1、Designation: D6352 04 (Reapproved 2009)D6352 12Standard Test Method forBoiling Range Distribution of Petroleum Distillates inBoiling Range from 174 to 700C by Gas Chromatography1This standard is issued under the fixed designation D6352; the number immediately following the designation indicates the
2、year oforiginal 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
3、the boiling range distribution of petroleum distillate fractions. The test methodis applicable to petroleum distillate fractions having an initial boiling point greater than 174C (345F) and a final boiling pointof less than 700C (1292F) (C10 to C90) at atmospheric pressure as measured by this test m
4、ethod.1.2 The test method is not applicable for the analysis of petroleum or petroleum products containing low molecular weightcomponents (for example naphthas, reformates, gasolines, crude oils). Materials containing heterogeneous components (forexample alcohols, ethers, acids, or esters) or residu
5、e are not to be analyzed by this test method. See Test Methods D3710, D2887,or D5307 for possible applicability to analysis of these types of materials.1.3 The values stated in SI units are to be regarded as standard. The values stated in inch-pound units are for information onlyand may be included
6、as parenthetical values.1.4 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 regulatorylimitations prior
7、to use.2. Referenced Documents2.1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products at Atmospheric PressureD1160 Test Method for Distillation of Petroleum Products at Reduced PressureD2887 Test Method for Boiling Range Distribution of Petroleum Fractions by Gas ChromatographyD28
8、92 Test Method for Distillation of Crude Petroleum (15-Theoretical Plate Column)D3710 Test Method for Boiling Range Distribution of Gasoline and Gasoline Fractions by Gas ChromatographyD4626 Practice for Calculation of Gas Chromatographic Response FactorsD5307 Test Method for Determination of Boilin
9、g Range Distribution of Crude Petroleum by Gas Chromatography (Withdrawn2011)3E355 Practice for Gas Chromatography Terms and RelationshipsE594 Practice for Testing Flame Ionization Detectors Used in Gas or Supercritical Fluid ChromatographyE1510 Practice for Installing Fused Silica Open Tubular Capi
10、llary Columns in Gas Chromatographs3. Terminology3.1 DefinitionsThis test method makes reference to many common gas chromatographic procedures, terms, and relationships.For definitions of these terms used in this test method, refer to Practices E355, E594, and E1510.3.2 Definitions of Terms Specific
11、 to This Standard:3.2.1 area sliceslice, nthe area resulting from the integration of the chromatographic detector signal within a specifiedretention time interval. In area slice mode (see 6.4.2), peak detection parameters are bypassed and the detector signal integral isrecorded as area slices of con
12、secutive, fixed duration time intervals.1 This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.04.0Hon Chromatographic Distribution Methods.Current edition approved April 15, 2009Nov. 1, 2012. Publi
13、shed July 2009April 2013. Originally approved in 1998. Last previous edition approved in 20042009 asD6352D635204(2009). 041. DOI: 10.1520/D6352-04R09.10.1520/D6352-12.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual B
14、ook of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.org.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indica
15、tion 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 cases only the current versionof the standard as published by ASTM is to be con
16、sidered 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 States13.2.2 corrected area sliceslice, nan area slice corrected for baseline offset by subtractio
17、n of the exactly corresponding areaslice in a previously recorded blank (non-sample) analysis.3.2.3 cumulative corrected areaarea, nthe accumulated sum of corrected area slices from the beginning of the analysisthrough a given retention time, ignoring any non-sample area (for example, solvent).3.2.4
18、 final boiling point (FBP)(FBP), nthe temperature (corresponding to the retention time) at which a cumulativecorrected area count equal to 99.5 % of the total sample area under the chromatogram is obtained.3.2.5 initial boiling point (IBP)(IBP), nthe temperature (corresponding to the retention time)
19、 at which a cumulativecorrected area count equal to 0.5 % of the total sample area under the chromatogram is obtained.3.2.6 slice raterate, nthe time interval used to integrate the continuous (analog) chromatographic detector response duringan analysis. The slice rate is expressed in Hz (for example
20、 integrations or slices per second).3.2.7 slice timetime, nthe analysis time associated with each area slice throughout the chromatographic analysis. The slicetime is the time at the end of each contiguous area slice.3.2.8 total sample areaarea, nthe cumulative corrected area, from the initial area
21、point to the final area point, where thechromatographic signal has returned to baseline after complete sample elution.3.3 AbbreviationsA common abbreviation of hydrocarbon compounds is to designate the number of carbon atoms in thecompound. A prefix is used to indicate the carbon chain form, while a
22、 subscripted suffix denotes the number of carbon atoms (forexample n-C10 for normal-decane, i-C14 for iso-tetradecane).4. Summary of Test Method4.1 The boiling range distribution determination by distillation is simulated by the use of gas chromatography.Anon-polar opentubular (capillary) gas chroma
23、tographic column is used to elute the hydrocarbon components of the sample in order of increasingboiling point.4.2 A sample aliquot is diluted with a viscosity reducing solvent and introduced into the chromatographic system. Samplevaporization is provided by separate heating of the point of injectio
24、n or in conjunction with column oven heating.4.3 The column oven temperature is raised at a specified linear rate to affect separation of the hydrocarbon components in orderof increasing boiling point. The elution of sample components is quantitatively determined using a flame ionization detector. T
25、hedetector signal is recorded as area slices for consecutive retention time intervals during the analysis.4.4 Retention times of known normal paraffin hydrocarbons, spanning the scope of the test method, are determined andcorrelated to their boiling point temperatures. The normalized cumulative corr
26、ected sample areas for each consecutive recordedtime interval are used to calculate the boiling range distribution. The boiling point temperature at each reported percent offincrement is calculated from the retention time calibration.5. Significance and Use5.1 The boiling range distribution of mediu
27、m and heavy petroleum distillate fractions provides an insight into the compositionof feed stocks and products related to petroleum refining processes (for example, hydrocracking, hydrotreating, visbreaking, ordeasphalting). The gas chromatographic simulation of this determination can be used to rep
28、lace conventional distillation methodsfor control of refining operations. This test method can be used for product specification testing with the mutual agreement ofinterested parties.5.2 This test method extends the scope of boiling range determination by gas chromatography to include medium and he
29、avypetroleum distillate fractions beyond the scope of Test Method D2887 (538C).5.3 Boiling range distributions obtained by this test method have not been analyzed for correlation to those obtained by lowefficiency distillation, such as with Test Method D86 or D1160.6. Apparatus6.1 ChromatographThe g
30、as chromatographic system used shall have the following performance characteristics:6.1.1 Carrier Gas Flow ControlThe chromatograph shall be equipped with carrier gas pressure or flow control capable ofmaintaining constant carrier gas flow control through the column throughout the column temperature
31、 program cycle.6.1.2 Column OvenCapable of sustained and linear programmed temperature operation from near ambient (for example, 30to 35C) up to 450C.6.1.3 Column Temperature ProgrammerThe chromatograph shall be capable of linear programmed temperature operation upto 450C at selectable linear rates
32、up to 20C/min. The programming rate shall be sufficiently reproducible to obtain the retentiontime repeatability of 0.1 min (6 s) for each component in the calibration mixture described in 7.5.6.1.4 DetectorThis test method requires the use of a flame ionization detector (FID). The detector shall me
33、et or exceed thefollowing specifications in accordance with Practice E594. The flame jet should have an orifice of approximately 0.05 to 0.070 mm(0.020 to 0.030 in.).D6352 1226.1.4.1 Operating Temperature100 to 450C.6.1.4.2 Sensitivity0.005 C/g carbon.6.1.4.3 Minimum Detectability1 10-11 g carbon/s.
34、6.1.4.4 Linear Range1066.1.4.5 Connection of the column to the detector shall be such that no temperature below the column temperature exists betweenthe column and the detector. Refer to Practice E1510 for proper installation and conditioning of the capillary column.6.1.5 Sample Inlet SystemAny samp
35、le inlet system capable of meeting the performance specification in 7.6 and 8.2.2 may beused. Programmable temperature vaporization (PTV) and cool on-column injection systems have been used successfully.6.2 MicrosyringeA microsyringe with a 23-gage or smaller stainless steel needle is used for on-co
36、lumn sample introduction.Syringes of 0.1 to 10-L capacity are available.6.2.1 Automatic syringe injection is recommended to achieve best precision.6.3 ColumnThis test method is limited to the use of non-polar wall coated open tubular (WCOT) columns of high thermalstability (see Note 1). Glass, fused
37、 silica, and stainless steel columns with 0.53 to 0.75-mm internal diameter have beensuccessfully used. Cross-linked or bonded 100 % dimethyl-polysiloxane stationary phases with film thickness of 0.10 to 0.20 mhave been used. The column length and liquid phase film thickness shall allow the elution
38、of at least C90 n-paraffin (BP = 700C).The column and conditions shall provide separation of typical petroleum hydrocarbons in order of increasing boiling point andmeet the column performance requirements of 8.2.1. The column shall provide a resolution between three (3) and ten (10) usingthe test me
39、thod operating conditions.NOTE 1Based on recent information that suggests that true boiling points (atmospheric equivalent temperatures) versus retention times for allcomponents do not fall on the same line, other column systems that can meet this criteria will be considered. These criteria will be
40、specified after a roundrobin evaluation of the test method is completed.6.4 Data Acquisition System:6.4.1 RecorderA 0 to 1 mV range recording potentiometer or equivalent with a full-scale response time of 2 s or less maybe used. It is, however, not a necessity if an integrator/computer data system i
41、s used.6.4.2 IntegratorMeans shall be provided for determining the accumulated area under the chromatogram. This can be done bymeans of an electronic integrator or computer-based chromatography data system. The integrator/computer system shall havenormal chromatographic software for measuring the re
42、tention time and areas of eluting peaks (peak detection mode). In addition,the system shall be capable of converting the continuously integrated detector signal into area slices of fixed duration. Thesecontiguous area slices, collected for the entire analysis, are stored for later processing. The el
43、ectronic range of theintegrator/computer (for example 1 V, 10 V) shall be operated within the linear range of the detector/electrometer system used.NOTE 2Some gas chromatographs have an algorithm built into their operating software that allows a mathematical model of the baseline profile tobe stored
44、 in memory. This profile is automatically subtracted from the detector signal on subsequent sample runs to compensate for the column bleed.Some integration systems also store and automatically subtract a blank analysis from subsequent analytical determinations.7. Reagents and Materials7.1 Carrier Ga
45、sHelium, hydrogen, or nitrogen of high purity (Warning Helium and nitrogen are compressed gases underhigh pressure). Additional purification is recommended by the use of molecular sieves or other suitable agents to remove water,oxygen, and hydrocarbons. Available pressure shall be sufficient to ensu
46、re a constant carrier gas flow rate.7.2 HydrogenHydrogen of high purity (for example, hydrocarbon free) is used as fuel for the FID. Hydrogen can also be usedas the carrier gas. ( WarningHydrogen is an extremely flammable gas under high pressure).7.3 AirHigh purity (for example, hydrocarbon free) co
47、mpressed air is used as the oxidant for the FID. (WarningCompressed air is a gas under high pressure and supports combustion).7.4 SolventsUnless otherwise indicated, it is intended that all solvents conform to the specifications of the Committee onAnalytical Reagents of the American Chemical Society
48、 where such specifications are available.4 Other grades may be used,provided it is first ascertained that the solvent is of sufficiently high purity to permit its use without lessening the accuracy of thedetermination.7.4.1 Carbon Disulfide (CS2)(99+ % pure) is used as a viscosity-reducing solvent a
49、nd as a means of reducing mass of sampleintroduced onto the column to ensure linear detector response and reduced peak skewness. It is miscible with asphaltichydrocarbons and provides a relatively small response with the FID. The quality (hydrocarbon content) should be determined bythis test method prior to use as a sample diluent. (WarningCS2 is extremely flammable and toxic.)7.4.2 Cyclohexane (C6H12)(99+ % pure) may be used in place of CS2 for the preparation of the calibration mixture.4 Reagent Chemicals, American Ch
