to 6.4.6.2 Data SystemA data system capable of measuring the retention time and areas of eluting peaks accurately and repeatedlyas well as possess a data rate to achieve 10 points to
28、 20 points per peak.4 HPLIS (trademarked) has been found to be a suitable injector. The sole source of supply of the HPLIS known to the committee at this time is Transcendent EnterprisesInc., #33: 17715 - 96 Ave Edmonton, Alberta, Canada, T5T 6W9, www.transcendent.ca. If you are aware of alternative
29、 suppliers, please provide this information to ASTMInternational Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,1 which you may attend.D8003 15a26.3 Flame Ionization Detector (FID)A FID system shall be connected to the column to avo
30、id any cold spots and have theability to operate at a temperature equivalent to the maximum column temperature used. The detector shall have sufficientsensitivity to detect n-heptane at a mass fraction of 0.01 % with a signal-to-noise greater than 5.6.4 HighHeated Pressure Liquid Injection System (H
31、PLIS)A HPLIS system that is compatible with a split/splitless inlet andcapable of linearly introducing C1 to C24 components should be used. The unit should possess an internal dead volume of 80 Lin sample transfer zone and a 0.5 uL stem volume to contain the pressurized liquid sample. The sample pre
32、ssure rating for the unitshould be 8300 kPa (1200 psig) at 30 C using helium as the test media. Other injection systems may be employed provided theperformance criteria in Section 7 are met.7. Column and Performance Criteria7.1 A 100 % polydimethylsiloxane (PDMS) phase column of a 15 m length with a
33、n inside diameter of 0.28 mm and 3 m filmthickness is recommended. The column shall possess stability at 380 C. Metal columns have been successfully used for this testmethod. The column should be installed according to Practice E1510. To prevent column overloading, the skewness is measuredfor nC6. T
34、he value shall not be less than 1 or more than 4. Skewness is determined drawing a straight line down the apex, as wellas one across the length of the nC6 peak at 5 % height. The width of the right section of the peak at 5 % height (B) is divided bythat of the left section (A) (see Fig. 1).7.2 Basel
35、ine resolution for C1, C2, C3, isobutane and butane shall be achieved (R 1.0). The resolution is calculated as follows:R 523t 2 2 t 1!1.699w 11w 2! (1)TABLE 1 Gas Chromatograph ParametersInitial Oven Temperature 35 CInitial Oven Time 2 minOven Temperature Program 20 C/minFinal Oven Temperature 310 C
36、Final Hold Time 10 minHPLIS Collar Heater Temperature 200 CInlet Temperature 400 CColumn 15 m 0.28 mm 3 m PDMSColumn Flow (Hydrogen) 2 mL/minCarrier Control Constant FlowDetector FIDDetector Temperature 425 CDetector Gases:Hydrogen 40 mL/minAir 450 mL/minMake-Up (N2) 25 mL/minVolume Injected 0.5 LSp
37、lit Ratio 30:1Data Acquisition Rate 10 HzHPLIS Valve Timing On 0 minHPLIS Valve Timing Off 0.3 minTotal Acquisition Time 25.75 minFIG. 1 Calculation of Peak SkewnessD8003 15a3where:t2 = retention time of peak 1,t1 = retention time of peak 2,w1 = peak width at half height for peak 1, andw2 = peak wid
38、th at half height for peak 2.7.3 Splitter Linearity VerificationUsing the calibration standard (see 8.1.4), inject this sample according to the parameterslisted in Table 1. Identify and quantify the normal paraffins C1 to C24. Compare the calculated mass % concentrations to the knownstandard concent
39、rations after calculating the corrected area normalization using the response factors from Table 2 procedures inSection 13. Verify that for each component selected, its concentration does not vary by more than 3 % relative error.percent relative error51003concentration determined 2 concentration kno
40、wn!concentration known (2)7.4 The sensitivity of the system shall be determined by analyzing a 10 mgkg pentane standard (Practice D4307). The signalto noise ratio shall be greater than 5.8. Reagents and Materials8.1 Gas Chromatograph GasesThe purity of the volume fraction for all gases used in this
41、system should be 99.995 %.8.1.1 Carrier GasHydrogen. Follow proper safety procedures. (WarningExtremely flammable under high pressure; use ofa safety hydrogen sensor in GC oven containing the column is highly recommended.)8.1.2 Detector GasesAir, hydrogen and make-up gas (helium or nitrogen) are use
42、d for Flame Ionization Detector operation(WarningCompressed gas under high pressure. Hydrogen is extremely flammable under high pressure.)8.1.3 Injection system washMethylene chloride, with a purity of 99 %, used to remove any residual components from HPLISsample injection. (WarningToxic material. M
43、ay be combustible at high temperatures.) Toluene, with a purity of 99 %, or othersuitable solvents may be used as an alternative to methylene chloride but caution shall be taken to eliminate residual sample andsolvent in the HPLIS sample lines.TABLE 2 Component Properties and Theoretical Response Fa
44、ctorsAComponent Molecular Weight ofCompound (g/mol) Density of Compound 20 C (g/mL)Generalized BoilingPoint of Cut PointFraction Interval CGeneralized MolecularWeight of Cut PointFraction Interval(g/mol)Generalized Density ofCut Point FractionInterval 20 C(g/mL)Theoretical MassResponse FactorC1 16.0
45、4 0.26 1.00C2 30.08 0.34 0.937C3 44.10 0.505 0.916iC4 58.12 0.557 0.906n-C4 58.12 0.5788 0.906iC5 72.15 0.6201 0.899n-C5 72.15 0.6262 0.899n-C6 86.18 0.6603 63.9 84 0.685 0.895Benzene 78.12 0.8765 0.812n-C7 100.21 0.6837 91.9 96 0.722 0.892n-C8 114.22 0.7025 116.7 107 0.745 0.890n-C9 128.26 0.7176 1
46、42.2 121 0.764 0.888n-C10 142.28 0.73 165.8 134 0.778 0.887n-C11 156.32 0.7402 187.2 147 0.789 0.886n-C12 170.34 0.7487 208.3 161 0.800 0.885n-C13 184.37 0.7564 227.2 175 0.811 0.884n-C14 198.39 0.7628 246.4 190 0.822 0.883n-C15 212.41 0.7685 266 206 0.832 0.883n-C16 226.45 0.7733 283 222 0.839 0.88
47、2n-C17 240.48 0.778 300 237 0.847 0.882n-C18 254.51 0.782 313 251 0.852 0.881n-C19 268.53 0.7855 325 263 0.857 0.881n-C20 282.56 0.7886 338 275 0.862 0.881n-C21 296.59 0.7919 351 291 0.867 0.880n-C22 310.61 0.7944 363 305 0.872 0.880n-C23 324.67 0.7969 375 318 0.877 0.880n-C24 338.67 0.7991 386 331
48、0.881 0.880Residue 540 500 0.925 0.88A Density and molecular weight values for C1 to benzene obtained from CRC Handbook of Chemistry and Physics, 61st ed, CRC Press, Boca Raton, FL, 1981.Theoretical Mass response factors up to nC15 obtained from Test Method: CAN/CGSB-3.0 No. 14.3-99.Generalized comp
49、onent properties of boiling point, molecular weight and density are averages and best estimates obtained from Katz, D. L., Firoozabadi,A., “PredictingPhase Behavior of Condensate/Crude-Oil Systems Using Methane Interaction Coefficients, Society of Petroleum Engineers,” (SPE 6721), 1978.Residue properties are estimates only and will vary for sample type.D8003 15a48.1.4 Calibration StandardThe calibration standard may serve three purposes. A retention time calibration for n-paraffinscovering the range of C1 to nC24, the
