1、Designation: D6560 17Designation: IP 14301Standard Test Method forDetermination of Asphaltenes (Heptane Insolubles) in CrudePetroleum and Petroleum Products1,2This standard is issued under the fixed designation D6560; the number immediately following the designation indicates the year oforiginal ado
2、ption or, in 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.1. Scope*1.1 This test method covers a procedure for the determina-tion of the hept
3、ane insoluble asphaltene content of gas oil,diesel fuel, residual fuel oils, lubricating oil, bitumen, andcrude petroleum that has been topped to an oil temperature of260 C (see A1.2.1.1).1.2 The precision is applicable to values between0.50 % mm and 30.0 % mm. Values outside this range maystill be
4、valid but may not give the same precision values.1.3 Oils containing additives may give erroneous results.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.5 This standard does not purport to address all of thesafety concern
5、s, 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 of regulatory limitations prior to use.1.6 This international standard was developed in accor-dance with int
6、ernationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:3D86
7、 Test Method for Distillation of Petroleum Products andLiquid Fuels at Atmospheric PressureD1298 Test Method for Density, Relative Density, or APIGravity of Crude Petroleum and Liquid Petroleum Prod-ucts by Hydrometer MethodD4052 Test Method for Density, Relative Density, and APIGravity of Liquids b
8、y Digital Density MeterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum Products2.2 Energy Institute Standard:4Specifications for IP Standard Thermometers3. Terminology3.1 Definitions:3.1.1 asphaltenes, n(rarely used
9、 in the singular) inpetroleum technology, represent an oil fraction that is solublein a specified aromatic solvent but separates upon addition ofan excess of a specified paraffinic solvent.3.1.1.1 DiscussionIn this test method, the aromatic sol-vent is hot toluene and the paraffinic solvent is hepta
10、ne.3.1.1.2 DiscussionHistorically, benzene was the aromaticsolvent, but benzene is not typically used now for healthreasons. The precision of this test method when using toluenehas been found to be the same as when using benzene.4. Summary of Test Method4.1 A test portion of the sample is mixed with
11、 heptane andthe mixture heated under reflux, and the precipitatedasphaltenes, waxy substances, and inorganic material are1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.14 on Stab
12、ility, Cleanliness and Compatibility of Liquid Fuels.Current edition approved Dec. 1, 2017. Published March 2018. Originallyapproved in 2000. Last previous edition approved in 2012 as D6560 12. DOI:10.1520/D6560-17.2This standard is based on material published in the IP Standard methods forAnalysis
13、and Testing of Petroleum and Related Products and British Standard 2000Parts, copyright Energy Institute, 61 New Cavendish Street, London, W1M 8AR.Adapted with permission of Energy Institute.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serv
14、iceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4Available from Energy Institute, 61 New Cavendish St., London, WIM 8AR,UK.*A Summary of Changes section appears at the end of this standardCopyright ASTM International,
15、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 Standards, Guides and
16、 Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.1collected on a filter paper. The waxy substances are removedby washing with hot heptane in an extractor.4.2 After removal of the waxy substances, the asphaltenesare separated from the inorganic mater
17、ial by dissolution in hottoluene, the extraction solvent is evaporated, and the as-phaltenes weighed.5. Significance and Use5.1 Asphaltenes are the organic molecules of highest mo-lecular mass and carbon-hydrogen ratio normally occurring incrude petroleum and petroleum products containing residualma
18、terial. They may give problems during storage and handlingif the suspension of asphaltene molecules is disturbed throughexcess stress or incompatibility. They are also the last mol-ecules in a product to combust completely, and thus may beone indicator of black smoke propensity. Their compositionnor
19、mally includes a disproportionately high quantity of thesulfur, nitrogen, and metals present in the crude petroleum orpetroleum product.6. Apparatus6.1 GeneralGround-glass joints from different sourcesmay have one of two diameter to length ratios. For thepurposes of this test method, either is suita
20、ble, and for someapplications, the diameter itself can be one of two. However, itis critical that the male and female parts of each joint are fromthe same series to avoid recession or protuberance.6.2 Condenser, with a coil or double surface, fitted with a34/45 or 34/35 ground-glass joint at the bot
21、tom to fit the top ofthe extractor. Minimum length is 300 mm.6.3 Reflux Extractor, conforming to the dimensions given inFig. 1. Tolerances are 61 mm on the height and outer diameter(OD) of the extractor body and 60.5 mm on all other dimen-sions. The female ground-glass joint at the top shall match t
22、hemale at the bottom of the condenser, and the male ground-glassjoint at the bottom shall match the female of the conical flask.6.4 Conical Flasks, of borosilicate glass of appropriatecapacity (see 11.2 and Table 1), with ground-glass joints to fitthe bottom of the extractor.NOTE 1Sizes 24/39, 24/29
23、, 29/43, or 29/32 are suitable.6.5 Stopper, of borosilicate glass of a size to fit the conicalflask.6.6 Evaporating Vessel, of borosilicate glass. Either a hemi-spherical dish of approximately 90 mm diameter, or anothersuitable vessel used in conjunction with a rotovapor.NOTE 2A rotovapor in conjunc
24、tion with a nitrogen atmospherereduces the hazard of toluene evaporation (see 11.7).6.7 Filter Funnel, of borosilicate glass, approximately100 mm diameter.6.8 Filter Papers, Whatman5Grade 42, 110 mm or 125 mmdiameter.6.9 Analytical Balance, capable of weighing with an accu-racy of 0.1 mg.6.10 Forcep
25、s, of stainless steel, spade ended.6.11 Timing Device, electronic or manual, accurate to 1.0 s.6.12 Oven, capable of maintaining a temperature from100 C to 110 C.6.13 Graduated Cylinders, of 50 mL and 100 mL capacity.6.14 Stirring Rods, of glass or polytetrafluoroethylene(PTFE), 150 mm by 3 mm diame
26、ter.6.15 Cooling Vessel, consisting of either a dessicator with-out desiccant, or another suitable tightly-stoppered vessel.5The sole source of supply of the filter papers known to the committee at thistime is Whatman Int. Ltd., Maidstone, UK. If you are aware of alternative suppliers,please provide
27、 this information to ASTM International Headquarters. Your com-ments will receive careful consideration at a meeting of the responsible technicalcommittee,1which you may attend.FIG. 1 ExtractorTABLE 1 Test Portion Size, Flask, and Heptane VolumesEstimated AsphalteneContent%m/mTest PortionSizegFlask
28、VolumemLHeptane VolumemLLess than 0.5 10 2 1000 300 600.5to2.0 82 500 24060Over 2.0 to 5.0 4 1 250 120 30Over 5.0 to 10.0 2 1 150 60 15Over 10.0 to 25.0 0.8 0.2 100 25 to 30Over 25.0 0.5 0.2 100 25 1D6560 1726.16 Mixer, high-speed, nonaerating.7. Reagents7.1 Toluene (methylbenzene) C6H5CH3, analytic
29、al reagentor nitration grade.7.2 Heptane C7H16, analytical reagent grade.8. Sampling8.1 Unless otherwise specified, take samples by the proce-dures described in Practice D4057 or D4177.9. Test Portion Preparation9.1 Test portions from the laboratory samples shall bedrawn after thorough mixing and su
30、bdivision. Heat viscoussamples of residual fuels to a temperature that renders thesample liquid, but not above 80 C, and homogenize, using themixer (see 6.16) as necessary.9.2 Heat samples of penetration grade bitumens to a tem-perature not exceeding 120 C, and stir well before taking analiquot.9.3
31、Samples of hard bitumens shall be ground to a powderbefore an aliquot is taken.9.4 Samples of crude petroleum shall be prepared in accor-dance with the procedure described in the Annex A1, unless itis known that the crude petroleum contains negligible quanti-ties of material boiling below 80 C.10. A
32、pparatus Preparation10.1 Clean all glass flasks (see 6.4) and dishes (see 6.6)bya means that matches the cleanliness obtained by the use of astrongly oxidizing agent, such as ammonium peroxydisulfatein concentrated sulfuric acid at approximately 8 gL, or sulfu-ric acid itself, soaking for at least 1
33、2 h, followed by rinses intap water, distilled water, and the acetone, using forceps onlyfor handling. Strong oxidizing acid cleaning solutions arehighly corrosive and potentially hazardous in contact withorganic materials.10.2 For routine analysis, use a proprietary laboratorydetergent to clean the
34、 glassware, followed by the rinsesdescribed in 10.1. When the detergent cleaning no longermatches the cleanliness required based on visual appearance,use a strong oxidizing agent.10.3 After rinsing, place the glassware in the oven (see6.12) for 30 min, and cool in the cooling vessel (see 6.15) for30
35、 min before weighing.11. Procedure11.1 Estimate the asphaltene content of the sample, orresidue obtained from the procedure in Annex A1, and weighthe quantity, to the nearest 1 mg for masses above 1 g and tothe nearest 0.1 mg for masses of 1 g and below (see Table 1),into a flask (see 6.4) of approp
36、riate capacity (see Table 1).11.2 Add heptane (see 7.2) to the test portion in the flask ata ratio of 30 mL to each 1 g of sample if the expectedasphaltene content is below 25 % mm. For samples with anexpected asphaltene content of above 25 % mm, a minimumheptane volume of 25 mL shall be used (see T
37、able 1).11.3 Boil the mixture under reflux for 60 min 6 5 min.Remove the flask and contents at the end of this period, cool,close with a stopper (see 6.5), and store in a dark cupboard for90 min to 150 min, calculated from the time of removal fromreflux.11.4 Place the filter paper, folded as shown i
38、n Fig. 2 (so asto prevent loss of asphaltenes by creeping), in the filter funnel,using forceps. Thereafter, handle the filter paper only withforceps. Without agitation, decant the liquid into the filterpaper, and then transfer the residue in the flask as completelyas possible with successive quantit
39、ies of hot heptane, using thestirring rod (see 6.14) as necessary. Give the flask a final rinsewith hot heptane, and pour the rinsings through the filter. Setthe flask aside, without washing, for use as specified in 11.6.11.5 Remove the filter paper and contents from the funnel,and place in the refl
40、ux extractor (see 6.3). Using a flaskdifferent from that used initially, reflux with heptane (see 7.2)at a rate of 2 dropss to 4 dropss from the end of the condenserfor an extraction period of not less than 60 min, or until a fewdrops of heptane from the bottom of the extractor leave noresidue on ev
41、aporation on a glass slide.11.6 Replace the flask by the one used initially, and to whichhas been added 30 mL to 60 mL of toluene (see 7.1), andcontinue refluxing until all the asphaltenes have been dissolvedfrom the paper.11.7 Transfer the contents of the flask to a clean and dry (seeSection 10) ev
42、aporating vessel (see 6.6), weighed to the nearest0.2 mg by tare against a similar dish. Wash out the flask withsuccessive small quantities of toluene to a total not exceeding30 mL. Remove the toluene by evaporation on a boiling waterbath, or by evaporation in a rotovapor under an atmosphere ofnitro
43、gen. (WarningPerform the evaporation in a fumehood.)11.8 Dry the dish and contents in the oven (see 6.12)at100 C to 110 C for 30 min. Cool in the cooling vessel (see6.15) for 30 min to 60 min and reweigh by tare against the dishused previously for this purpose, and which has been subjectedto the sam
44、e heating and cooling procedure as was the dishcontaining asphaltenes.NOTE 3Asphaltenes are very susceptible to oxidation, and it isimportant that the procedure specified in the final drying stage is adheredto exactly as regards to temperature and time 61 min.FIG. 2 Filter PaperD6560 17312. Calculat
45、ion12.1 Calculate the asphaltene content, A, in % m/m, ofpetroleum products as follows:A 5 100 M/G! (1)where:M = is the mass of asphaltenes, in grams, andG = is the mass of test portion, in grams.12.2 Calculate the asphaltene content, C, in % m/m, ofcrude petroleum prepared in the manner described i
46、n theAnnex, as follows:C 5 100 MR/GD! (2)where:M = is the mass of asphaltenes, in grams,R = is the mass of the residue from distillation, in grams,G = is the mass of the residue aliquot, in grams, andD = is the mass of crude petroleum sample distilled, ingrams.13. Report13.1 Report the following inf
47、ormation:13.1.1 The heptane insoluble asphaltene content of valuesless than 1.00 % mm, to the nearest 0.05 % mm, by TestMethod D6560.13.1.2 The heptane insoluble asphaltene content of valuesof 1.0 % mm and greater, to the nearest 0.1 % mm, by TestMethod D6560.14. Precision and Bias14.1 PrecisionThe
48、precision values were determined in aninterlaboratory program, using benzene as solvent, in 1956. Asecond interlaboratory program, using toluene as solvent, wascarried out in 1975 to confirm the precision. No data from the1956 evaluation program can be found.NOTE 4A recent (1998) interlaboratory pro
49、gram in France on foursamples with asphaltene contents in the range from 0.50 % m m to22.0 % m m resulted in estimated precision values very similar to thosegiven in 14.2 and 14.3, except for the reproducibility at very low levels(2.0 % m m), which was significantly worse.14.2 RepeatabilityThe difference between two successivetest results obtained by the same operator with the sameapparatus under constant operating conditions on identical testmaterial would, in the normal and correct operation of the testmethod, exceed
