1、Designation: D4124 09 (Reapproved 2018)Standard Test Method forSeparation of Asphalt into Four Fractions1This standard is issued under the fixed designation D4124; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last re
2、vision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the separation of four definedfractions from petroleum asphalts. The four fractions aredefined as sat
3、urates, naphthene aromatics, polar aromatics, andiso-octane insoluble asphaltenes. This method can also be usedto isolate saturates, naphthene aromatics, and polar aromaticsfrom distillate products such as vacuum gas oils, lubricatingoils, and cycle stocks. These distillate products usually do notco
4、ntain asphaltenes.1.2 The values stated in SI units are to be regarded asstandard.1.3 Since a precision estimate for this standard has not beendeveloped, this test method is to be used for research orinformational purposes only. Therefore, this standard shouldnot be used for acceptance or rejection
5、of a material forpurchasing purposes.1.4 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, health, and environmental practices and deter-mine the applicability o
6、f regulatory limitations prior to use.Specific precautionary statements are given in Section 8.1.5 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Sta
7、ndards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D140 Practice for Sampling Bituminous Materials2.2 Other Documents:Manual on Hydrocarbon Analysis33. Terminology3.1 Definitions of Terms Sp
8、ecific to This Standard:3.1.1 asphaltenes or alkane insolublesinsoluble matterthat can be separated from asphalt following digestion of theasphalt in n-alkane (and in some cases, branched alkanes)under the specified conditions in this test method.3.1.2 naphtheneany of a group of hydrocarbon ring com
9、-pounds of the general formula, CnH2n, derivatives of cyclopen-tane and cyclohexane, found in certain petroleum stocks.3.1.3 naphthene aromaticsmaterial that is adsorbed oncalcined CG-20 alumina in the presence of n-heptane, anddesorbed by toluene, after removal of saturates under theconditions spec
10、ified.3.1.4 petrolenes (also referred to as maltenes)(1) any ofthe constituents of a bitumen, as asphalt, that are soluble inn-alkanes (and in some cases, branched alkanes), whichgenerally range in carbon number between n-C5to n-C10alkanes, n-heptane being the most common solvent used; (2)the low mo
11、lecular weight alkane-soluble matter recoveredfollowing separation of asphaltenes from the digested mixtureunder the specified conditions described in this and similar testmethods.3.1.5 polar aromatics (resins)material desorbed from cal-cined CG-20 alumina absorbent, after the saturates fraction and
12、naphthenic aromatics fraction have been removed, using tolu-ene:methanol (50:50, vol:vol) and trichloroethylene eluateunder the conditions specified.3.1.6 saturatesmaterial that, on percolation in an alkaneeluate, is not absorbed on calcined CG-20 alumina absorbentunder the conditions specified.4. S
13、ummary of Test Method4.1 The sample containing the four defined fractions is firstseparated into alkane-insoluble asphaltenes and alkane-solublepetrolenes. Petrolenes are then adsorbed onto calcined CG-20alumina and further fractionated into saturate, naphthene1This test method is under the jurisdic
14、tion of ASTM Committee D04 on Roadand Paving Materials and is the direct responsibility of Subcommittee D04.47 inMiscellaneous Asphalt Tests.Current edition approved Jan. 1, 2018. Published January 2018. Originallyapproved in 1982. Last previous edition approved in 2009 as D4124 09. DOI:10.1520/D412
15、4-09R18.2For 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 page onthe ASTM website.3Available from ASTM as MNL3-6TH-EB.Copyright ASTM In
16、ternational, 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 theDevelopment of International Standard
17、s, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1aromatic, and polar aromatic fractions by pumping an eluo-tropic series of elution solvents upwards through a glasschromatographic column packed with calcined alumina. Elutedfractions ar
18、e recovered by solvent removal prior to finalweighing. The three eluted fractions plus the alkane-precipitated asphaltenes comprise the four fractions as definedin Section 3.5. Significance and Use5.1 This test method separates asphalts into four well-defined fractions. Analysis of these fractions c
19、an be used toevaluate asphalt composition (1, 2).4For example, one cancompare the ratios of the fractions with other asphalt systemsto evaluate processing and aging parameters that relate toperformance properties of the asphalt.6. Apparatus and Materials6.1 Reflux Apparatus for Asphaltene/Maltene Se
20、paration,with features as specified in Fig. 1. (See 6.1.1.)6.1.1 Apparatus (Fig. 1)(a) ring stand with clamp; (b)heater stirring plate; (c) 500-mL Erlenmeyer flask with 29/42sintered glass neck; (d) reducer, 29/42 to 24/40 sintered glassnecks; (e) Allihn-type reflux condenser with 24/40 sinteredglas
21、s neck.6.2 Chromatographic Column Apparatus, with features asspecified in Fig. 2 (see 6.2.1 6.2.5).6.2.1 LC Apparatus (Fig. 2)(a) ring stand with clamp,flask (25-mL round bottom or Erlenmeyer flask); (b) meteringpump; (c) sealed glass LC column; (d) UV detector with dataacquisition system (wavelengt
22、h range 200 to 500 nm at0.1 nm); (e) graduated cylinder (Fig. 2).6.2.2 UV Detector with Data Acquisition System (Fig. 2)AUV detector with data acquisition system suitable for use withliquid chromatography or HPLC used to detect the occurrenceof material fractions (peak response) as they are eluted f
23、romthe column.6.2.3 Metering Pump (Fig. 2)Piston and piston chamberwill be constructed of materials resistant to deterioration bysolvents that will be used to perform the method. Flow raterange of the pump will be 0.1 to 5.0 mL/min 6 0.1 mL/minflow rate stability.6.2.4 LC Column with Water JacketClo
24、sed glass liquidchromatography column, 70 cm long and 1.5 cm insidediameter (volume, 124 cc). The LC column will be a closedcolumn with end plates containing solvent-permeable dia-phragms and fitting ports for 6.35-mm (14-in.) tubing fittings.6.2.5 Refrigerated/Heating CirculatorA refrigerated/heati
25、ng circulator, temperature range between 0 and 100 C 60.1 C stability, with water circulation through the LC columnwater jacket via high-pressure hose 15.9-mm (58-in. ID).6.3 Materials:6.3.1 UtilitiesFume hood, vacuum source, nitrogen gassource, cold water source, nitrogen gas-purged vacuum dryingov
26、en, rotary solvent evaporator (water bath and oil bath type),nitrogen gas stream evaporator with heater water bath.4The boldface numbers in parentheses refer to a list of references at the end ofthis standard.NOTE 1Key: (a) ring stand with large test tube clamp; (b) heater/stirring plate; (c) 500-mL
27、 Erlenmeyer flask with 29/42 sintered glass neck; (d)reducer 29/42 to 24/40 sintered glass spout to neck; (e) Allihn-type reflux condenser with 24/40 sintered glass spout.FIG. 1 Asphaltene/Maltene Separation ApparatusD4124 09 (2018)26.3.2 Erlenmeyer Flasks, 25-mL with glass stopper (1),500-mL with g
28、lass stoppers (5).6.3.3 Pear-Shaped Flask.6.3.4 Graduated Cylinder.6.3.5 Bchner-Style Funnel, Fritted Glass, 60 to 100-mL,ASTM 10 to 15-L medium porosity.6.3.6 Flask, Suction, 1Lto2L.6.3.7 Rinse Squeeze Bottle, 0.5-L size, TFE-fluorocarbon.6.3.8 Analytical Balance, 0.0001 to 250 g 6 0.0001 g.6.3.9 S
29、tirrer/Heater Plate, electric.6.3.10 Sample Vials, borosilicate, 25-mL (6) and 50-mL (2),clear, with Teflon-lined cap.6.3.11 Glass Funnels, (2), small.6.3.12 Teflon or Solvent-Resistant Funnels, (1), small.6.3.13 Teflon Flask-Neck Sleeves, (3) 24/40 size, (1) 29/42size.6.3.14 Hose, reinforced, high
30、pressure, 1.59-mm ID (58-in.ID).6.3.15 Tubing, clear, resistant to organic solvents, 1.59-mmID/3.17-mm OD (116-in. ID/18-in. OD).6.3.16 Tubing Fittings, standard 6.35-mm (14-in.) nut with3.17-mm OD (18-in. ID) hole and 3.17-mm (18-in.) ferrule.7. Absorbent and Reagents7.1 Alumina,5CG-20 chromatograp
31、hic grade, calcined at425 C for 16 h and stored in an evacuated desiccator inairtight bottles for 3 to 5 h.7.2 Purity of ReagentsHPLC grade chemicals shall beused in all sample preparations and tests. Unless otherwiseindicated, it is intended that all reagents conform to thespecifications of the Com
32、mittee on Analytical Reagents of theAmerican Chemical Society where such specifications areavailable.6Other grades may be used, provided it is firstascertained that the reagent is of sufficiently high purity topermit its use without lessening the accuracy of the determi-nation.5Aluminum Oxide availa
33、ble from EMD Chemicals, Inc., P.O. Box 70, 480Democrat Road, Gibbstown, NJ 08027 (Product Code AX0612), CASNumber:1344-28-1, 2.5 kg Chromatographic Grade Alumina (Al2O3) 80-200 meshCAS 1344-28-1, Cat # EM-AXO612-3.6Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society
34、, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.NOT
35、E 1Key: LC apparatus: (a) clamp stand with sample or solvent flask (round bottom or Erlenmeyer type); (b) metering pump; (c) sealed glass LCcolumn packed with alumina; (c1) glass column; (c2) collar; (c3) diaphragm; (c4) end plate; (c5) tubing nut/ferrule and tubing; (d) UV-VISspectrophotometric det
36、ector (200 to 500 nm at 0.1 nm); (e) graduated cylinders of various sizes for fraction collection.FIG. 2 Chromatographic Column for Separation of Asphalt by Elution-AdsorptionD4124 09 (2018)37.3 Reagents:7.3.1 iso-Octane (2,2,4-trimethyl pentane), HPLC grade,0.01 % water.7.3.2 n-Heptane, HPLC grade,
37、 0.01 % water.7.3.3 Methanol, anhydrous, HPLC grade, 0.01 % water.7.3.4 Toluene, HPLC grade, 0.001 % water.7.3.5 Trichloroethylene, ACS grade, 0.02 % water, boilingpoint 86.5 to 87.5 C.8. Safety Precautions8.1 Most organic solvents used in these methods are flam-mable and to some degree toxic. Refer
38、ence should be made toMaterial Safety Data Sheets available from the supplier. Thesesolvents should be handled with care and only in well-ventilated areas such as a fume hood. All working areas shouldbe kept free of sparks, flames, or other sources of hightemperature.9. Separation of Asphalt into As
39、phaltenes and Petrolenes(Maltenes)9.1 Representative asphalt samples free of foreign sub-stances will be collected in accordance with Practice D140.Samples for testing can be transferred by chilling to facilitatefracturing the sample or by heating the sample until it becomessufficiently fluid to pou
40、r. WarningIn no case shall thesamples be heated more than 50 C above the expectedsoftening point of the material, which is approximately 100 C.9.2 Transfer to the nearest 0.001 g, 2.000 g of the asphaltinto a tared 500-mL Erlenmeyer flask and record the mass ofthe asphalt, Masphalt. Allow the sample
41、 to cool if transferred byheating and pouring prior to adding the iso-octane in the ratioof 100 mL of solvent per1gofsample. Add 200 6 0.1 mL ofHPLC grade iso-octane to the sample asphalt in the 500-mLErlenmeyer flask.9.3 In a fume hood of sufficient size to accommodate allrequired components of the
42、 apparatus and supplies used toperform this procedure, assemble a reflux apparatus in accor-dance with the setup shown in Fig. 1. Place a stir bar into the500-mLErlenmeyer flask containing the sample solution. Placethe 500-mL Erlenmeyer flask on a stirrer/heater plate. Place anAllihn-type reflux con
43、denser into the neck of 500-mL Erlen-meyer flask (Note 1). Ensure that the reflux apparatus issecured with lab clamps to a heavy ring stand or a laboratorymounting assembly housed in the fume hood by clamping boththe neck of the 500-mL Erlenmeyer flask and the Allihn-typereflux condenser. Connect th
44、eAllihn-type reflux condenser to acold water source using high pressure hose 15.9-mm (58-in.ID) and secure with hose clamps at all connections.NOTE 1Place Teflon flask-neck sleeves between sintered glass fittingsto ensure easy disassembly of the reflux apparatus.9.4 Slowly heat the sample solution o
45、n a stirrer/heater plateuntil the solution is observed to begin to reflux. Maintain thesolution temperature near the boiling point of iso-octane(99 C). Begin to stir the contents of the flask at a moderate rateonce the solution begins to reflux. Stir the contents of the500-mL Erlenmeyer flask for 1
46、to2horuntil no visualevidence of undissolved (undigested) asphalt adheres to thesides of the flask. Once the sample has been observed to go intosolution, stir the solution with refluxing for an additional 1 h(Note 2).NOTE 2Normally2hisasufficient amount of time to dissolve (digest)straight reduced a
47、sphalts, but for air-blown or chemically modifiedasphalts, the dissolution time may need to be extended to 3 h.9.5 After the 2 to 3-h period of time required for refluxingwith stirring, turn off the heater element of the stirrer/heaterplate and allow the sample solution to cool with stirring.Continu
48、e to stir the cooled sample solution for an additional2 h after cooling, at which time discontinue stirring, removethe Allihn-type reflux condenser, stopper the flask, and allowthe sample solution to settle for 2 h prior to filtering (Note 3).NOTE 3At some time during the stirring process, after hea
49、ting hasbeen discontinued, rinse down the reflux assembly with 10 to 20 mL ofiso-octane by dispensing solvent from the top of the Allihn-type refluxcondenser into the flask using a squeeze bottle.9.6 Set up a Bchner-style fritted-glass funnel (60-mL,ASTM 10 to 15-L medium porosity) by placing the funnel ona 1-L suction flask with a filter ring. Attach the suction flask toa cold-trapped vacuum source with high-pressure hose andhose clamps and secure the suction flask to a ring stand ormount rack with a clamp. Prior to filtrat
