1、Designation: D 1319 03e1Designation: 156/97An American National StandardStandard Test Method forHydrocarbon Types in Liquid Petroleum Products byFluorescent Indicator Adsorption1This standard is issued under the fixed designation D 1319; 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 (e) indicates an editorial change since the last revision or reapproval.This standard has been approved for use by agencies of the Dep
3、artment of Defense.e1NOTEFootnote 7 and Table 2 were updated editorially in June 2006.1. Scope*1.1 This 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 frac
4、tions that distill below 315C. Thistest method may apply to concentrations outside these ranges,but the precision has not been determined. Samples containingdark-colored components that interfere in reading the chro-matographic bands cannot be analyzed.1.2 This test method is intended for use with f
5、ull 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 fuel
6、s 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 blend
7、ing 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 olefi
8、ns, 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 in commercial blen
9、ds. 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 The values stated in SI units ar
10、e to be regarded asstandard.NOTE 1For the determination of olefins below 0.3 volume %, othertest methods are available, such as Test Method D 2710.1.7 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 sta
11、ndard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. For specific hazardstatements, see Section 7, 8.1, and 10.5.2. Referenced Documents2.1 ASTM Standards:2D86 Test Method for Distillation of Petroleum Products atAtmosph
12、eric PressureD 1655 Specification for Aviation Turbine FuelsD 2710 Test Method for Bromine Index of Petroleum Hy-drocarbons by Electrometric TitrationD 3663 Test Method for Surface Area of Catalysts andCatalyst CarriersD 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4815 Test
13、 Method for Determination of MTBE, ETBE,TAME, DIPE, tertiary-Amyl Alcohol and C1to C4Alco-hols in Gasoline by Gas Chromatography1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04 on Hydrocarbon
14、Analysis.In the IP, this test method is under the jurisdiction of the StandardizationCommittee. This test method has been approved by the sponsoring committees andaccepted by the cooperating societies in accordance with established procedures.Current edition approved Nov. 1, 2003. Published January
15、2004. Originallyapproved in 1954. Last previous edition approved in 2002 as D 131902a.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary
16、 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 Box C700, West Conshohocken, PA 19428-2959, United States.D 5599 Test Method for Determination of Oxygenates inGasoline by Gas Chromatography and Oxygen
17、 SelectiveFlame Ionization DetectionE11 Specification for Wire Cloth and Sieves for TestingPurposes2.2 Other Standards:GC/OFID EPA Test MethodOxygen and Oxygenate Con-tent Analysis3BS4101 2000 Test sieves. Technical requirements andtesting. Test sieves of metal wire cloth43. Terminology3.1 Definitio
18、ns 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 volume % of alkenes, plus cyc
19、loalkenes,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 a mixture offluorescent dyes
20、. 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 selectively, with the hydro-carbon type
21、s, 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 % of saturates,olefins, and ar
22、omatics 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 catalytic reforming andfrom thermal a
23、nd 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 D 1655.6. Apparatus6.1 Adsorption Columns, with precision bore (“true bore” IPdesignation) tubing, as shown on the right
24、 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 analyzer section for theprecision
25、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 of shoulderedconnections. Su
26、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
27、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
28、 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-mm analyzer section,having an
29、 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 to provide aleakproof connec
30、tion 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 irregularities in theinner diameter a
31、nd 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 suitable length of vinyl tubing
32、,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 to melt the vinyl, then inser
33、t 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 separator section (which has been
34、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.6.2 Zone-Measuring DeviceThe zones may be markedwith a glass-wri
35、ting 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 convenient to have each rule fitted3Code of Federal Regulations, Part 80 of Title 40, 80.46 (g); also publi
36、shed inthe Federal Register, Vol 59, No. 32, Feb. 16, 1994, p. 7828. No longer available.4Available from British Standards Institution (BSI) Customer Services, 389Chiswick High Road, London, W4 4ALD131903e12with four movable metal index clips (Fig. 1) for marking zoneboundaries and measuring the len
37、gth 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 vibrating individual columns or
38、the 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 gage are satisfactory.6.6 Regulator(s), capable of adjusting and maintaining thepressure within the 0 to 103 kPa delivery range.7. Reagents and M
39、aterials7.1 Silica Gel,5,6manufactured to conform to the specifica-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 slurryo
40、n a magnetic stirrer for 20 min and then determine the pH5If 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 you may attend.6The sol
41、e source of supply of the silica gel known to the committee at this timeis W. R. Grace and Co., Davison Chemical Div., Baltimore, MD 21203; specifyCode 923.FIG. 1 Adsorption Columns with Standard Wall (left) and Precision Bore (right) Tubing in Analyzer SectionD131903e13with the calibrated meter. Be
42、fore 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 olefin boundary fading. The ex
43、act 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 adsorption, following a def
44、inite, 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 transferred as required to
45、 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 nitrogen) delivered to t
46、he topof the column at pressures controllable over the range from 0to 103 kPa gage. (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 with
47、sampling procedures in Practice D 4057. 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 of Apparatus9.1 Mount the
48、 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 col
49、umns.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 3One way to prepare the column for analysis is to freelysuspend the column from a loose-fitting clamp placed immediately belowthe spherical joint of the charger section. While vibrating the columnalong its entire length, add small increment
