ASTM D1319-2018 Standard Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption.pdf

1、Designation: D1319 18Standard Test Method forHydrocarbon Types in Liquid Petroleum Products byFluorescent Indicator Adsorption1This standard is issued under the fixed designation D1319; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revisio

2、n, 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.This standard has been approved for use by agencies of the U.S. Department of Defense.1. Scope*1.1 This test method

3、 covers the determination of hydrocar-bon types over the concentration ranges from 5 % to 99 % byvolume aromatics, 0.3 % to 55 % by volume olefins, and 1 %to 95 % by volume saturates in petroleum fractions that distillbelow 315 C. This test method may apply to concentrationsoutside these ranges, but

4、 the precision has not been determined.Samples containing dark-colored components that interfere inreading the chromatographic bands cannot be analyzed.NOTE 1For the determination of olefins below 0.3 % by volume, othertest methods are available, such as Test Method D2710.1.2 This test method is int

5、ended for use with full boilingrange products. Cooperative data have established that theprecision statement does not apply to narrow boiling petroleumfractions near the 315 C limit. Such samples are not elutedproperly, and results are erratic.1.3 This test method includes a relative bias section ba

6、sedon Practice D6708 accuracy assessment between Test MethodD1319 and Test Method D5769 for total aromatics in spark-ignition engine fuels as a possible Test Method D1319 alter-native to Test Method D5769 for U.S. EPA spark-ignitionengine fuel regulations reporting. The Practice D6708 derivedcorrela

7、tion equation is only applicable for fuels in the totalaromatic concentration range from 3.3 % to 34.4 % by volumeas measured by Test Method D1319 and the distillationtemperature T95, at which 95 % of the sample has evaporated,ranges from 149.1 C to 196.6 C (300.3 F to 385.8 F) whentested according

8、to Test Method D86.1.3.1 The applicable Test Method D5769 range for totalaromatics is 3.7 % to 29.4 % by volume as reported by TestMethod D5769 and the distillation temperature T95values, atwhich 95 % of the sample has evaporated, when testedaccording to Test Method D86 is from 149.1 C to 196.6 C(30

9、0.3 F to 385.8 F).1.4 The applicability of this test method to products derivedfrom fossil fuels other than petroleum, such as coal, shale, ortar sands, has not been determined, and the precision statementmay or may not apply to such products.1.5 This test method has two precision statements depicte

10、din tables. The first table is applicable to unleaded fuels that donot contain oxygenated blending components. It may or maynot apply to automotive gasolines containing lead antiknockmixtures. The second table is applicable to oxygenate blended(for example, MTBE, ethanol) automotive spark ignition f

11、uelsamples with a concentration range of 13 % to 40 % by volumearomatics, 4 % to 33 % by volume olefins, and 45 % to 68 %by volume saturates.1.6 The oxygenated blending components, methanol,ethanol, methyl-tert-butylether (MTBE), tert-amylmethylether(TAME), and ethyl-tert-butylether (ETBE), do not i

12、nterferewith the determination of hydrocarbon types at concentrationsnormally found in commercial blends. These oxygenatedcomponents are not detected since they elute with the alcoholdesorbent. Other oxygenated compounds shall be individuallyverified. When samples containing oxygenated blending com-

13、ponents are analyzed, correct the results to a total-sample basis.1.7 WARNINGMercury has been designated by manyregulatory agencies as a hazardous substance that can causeserious medical issues. Mercury, or its vapor, has been dem-onstrated to be hazardous to health and corrosive to materials.Use Ca

14、ution when handling mercury and mercury-containingproducts. See the applicable product Safety Data Sheet (SDS)for additional information. The potential exists that sellingmercury or mercury-containing products, or both, is prohibitedby local or national law. Users must determine legality of salesin

15、their location.1.8 The values stated in SI units are to be regarded asstandard. The values given in parentheses after SI units areprovided for information only and are not considered standard.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lu

16、bricants and is the direct responsibility ofSubcommittee D02.04.0C on Liquid Chromatography.Current edition approved Oct. 1, 2018. Published December 2018. Originallyapproved in 1954. Last previous edition approved in 2015 as D1319 15. DOI:10.1520/D1319-18.*A Summary of Changes section appears at th

17、e end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for t

18、heDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.11.9 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of th

19、is standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.For specific warning statements, see Section 7, 8.1, and 10.5.1.10 This international standard was developed in accor-dance with internationally r

20、ecognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D86 Test Method f

21、or Distillation of Petroleum Products andLiquid Fuels at Atmospheric PressureD1655 Specification for Aviation Turbine FuelsD2710 Test Method for Bromine Index of Petroleum Hydro-carbons by Electrometric TitrationD3663 Test Method for Surface Area of Catalysts andCatalyst CarriersD4057 Practice for M

22、anual Sampling of Petroleum andPetroleum ProductsD4815 Test Method for Determination of MTBE, ETBE,TAME, DIPE, tertiary-Amyl Alcohol and C1to C4Alco-hols in Gasoline by Gas ChromatographyD5599 Test Method for Determination of Oxygenates inGasoline by Gas Chromatography and Oxygen SelectiveFlame Ioni

23、zation DetectionD5769 Test Method for Determination of Benzene, Toluene,and Total Aromatics in Finished Gasolines by GasChromatography/Mass SpectrometryD6708 Practice for Statistical Assessment and Improvementof Expected Agreement Between Two Test Methods thatPurport to Measure the Same Property of

24、a MaterialE11 Specification for Woven Wire Test Sieve Cloth and TestSieves2.2 Other Standards:GC/OFID EPA Test MethodOxygen and Oxygenate Con-tent Analysis3BS 4101:2000 Test sieves. Technical requirements andtesting. Test sieves of metal wire cloth43. Terminology3.1 Definitions of Terms Specific to

25、This Standard:3.1.1 aromaticsthe volume percent of monocyclic andpolycyclic aromatics, plus aromatic olefins, some dienes,compounds containing sulfur and nitrogen, or higher boilingoxygenated compounds (excluding those listed in 1.6).3.1.2 olefinsthe volume percent of alkenes, pluscycloalkenes, and

26、some dienes.3.1.3 saturatesthe volume percent of alkanes, plus cy-cloalkanes.4. Summary of Test Method4.1 Approximately 0.75 mL of sample is introduced into aspecial glass adsorption column packed with activated silicagel. A small layer of the silica gel contains a mixture offluorescent dyes. When a

27、ll the sample has been adsorbed on thegel, alcohol is added to desorb the sample down the column.The hydrocarbons are separated in accordance with theiradsorption affinities into aromatics, olefins, and saturates. Thefluorescent dyes are also separated selectively, with the hydro-carbon types, and m

28、ake the boundaries of the aromatic, olefin,and saturate zones visible under ultraviolet light. The volumepercentage of each hydrocarbon type is calculated from thelength of each zone in the column.5. Significance and Use5.1 The determination of the total volume percent ofsaturates, olefins, and arom

29、atics in petroleum fractions isimportant in characterizing the quality of petroleum fractionsas gasoline blending components and as feeds to catalyticreforming processes. This information is also important incharacterizing petroleum fractions and products from catalyticreforming and from thermal and

30、 catalytic cracking as blendingcomponents for motor and aviation fuels. This information isalso important as a measure of the quality of fuels, such asspecified in Specification D1655.6. Apparatus6.1 Adsorption Columns, with precision bore (“true bore” IPdesignation) tubing, as shown on the right in

31、 Fig. 1, made ofglass and consisting of a charger section with a capillary neck,a separator section, and an analyzer section; or with standardwall tubing, as shown on the left in Fig. 1. Refer to Table 1 forcolumn tolerance limits.6.1.1 The inner diameter of the analyzer section for theprecision bor

32、e tubing shall be 1.60 mm to 1.65 mm. In additionthe length of an approximately 100 mm thread of mercury shallnot vary by more than 0.3 mm in any part of the analyzersection. In glass-sealing the various sections to each other,long-taper connections shall be made instead of shoulderedconnections. Su

33、pport the silica gel with a small piece of glasswool located between the ball and socket of the 12/2 sphericaljoint and covering the analyzer outlet. The column tip attachedto the 12/2 socket shall have a 2 mm internal diameter. Clampthe ball and socket together and ensure that the tip does nottend

34、to slide from a position in a direct line with the analyzersection during the packing and subsequent use of the column.Commercial compression-type connectors may be used tocouple the bottom of the separator section (which has been cutsquare), to the disposable 3 mm analyzer section, provided thatthe

35、 internal geometry is essentially similar to the aforemen-tioned procedure and provides for a smooth physical transitionfrom the inner diameters of the two glass column sections.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org.

36、For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Code of Federal Regulations, Part 80 of Title 40, 80.46 (g); also published inthe Federal Register, Vol 59, No. 32, Feb. 16, 1994, p. 7828. No longer available.4Available from Britis

37、h Standards Institution (BSI), 389 Chiswick High Rd.,London W4 4AL, U.K., http:/.D1319 182Similar commercial compression-type connectors may be em-ployed at the terminal end of the 3 mm analyzer section, havingan integral porous support to retain the silica gel.6.1.2 For convenience, adsorption colu

38、mns with standardwall tubing, as shown on the left in Fig. 1, can be used. Whenusing standard wall tubing for the analyzer section, it isnecessary to select tubing of uniform bore and to provide aleakproof connection between the separator and the analyzersections. Calibrations of standard wall tubin

39、g would be im-practical; however, any variations of 0.5 mm or greater, asmeasured by ordinary calipers, in the outside diameter alongthe tube can be taken as an indication of irregularities in theinner diameter and such tubing should not be used. Prepare theglassware to retain the gel. One way to ac

40、complish this is todraw out one end of the tubing selected for the analyzer sectionto a fine capillary. Connect the other end of the analyzer sectionto the separator section with a suitable length of vinyl tubing,making certain that the two glass sections touch. A 30 mm 65 mm length of vinyl tubing

41、has been found to be suitable. Toensure a leakproof glass-to-vinyl seal with the analyzer section,it is necessary to heat the upper end of the analyzer sectionuntil it is just hot enough to melt the vinyl, then insert the upperend of the analyzer section into the vinyl sleeve. Alternatively,this sea

42、l can be made by securing the vinyl sleeve to theanalyzer section by wrapping it tightly with soft wire. Com-mercial compression-type connectors may be used to couplethe bottom of the separator section (which has been cutsquare), to the 3 mm analyzer section, provided that theFIG. 1 Adsorption Colum

43、ns with Standard Wall (left) and Precision Bore (right) Tubing in Analyzer SectionD1319 183internal geometry is essentially similar to the aforementionedprocedure and provides for a smooth physical transition fromthe inner diameters of the two glass column sections. Similarcommercial compression-typ

44、e connectors may be employed atthe terminal end of the 3 mm analyzer section having anintegral porous support to retain the silica gel.6.1.3 An alternative pressuring gas connection is shown inFig. 2. Otherwise, all adsorption column dimensions andrequirements are unchanged.6.2 Zone-Measuring Device

45、The zones may be markedwith a glass-writing pencil and the distances measured with ameter rule, with the analyzer section lying horizontally.Alternatively, the meter rule may be fastened adjacent to thecolumn. In this case, it is convenient to have each rule fittedwith four movable metal index clips

46、 (Fig. 1) for marking zoneboundaries and measuring the length of each zone.6.3 Ultraviolet Light Source, with radiation predominantlyat 365 nm is required. A convenient arrangement consists ofone or two 915 mm or 1220 mm units mounted vertically alongthe apparatus. Adjust to give the best fluorescen

47、ce.6.4 Electric Vibrator, for vibrating individual columns or theframe supporting multiple columns.6.5 Hypodermic Syringe, 1 mL, graduated to 0.01 mL or0.02 mL, with needle 102 mm in length. Needles of No. 18gauge, 20 gauge, or 22 gauge are satisfactory.6.6 Regulator(s), capable of adjusting and mai

48、ntaining thepressure within the 0 kPa to 103 kPa delivery range.7. Reagents and Materials7.1 Silica Gel,5manufactured to conform to the specifica-tions shown in Table 2. To be suitable for use, dry the gel in ashallow vessel at 175 C for 3 h. Transfer the dried gel to an airtight container while sti

49、ll hot, and protect it thereafter fromatmospheric moisture.NOTE 2Some batches of silica gel that otherwise meet specificationshave been found to produce olefin boundary fading. The exact reason forthis phenomenon is unknown but will affect accuracy and precision.7.2 Fluorescent Indicator Dyed GelA standard dyed gel,5,6consisting of a mixture of recrystallized Petrol RedAB4 andpurified portions of the olefin and aromatic dyes obtained bychromatographic adsorption, following a definite, uniformprocedure, and deposited on silica gel. The dyed gel