1、Designation: D1319 14Standard 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 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 the precision h
4、as 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 intended for use wit
5、h 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 derivedfrom fossil f
6、uels 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 oxygenated bl
7、ending 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 volume percent ol
8、efins, and 4568 volumepercent saturates.1.5 The oxygenated blending components, methanol,ethanol, methyl-tert-butylether (MTBE), tert-amylmethylether(TAME), and ethyl-tert-butylether (ETBE), do not interferewith the determination of hydrocarbon types at concentrationsnormally found in commercial ble
9、nds. 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 has been designa
10、ted 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 applicable product M
11、a-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 are to be regar
12、ded 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 practices and determin
13、e 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 PressureD1655 Specification for Aviation Turbine FuelsD2710 Test M
14、ethod for Bromine Index of Petroleum Hydro-carbons by Electrometric TitrationD3663 Test Method for Surface Area of Catalysts andCatalyst Carriers1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSub
15、committee D02.04.0C on Liquid Chromatography.Current edition approved Oct. 1, 2014. Published October 2014. Originallyapproved in 1954. Last previous edition approved in 2013 as D1319 13. DOI:10.1520/D1319-14.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Custom
16、er Service at serviceastm.org. For Annual Book of 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
17、 19428-2959. United States1D4057 Practice for Manual 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 Ga
18、s Chromatography and Oxygen SelectiveFlame Ionization DetectionE11 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 clot
19、h43. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 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
20、volume % of alkenes, plus cycloalkenes,and some dienes.3.1.3 saturatesthe 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
21、 a mixture offluorescent dyes. When all 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 selectivel
22、y, with the hydro-carbon types, and make 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 %
23、 of saturates,olefins, and aromatics in petroleum fractions is important 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 catalyti
24、c reforming andfrom thermal and catalytic cracking as blending componentsfor 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) t
25、ubing, as shown on the right in 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 analyz
26、er section for theprecision bore tubing shall be 1.60 to 1.65 mm. In 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
27、of shoulderedconnections. Support 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 ensur
28、e that the tip does nottend 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 analyz
29、er section, provided thatthe 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.Similar commercial compression-type connectors may be em-ployed at the terminal end of the 3-m
30、m analyzer section,having an integral porous support to retain the silica 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
31、to provide aleakproof connection between the separator and the analyzersections. 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 irregular
32、ities in theinner diameter and such tubing should not be used. Prepare 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 sui
33、table length of vinyl tubing,making certain that the two glass sections 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 t
34、o melt the vinyl, then insert the upper endof the analyzer section into 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 separa
35、tor section (which has been cut square), to the3-mm analyzer section, provided that the internal geometry isessentially 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
36、connectors may be employed at the terminal3Code 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
37、.bsi-).D1319 142end of the 3-mm analyzer section having an integral poroussupport 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 DeviceThe zones may be markedwith
38、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 (Fig. 1) for marking zonebo
39、undaries 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 vertically along theapparatus. Adjust to give the best fluorescence.6.4 Electric Vibrator, for v
40、ibrating individual columns or theframe 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 satisfactory.6.6 Regulator(s), capable of adjusting and maintaining thepressure within the 0 to 103 kPa d
41、elivery range.FIG. 1 Adsorption Columns with Standard Wall (left) and Precision Bore (right) Tubing in Analyzer SectionD1319 1437. Reagents and Materials7.1 Silica Gel,5manufactured to conform to the specifica-tions shown in Table 2. Determine the pH of the silica gel asfollows: Calibrate a pH meter
42、 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 the calibrated meter. Before use, dry the gel in a shallowvessel at 175C for 3 h. Transfer the
43、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 olefin boundary fading. The exact reason forthis phenomenon is unknown but will affect accuracy and p
44、recision.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 shal
45、l 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 transferred as required to a smaller working vialfrom which the dyed gel is routinely taken for a
46、nalyses.7.3 Isoamyl Alcohol, (3-methyl-1-butanol) 99 %.(WarningFlammable. Health hazard.)7.4 Isopropyl Alcohol, (2-propanol) minimum 99 % purity.(Warning Flammable. Health hazard.)7.5 Pressuring GasAir (or nitrogen) delivered to the topof the column at pressures controllable over the range from 0to
47、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 sample in accordance withsampling procedures in Practice D4057. For samples thatwould meet vol
48、atility 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 of Apparatus9.1 Mount the apparatus assembly in a darkened room orarea to facilitate observatio
49、n 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 providing a connection to the desired numberof columns.10. Procedure10.1 Ensure that the silica gel is tightly packed in thecolumn and charger section (up to the appropriate level), whichincludes the appropriate amount of dyed gel (3 to 5 mm) addedto an approximately half-full separator section, prior to the startof the sample analysis. See Note 3 for specific guidance.NOTE 3
