1、Designation: D1319 10Designation: 156/97Standard 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
2、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.This standard has been approved for use by agencies of the Department of Defense.1. Scope*1.1 Th
3、is test method covers the determination of hydrocar-bon types over the concentration ranges from 5 to 99 volume %aromatics, 0.3 to 55 volume % olefins, and 1 to 95 volume %saturates in petroleum fractions that distill below 315C. Thistest method may apply to concentrations outside these ranges,but t
4、he precision has not been determined. Samples containingdark-colored components that interfere in reading the chro-matographic bands cannot be analyzed.NOTE 1For the determination of olefins below 0.3 volume %, othertest methods are available, such as Test Method D2710.1.2 This test method is intend
5、ed for use with full boilingrange products. Cooperative data have established that theprecision statement does not apply to narrow boiling petroleumfractions near the 315C limit. Such samples are not elutedproperly, and results are erratic.1.3 The applicability of this test method to products derive
6、dfrom 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.1.4 This test method has two precision statements depictedin tables. The first table is applicable to unleaded fuels that donot contain
7、 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 fuelsamples with a concentration range of 1340 volume percentaromatics, 433 vol
8、ume percent olefins, and 4568 volumepercent saturates.1.5 The oxygenated blending components, methanol, etha-nol, methyl-tert-butylether (MTBE), tert-amylmethylether(TAME), and ethyl-tert-butylether (ETBE), do not interferewith the determination of hydrocarbon types at concentrationsnormally found i
9、n 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-ponents are analyzed, correct the results to a total-sample basis.1.6 WARNINGMercury
10、has been designated by manyregulatory agencies as a hazardous material that can causecentral nervous system, kidney and liver damage. Mercury, orits vapor, may be hazardous to health and corrosive tomaterials. Caution should be taken when handling mercury andmercury containing products. See the appl
11、icable product Ma-terial Safety Data Sheet (MSDS) for details and EPAswebsitehttp:/www.epa.gov/mercury/faq.htmfor addi-tional information. Users should be aware that selling mercuryand/or mercury containing products into your state or countrymay be prohibited by law.1.7 The values stated in SI units
12、 are to be regarded asstandard. No other units of measurement are included in thisstandard.1.8 This standard does 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 practi
13、ces and determine the applica-bility of regulatory limitations prior to use. For specificwarning statements, see Section 7, 8.1, and 10.5.2. Referenced Documents2.1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products atAtmospheric Pressure1This test method is under the jurisdictio
14、n of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04.0C on Liquid Chromatography.In the IP, this test method is under the jurisdiction of the StandardizationCommittee. This test method has been approved by the sponsoring committees andacc
15、epted by the cooperating societies in accordance with established procedures.Current edition approved May 1, 2010. Published June 2010. Originallyapproved in 1954. Last previous edition approved in 2008 as D131908. DOI:10.1520/D1319-10.2For referenced ASTM standards, visit the ASTM website, www.astm
16、.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Bo
17、x C700, West Conshohocken, PA 19428-2959, United States.D1655 Specification for Aviation Turbine FuelsD2710 Test Method for Bromine Index of Petroleum Hy-drocarbons by Electrometric TitrationD3663 Test Method for Surface Area of Catalysts andCatalyst CarriersD4057 Practice for Manual Sampling of Pet
18、roleum 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 Ionization DetectionE11 S
19、pecification 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 This Standard:3
20、.1.1 aromaticsthe volume % of monocyclic and polycy-clic aromatics, plus aromatic olefins, some dienes, compoundscontaining sulfur and nitrogen, or higher boiling oxygenatedcompounds (excluding those listed in 1.5).3.1.2 olefinsthe volume % of alkenes, plus cycloalkenes,and some dienes.3.1.3 saturat
21、esthe volume % of alkanes, plus cycloal-kanes.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 all the sample has been adsorbed
22、 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 make the boundaries of the aroma
23、tic, 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 % of saturates,olefins, and aromatics in petroleum fractions is impor
24、tant incharacterizing the quality of petroleum fractions as gasolineblending components and as feeds to catalytic reformingprocesses. This information is also important in characterizingpetroleum fractions and products from catalytic reforming andfrom thermal and catalytic cracking as blending compo
25、nentsfor motor and aviation fuels. This information is also importantas a measure of the quality of fuels, such as specified inSpecification D1655.6. Apparatus6.1 Adsorption Columns, with precision bore (“true bore” IPdesignation) tubing, as shown on the right in Fig. 1, made ofglass and consisting
26、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 bore tubing shall be 1.60 to 1.65 mm. In
27、 addition thelength 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. Support the silica gel with a small piece
28、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 to slide from a position in a direct lin
29、e 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 internal geometry is essentially simila
30、r to the aforemen-tioned procedure and provides for a smooth physical transitionfrom the inner diameters of the two glass column sections.Similar commercial compression-type connectors may be em-ployed at the terminal end of the 3-mm analyzer section,having an integral porous support to retain the s
31、ilica gel.6.1.2 For convenience, adsorption columns 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 analy
32、zersections. Calibrations of standard wall tubing 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. Prepa
33、re theglassware to retain the gel. One way to accomplish 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 secti
34、ons touch. A 30 6 5mmlength of vinyl tubing has been found to be suitable. To ensurea leakproof glass-to-vinyl seal with the analyzer section, it isnecessary to heat the upper end of the analyzer section until itis just hot enough to melt the vinyl, then insert the upper endof the analyzer section i
35、nto the vinyl sleeve. Alternatively, thisseal can be made by securing the vinyl sleeve to the analyzersection by wrapping it tightly with soft wire. Commercialcompression-type connectors may be used to couple the bottomof the separator section (which has been cut square), to the3-mm analyzer section
36、, provided that the internal geometry is3Code 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 BSI British Standards, 389 Chiswick High Road, London, W44AL, United Kingdom (www.b
37、si-).D1319 102essentially similar to the aforementioned procedure and pro-vides for a smooth physical transition from the inner diametersof the two glass column sections. Similar commercialcompression-type connectors may be employed at the terminalend of the 3-mm analyzer section having an integral
38、poroussupport to retain the silica gel.6.2 Zone-Measuring DeviceThe zones may be markedwith a glass-writing pencil and the distances measured with ameter rule, with the analyzer section lying horizontally. Alter-natively, the meter rule may be fastened adjacent to thecolumn. In this case, it is conv
39、enient to have each rule fittedwith four movable metal index clips (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 or 1220-mm units mounted ve
40、rtically along theapparatus. Adjust to give the best fluorescence.6.4 Electric Vibrator, for vibrating individual columns orthe frame supporting multiple columns.6.5 Hypodermic Syringe, 1 mL, graduated to 0.01 or 0.02mL, with needle 102 mm in length. Needles of No. 18, 20, or22 gauge are satisfactor
41、y.FIG. 1 Adsorption Columns with Standard Wall (left) and Precision Bore (right) Tubing in Analyzer SectionD1319 1036.6 Regulator(s), capable of adjusting and maintaining thepressure within the 0 to 103 kPa delivery range.7. Reagents and Materials7.1 Silica Gel,5,6manufactured to conform to the spec
42、ifica-tions shown in Table 2. Determine the pH of the silica gel asfollows: Calibrate a pH meter with standard pH 4 and pH 7buffer solutions. Place5gofthegelsample in a 250-mLbeaker. Add 100 mL of water and a stirring bar. Stir the slurryon a magnetic stirrer for 20 min and then determine the pHwith
43、 the calibrated meter. Before use, dry the gel in a shallowvessel at 175C for 3 h. Transfer the dried gel to an air tightcontainer while still hot, and protect it thereafter from atmo-spheric moisture.NOTE 2Some batches of silica gel that otherwise meet specificationshave been found to produce olefi
44、n boundary fading. The exact reason forthis phenomenon is unknown but will affect accuracy and precision.7.2 Fluorescent Indicator Dyed GelA standard dyedgel,5,7consisting of a mixture of recrystallized Petrol Red AB4and purified portions of the olefin and aromatic dyes obtainedby chromatographic ad
45、sorption, following a definite, uniformprocedure, and deposited on silica gel. The dyed gel shall bestored in a dark place under an atmosphere of nitrogen. Whenstored under these conditions, the dyed gel can have a shelf lifeof at least five years. It is recommended that portions of thedyed gel be t
46、ransferred as required to a smaller working vialfrom which the dyed gel is routinely taken for analyses.7.3 Isoamyl Alcohol, (3-methyl-1-butanol) 99 %.(WarningFlammable. Health hazard.)7.4 Isopropyl Alcohol, (2-propanol) minimum 99 % purity.(WarningFlammable. Health hazard.)7.5 Pressuring GasAir (or
47、 nitrogen) delivered to the topof the column at pressures controllable over the range from 0to 103 kPa gauge. (WarningCompressed gas under highpressure.)7.6 Acetone, reagent grade, residue free. (WarningFlammable. Health hazard.)7.7 Buffer Solutions, pH 4 and 7.8. Sampling8.1 Obtain a representative
48、 sample in accordance withsampling procedures in Practice D4057. For samples thatwould meet volatility conditions of Group 2 or less of TestMethod D86, ensure that the sample is maintained at atemperature of#4C when opening or transferring the sample.(WarningFlammable. Health hazard.)9. Preparation
49、of Apparatus9.1 Mount the apparatus assembly in a darkened room orarea to facilitate observation of zone boundaries. For multipledeterminations, assemble an apparatus that includes the ultra-violet light source, a rack to hold the columns, and a gasmanifold system with spherical joints to connect to the desirednumber of columns.5If you are aware of alternative suppliers, please provide this information toASTM International Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee,1which y
