1、Designation: D 4124 09Standard Test Method forSeparation of Asphalt into Four Fractions1This standard is issued under the fixed designation D 4124; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number
2、 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 saturates, naphthen
3、e 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 notcontain asphaltene
4、s.1.2 The values stated in SI units are to be regarded asstandard.1.3 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 determine the app
5、lica-bility of regulatory limitations prior to use. Specific precau-tionary statements are given in Section 8.1.4 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
6、for acceptance or rejection of a material forpurchasing purposes.2. Referenced Documents2.1 ASTM Standards:2D 140 Practice for Sampling Bituminous Materials2.2 Other Documents:Manual on Hydrocarbon Analysis33. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 asphaltenes or alkane
7、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-pounds of the general formula, CnH2n, derivatives o
8、f 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 specified.3.1.4 petrolenes (also referred to as maltenes
9、)(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 molecular weight alkane-soluble matter recoveredfollow
10、ing 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 andnaphthenic aromatics fraction have been removed, usi
11、ng 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. Summary of Test Method4.1 The sample containing the f
12、our defined fractions is firstseparated into alkane-insoluble asphaltenes and alkane-solublepetrolenes. Petrolenes are then adsorbed onto calcined CG-20alumina and further fractionated into saturate, naphthene aro-matic, and polar aromatic fractions by pumping an eluotropicseries of elution solvents
13、 upwards through a glass chromato-graphic column packed with calcined alumina. Eluted fractionsare recovered by solvent removal prior to final weighing. Thethree eluted fractions plus the alkane-precipitated asphaltenescomprise the four fractions as defined in Section 3.1This test method is under th
14、e jurisdiction of ASTM Committee D04 on Roadand Paving Materials and is the direct responsibility of Subcommittee D04.47 inMiscellaneous Asphalt Tests.Current edition approved July 1, 2009. Published August 2009. Originallyapproved in 1982. Last previous edition approved in 2001 as D 4124 01.2For re
15、ferenced 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 PCN 03-332030-12.1Copyright ASTM Internation
16、al, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5. Significance and Use5.1 This test method separates asphalts into four well-defined fractions. Analysis of these fractions can be used toevaluate asphalt composition (1, 2). For example, one cancompare the rati
17、os 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 Separation,with features as specified in Fig. 1. (see 6.1.1).6.1.1 Apparatus (Fig. 1)(a)
18、 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 sinteredglass neck.6.2 Chromatographic Column Apparatus, with features asspecified in Fig. 2, (see
19、 6.2.1-6.2.5).6.2.1 LC-Apparatus (Fig. 2)(a) ring stand w/clamp, flask(25-mL round-bottom or Erlenmeyer flask); (b) meteringpump; (c) sealed glass LC-column; (d) UV Detector w/ DataAcquisition System (wavelength range 200-500 nm 0.1-nm); (e) graduated cylinder (Fig. 2).6.2.2 UV Detector with Data Ac
20、quisition System (Fig.2)A UV Detector with Data Acquisition System suitable foruse with liquid chromatography or HPLC used to detect theoccurrence of material fractions (peak response) as they areeluted from the column.6.2.3 Metering Pump (Fig. 2)Piston and piston chamberwill be constructed of mater
21、ials 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-jacketClosed glass liquidchromatography column, 70 cm long and 1.5 cm insidediameter (volume, 124-cc). T
22、he LC-column will be a closedcolumn with endplates containing solvent permeable dia-phragms and fitting ports for 6.35-mm (14-in.) tubing fittings.6.2.5 Refrigerated/Heating Circulatora refrigerated/heating circulator, temperature range between 0C and 100C6 0.1C stability, with water circulation thr
23、ough the LC-column water 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 dryingoven, rotary solvent evaporator (water-bath and oil-bath type),nitrogen gas stream evaporator with
24、heater water bath.6.3.2 Erlenmeyer Flasks, 25-mL with Glass Stopper (1),500-mL with Glass 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 10-15 L medium porosity.6.3.6 Flask, Suction,1Lto2L.6.3.7 Rinse Squeeze Bottle, 0.5-L si
25、ze, TFE-fluorocarbon.NOTEKey: a. ring stand w/large test-tube clamp; b. heater/stirring plate; c. 500-mL Erlenmeyer flask with 29/42 sintered glass neck; d. reducer29/42-to-24/40 sintered glass spout-to-neck; e. Allihn-type reflux condenser with 24/40 sintered glass spout.FIG. 1 Asphaltene/Maltene S
26、eparation ApparatusD41240926.3.8 Analytical Balance, 0.0001 g to 250 g 6 0.0001 g.6.3.9 Stirrer/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
27、Teflon Flask-neck Sleeves, (3) 24/40-size, (1) 29/42-size.6.3.14 Hose, reinforced, high 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)-ho
28、le and 3.17-mm (18 in.) ferrule.7. Absorbent and Reagents7.1 Alumina,4CG-20 chromatographic grade, calcined at425C for 16 h and stored in an evacuated desiccator in airtightbottles for 3 to 5 h.7.2 Purity of ReagentsHPLC grade chemicals shall beused in all sample preparations and tests. Unless other
29、wiseindicated, it is intended that all reagents conform to thespecifications of the Committee on Analytical Reagents of theAmerican Chemical Society where such specifications areavailable.5Other grades may be used, provided it is firstascertained that the reagent is of sufficiently high purity toper
30、mit its use without lessening the accuracy of the determi-nation.7.3 Reagents7.3.1 iso-Octane (2,2,4trimethyl pentane), HPLC Grade,0.01 % water.7.3.2 n-Heptane, HPLC Grade, 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 Trichloroethyle
31、ne, ACS Grade, 0.02 % water, boilingpoint 86.5 to 87.5C.4Aluminum Oxide available 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-AXO612-3.5Reagent
32、 Chemicals, American Chemical Society Specifications, AmericanChemical Society, 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 Na
33、tional Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.NOTEKey: LC-Apparatus: a. clamp stand w/sample or solvent flask (round-bottom or Erlenmeyer type); b. metering pump; c. sealed glass LC columnpacked with alumina; c1. glass column; c2. collar; c3. diaphragm; c4. endplate; c5.
34、 tubing nut/ferrule and tubing; d. UV-VIS spectrophotometric detector(200-500 nm 0.1-nm); e. graduated cylinders of various sizes for fraction collection.FIG. 2 Chromatographic Column for Separation of Asphalt by Elution-AdsorptionD41240938. Safety Precautions8.1 Most organic solvents used in these
35、methods are flam-mable and to some degree toxic. Reference 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 sourc
36、es of hightemperature.9. Separation of Asphalt into Asphaltenes and Petrolenes(Maltenes)9.1 Representative asphalt samples free of foreign sub-stances will be collected in accordance with Practice D 140.Samples for testing can be transferred by chilling to facilitatefracturing the sample or by heati
37、ng the sample until it becomessufficiently fluid to pour. Warning: In no case shall thesamples be heated more than 50C above the expected soften-ing point of the material, which is approximately 100C.9.2 Transfer to the nearest 0.001 g, 2.000 g of the asphaltinto a tared 500-mL Erlenmeyer flask and
38、record the mass ofthe asphalt, Masphalt. Allow the sample to cool if transferred byheating and pouring prior to adding the iso-octane in the ratioof 100 mL of solvent per1gofsample.Add 200 mL 6 0.1 mLof HPLC grade iso-octane to the sample asphalt in the 500 mLErlenmeyer flask.9.3 In a fume hood of s
39、ufficient size to accommodate allrequired components of the 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 flas
40、k on a stirrer/heater plate. Place anAllihn-type reflux condenser 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 Erlen
41、meyer flask and the Allihn-typereflux condenser. Connect theAllihn-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
42、 the reflux apparatus.9.4 Slowly heat the sample solution on a stirrer/heater plateuntil the solution is observed to begin to reflux. Maintain thesolution temperature near the boiling point of iso-octane(99C). Begin to stir the contents of the flask at a moderate rateonce the solution begins to refl
43、ux. Stir the contents of the500-mL Erlenmeyer flask for 1 to2horuntil no visualevidence of un-dissolved (un-digested) 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 2Normally two hour
44、s is a sufficient amount of time to dissolve(digest) straight reduced asphalts, but for air blown or chemicallymodified asphalts, the dissolution time may need to be extended to threehours.9.5 After the 2 to 3-h period of time required for refluxingwith stirring, turn off the heater element of the s
45、tirrer/heaterplate and allow the sample solution to cool with stirring.Continue to stir the cooled sample solution for an additional 2h after cooling, at which time discontinue stirring, remove theAllihn-type reflux condenser, stopper the flask, and allow thesample solution to settle for 2 h prior t
46、o filtering (Note 3).NOTE 3At some time during the stirring process, after heating 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
47、fritted-glass funnel (60-mL,ASTM 1015-L medium porosity) by placing the funnel on a1-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 fil
48、tration, tare the Bchner-style fritted-glass funnel.9.7 Filter the sample solution prepared in 9.2-9.5, by quan-titatively decanting the liquid contents of the sample solutionfrom the 500-mL Erlenmeyer flask directly into the Bchner-style fritted-glass funnel while applying suction to the 1-Lsuction
49、 flask.9.8 Quantitatively transfer the filtered decant, using a glassfunnel, to a 1-L pear-shaped flask clamped to a ring stand, (thisdecant represents the first portion of petrolenes dissolved iniso-octane). Transfer the 1-L pear-shaped flask to a rotaryevaporator and distill the iso-octane off of the petrolenefraction. Return the Bchner-style fritted-glass funnel to thesuction flask.9.9 Wash the asphaltenes which remain in the 500-mLErlenmeyer flask with 100 mL of iso-octane. Place the 500-mLErlenmeyer flask back onto the heater/sti
