1、Designation: D7756 13Standard Test Method forResidues in Liquefied Petroleum (LP) Gases by GasChromatography with Liquid, On-Column Injection1This standard is issued under the fixed designation D7756; the number immediately following the designation indicates the year oforiginal adoption or, in the
2、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*1.1 This test method covers the determination, by gaschromatography, of soluble hydrocarbon
3、 materials, sometimescalled “oily residue,” which can be present in LiquefiedPetroleum (LP) Gases and which are substantially less volatilethan the LPG product.1.2 This test method quantifies, in the range of 10 to 600mg/kg (ppm mass), the residue with a boiling point between174C and 522C (C10to C40
4、) in LPG. Higher boilingmaterials, or materials that adhere permanently to the chro-matographic column, will not be detected.1.3 Appendix X3 and Appendix X4 describe additionalapplications which could be performed based on the hardwareand procedures described in this test method. Appendix X3describe
5、s a test procedure for expanding the analysis range tobenzene, and Appendix X4 describes a test procedure for theanalysis of diisopropanolamine in LPG.1.4 UnitsThe values stated in SI units are to be regardedas standard. The values given in parentheses are for informa-tion only.1.5 This standard doe
6、s not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Stan
7、dards:2D1265 Practice for Sampling Liquefied Petroleum (LP)Gases, Manual MethodD1835 Specification for Liquefied Petroleum (LP) GasesD2158 Test Method for Residues in Liquefied Petroleum(LP) GasesD2163 Test Method for Analysis of Liquefied Petroleum(LP) Gases and Propene Concentrates by Gas Chromato
8、g-raphyD2421 Practice for Interconversion of Analysis of C5andLighter Hydrocarbons to Gas-Volume, Liquid-Volume, orMass BasisD2598 Practice for Calculation of Certain Physical Proper-ties of Liquefied Petroleum (LP) Gases from Composi-tional AnalysisD3700 Practice for Obtaining LPG Samples Using a F
9、loat-ing Piston CylinderD6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6300 Practice for Determination of Precision and BiasData for Use in Test Methods for Petroleum Products andLubricantsD6667 Test Metho
10、d for Determination of Total VolatileSulfur in Gaseous Hydrocarbons and Liquefied PetroleumGases by Ultraviolet FluorescenceE355 Practice for Gas Chromatography Terms and Relation-shipsE594 Practice for Testing Flame Ionization Detectors Usedin Gas or Supercritical Fluid Chromatography3. Terminology
11、3.1 Definitions of Terms Concerning ChromatographyThis test method makes reference to many common gaschromatographic procedures, terms, and relationships. Detaileddefinitions of these can be found in Practices E355 and E594.3.2 Definitions of Terms Concerning Liquefied PetroleumGasesThis test method
12、 makes reference to the definitions ofliquefied petroleum gases as described in Specification D1835.3.3 Definitions of Terms Specific to This Standard:3.3.1 high pressure liquefied gas injector, nSample intro-duction device which injects liquefied gas samples underpressure and at room temperature di
13、rectly onto the chromato-graphic column thereby maintaining the sample in liquid phaseduring the injection process.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.H0 on Liquefied Petroleum Gas.C
14、urrent edition approved June 15, 2013. Published July 2013. Originallyapproved in 2011. Last previous edition approved in 2012 as D775612.DOI:10.1520/D7756-13.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of
15、ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.*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 States13.3.2 pressure station,
16、 nDevice that supplies high pres-sure nitrogen to a suitable sample cylinder and thereforemaintains sample in the liquid phase during the injectionprocedure.4. Summary of Test Method4.1 A sample cylinder of LPG is pressurized to 2500 kPa(363 psi) using nitrogen or helium.4.2 The injection system is
17、flushed with LPG in liquid phaseat room temperature.4.3 After flushing, the injection device is routed to the GCinjector port and LPG (25 milliseconds activation time equiva-lent to 30 L) is introduced via a high pressure valve andneedle which is inserted into a large volume cold on-columninjector.4
18、.4 The gas chromatograph is equipped with a solvent ventwhich routes most of the LPG light components out of theanalytical system and leaves behind the components of interest.4.5 The oily residue to be determined is retained on apre-column.4.6 After venting the LPG, the flow from the pre-column issw
19、itched to the analytical column and a temperature program isstarted.4.7 Oily residue contaminants are separated and identifiedbased on differences in boiling point temperature.4.8 Total residue is quantified using area summation ofcomponents corresponding to the expected range of C10to C40(174 to 52
20、2C).5. Significance and Use5.1 Control over the residue content as specified in Speci-fication D1835 is of considerable importance in end-useapplications of LPG. Oily residue in LPG is contaminationwhich can occur during production, transportation, or storage.5.2 This test method is quicker and much
21、 more sensitivethan manual methods, such as Test Method D2158, which isbased on evaporation of large sample volumes followed byvisual or gravimetric estimation of residue content.5.3 This test method provides enhanced sensitivity in mea-surements of heavier (oily) residues, with a quantification lim
22、itof 10 mg/kg total residue.5.4 This test method gives both quantitative results andinformation about contaminant composition such as boilingpoint range and fingerprint, which can be very useful in tracingthe source of a particular contaminant.6. Apparatus6.1 Gas Chromatograph (GC)Gas chromatographi
23、c in-strument equipped with a Large Volume Cold on-ColumnInjector (LVOCI), a linear temperature programmable columnoven, and a flame ionization detector (FID). The temperaturecontrol shall be capable of obtaining a retention time repeat-ability of 0.05 min (3 s) throughout the scope of this analysis
24、.6.2 Data AcquisitionAny commercial integrator or com-puterized data acquisition system may be used for display ofthe chromatographic detector signal and peak area integration.6.3 Solvent VentA controlled vent for venting the majorpart of the matrix.6.4 Retention GapUncoated stainless steel capillar
25、y. Suc-cessfully used columns and conditions are given in Table 1.6.5 Retaining Pre-ColumnA column with a polydimeth-ylsiloxane stationary phase. Successfully used columns andconditions are given in Table 1.6.6 Analytical ColumnA column with a polydimethylsi-loxane stationary phase. Successfully use
26、d columns and con-ditions are given in Table 1.6.7 Column CouplerCoupling DeviceSuitable for leak-free coupling of the retention gap to the retaining pre-column.TABLE 1 Typical Operating ConditionsOven program 35C for 3 min35 to 340C at 25C/min340C for 10 minInlet program Type: cool on-columnTempera
27、ture: 65C for 3 min55 to 340C at 25C/min340C for 9 minDetector settings Air flow: 400 mL/minHydrogen flow: 40 mL/minMake up gas flow: 45 mL/minTemperature: 350CData rate: 20 HzColumn Retention gap: SulfinertAstainless steel capillary with inner diameter 0.53 mm andlength of 5 mRetaining pre-column:
28、3 m 100%Dimethylpolysiloxane: 0.53 mm, 2.65 mAnalytical column: 100%Dimethylpolysiloxane 30 m, 0.32 mm, 0.25 mPressure station Sample flow: 2 mL/minNitrogen pressure: 2500 kPaNitrogen purge pressure: 500 kPaLiquefied GasInjectorInjection: 25 msASulfinert is a trademark of SilcoTek, 112 Benner Circle
29、, Bellefonte, PA 16823, www.SilcoT.D7756 132(See Fig. 1 for a schematic overview of the couplings inside theGC oven and the couplings to the solvent vent valve.)6.8 Column SplitterSplitter suitable for leak-free couplingof the retaining pre-column to one side of the analytical columnand the deactiva
30、ted capillary on the other side. (See Fig. 1 fora schematic overview of the couplings inside the GC oven andthe couplings to the solvent vent valve.)6.9 High Pressure Liquefied Gas InjectorA high pressurevalve directly connected to a needle which is inserted in theinjection port of the GC, after whi
31、ch the valve is triggered inorder to introduce a representative aliquot into the GC systemwithout sample discrimination. (See Fig. 2.)6.10 Pressure StationThis shall ensure a sample in liquidphase at a constant pressure. See Fig. 3 for a typical configu-ration.6.11 Typical Column OverviewSee Fig. 1.
32、6.12 Typical Operating ConditionsSee Table 1.7. Reagents and Materials7.1 Mineral Oil in LPG Calibration MixtureCertifiedcalibration mixture with mineral oil in LPG. The concentrationof the mineral oil shall be close to the expected concentrationof the contamination in the LPG sample.7.2 Mineral Oil
33、 in Pentane Calibration MixturePrepare acalibration standard of mineral oil in pentane. Record theweighed value to the nearest milligram of mineral oil andcalculate the concentration in mg/kg. The concentration of themineral oil shall be close to the expected concentration of thecontamination in the
34、 LPG sample.7.2.1 Standards that are prepared in pentane, normallyliquid at room temperature, should be stored in suitablecontainers under refrigeration and transferred to sample cylin-ders prior to use. Alternatively, they may be stored in airtightcylinders.7.3 Mineral Oil or Local Hydrocarbon Frac
35、tionBoilingpoint range approximately C10-C40. Alternatively, a well char-acterized local hydrocarbon fraction, within the range C10-C40,can be used to provide quantitative and qualitative comparisonto the contaminant in the sample. Care should be taken toensure no significant fraction falls outside
36、the C10-C40range.7.4 Validation Standard, Mineral Oil in PentanePrepare avalidation standard of mineral oil in pentane. Record the exactweighed value to the nearest milligram of mineral oil andcalculate the concentration in mg/kg. The concentration of themineral oil shall be close to the expected co
37、ncentration of thecontamination in the LPG sample.7.5 N-alkane Retention Time StandardMixture containingat least C10and C40in a concentration of (nominally) 5 mg/Leach, dissolved in pentane or heptane.7.6 SolventGC grade pentane.8. Hazards8.1 There is a significant fire hazard from LPG, and sincethe
38、 boiling point of LPG can be as low as -41C, there is a riskof freezing “burns.” Take appropriate safety precautions toprevent ignition or fire, and wear suitable protective equipmentto protect against skin contact with LPG.8.2 An appropriate laboratory ventilation system shall beused.8.3 An appropr
39、iate waste line shall be installed. The pres-sure station and injector shall be connected to this line. Thewaste line should vent outside the building.8.4 Pressure station, cylinder, injector, and controller shallbe grounded appropriately.9. Preparation of Apparatus9.1 Gas ChromatographInstall and v
40、erify performance inaccordance with the manufacturers instructions. Typical oper-ating conditions are shown in Table 1.FIG. 1 Overview of the Couplings Inside the GC Oven and the Couplings to the Solvent Vent ValveD7756 133FIG. 2 High Pressure ValveA Sample cylinderB Sample line inC Injection device
41、D Cool on column inletE Gas chromatographF Sample line outG RotometerH VaporizerI Waste systemP Pressure gaugeFIG. 3 Typical Configuration of a Pressure StationD7756 1349.2 Pressure StationInstall in accordance with the manu-facturers instructions. Purge sample and check carefully forleaks.9.3 High
42、Pressure Liquefied Gas InjectorInstall in accor-dance with the manufacturers instructions.9.4 Column ConfigurationInstall the columns as shown inFig. 1. Use low dead volume connections, and check for leaks.10. Calibration10.1 Perform a one point calibration at the startup of theinstrument, when the
43、result of the validation sample fallsoutside the acceptable SQC limits in accordance with Section14 or after changes in the application hardware or gas supply,or both.10.2 To verify system linearity over the range of expectedsample residues, a linearity check should be performed. Moreinformation can
44、 be found in Appendix X5.10.3 Run a blank run, without sample injection. Cycle theGC several times until the baseline is stable. A baseline isstable when the start and end signal (in pA) of two consecutiveblank runs are within 5%. An unstable baseline can be causedby a leak, detector gases, or by hi
45、gh boiling point componentsor materials that have not yet eluted from the column. Thesignal height (in pA) at the end of an analysis of a calibration,validation, or sample shall be equal or higher than the blankbaseline. A signal higher than 5% could indicate a poorlyconditioned column or the elutio
46、n of sample components witha boiling point higher than 522C. Refer to the datasheet of thecolumn for instructions on conditioning the column.10.4 Analyze the n-alkane retention time standard (7.6), andestablish the retention time for C10and C40. There should bebaseline separation between the solvent
47、 and the first normalalkane peak (C10). If the separation is not sufficient, adjust thetemperature program, re-establish the baseline, and then reana-lyze the retention time standard. An example is shown in Fig.4.10.5 Analyze the calibration mixture. The calibration mix-ture is either in LPG or in p
48、entane (7.1 and 7.2).10.6 Integrate the oily residue by summing the area fromC10through C40.10.7 Determine the response factor by dividing the knownconcentration by the total area, and use this for the calculationof unknown samples under the assumption that all samplecomponents have the same respons
49、e factor.10.8 Analyze the validation sample using the liquefied gasinjector. Analyze the validation sample once per day of usebefore the samples. Repeat the analysis when the result of thevalidation sample falls outside the acceptable SQC limits inaccordance with Section 14.11. Procedure11.1 Collect a representative sample according to PracticeD1265 or D3700.11.2 Connect the sample cylinder to the pressure station andpressurize to approximately 2500 6 200 kPa (363 6 29 psi). Itis important to maintain and reproduce this pressu
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