1、Designation: D 6560 00 (Reapproved 2005)Designation: IP 143/01An American National StandardStandard Test Method forDetermination of Asphaltenes (Heptane Insolubles) in CrudePetroleum and Petroleum Products1, 2This standard is issued under the fixed designation D 6560; the number immediately followin
2、g the designation indicates the 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.1. Scope1.1 This test method co
3、vers a procedure for the determina-tion of the heptane insoluble asphaltene content of gas oil,diesel fuel, residual fuel oils, lubricating oil, bitumen, andcrude petroleum that has been topped to an oil temperature of260C (see A1.2.1.1).1.2 The precision is applicable to values between 0.50 and30.0
4、 % m/m. Values outside this range may still be valid butmay 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 n
5、ot 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 applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standar
6、ds:3D86 Test Method for Distillation of Petroleum Products atAtmospheric PressureD 1298 Test Method for Density, Relative Density (SpecificGravity), or API Gravity of Crude Petroleum and LiquidPetroleum Products by Hydrometer MethodD 4052 Test Method for Density and Relative Density ofLiquids by Dig
7、ital Density MeterD 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4177 Practice for Automatic Sampling of Petroleum andPetroleum Products2.2 IP Standard:4Specifications for IP Standard Thermometers3. Terminology3.1 Definitions:3.1.1 asphaltenes, nwax-free organic material ins
8、olublein heptane, but soluble in hot toluene (benzene).NOTE 1Benzene is included in this definition solely on the basis of itsclassical references in the definition of asphaltenes. The precision of thistest method when using toluene has been found to be the same as whenusing benzene.4. Summary of Te
9、st Method4.1 A test portion of the sample is mixed with heptane andthe mixture heated under reflux, and the precipitated asphalt-enes, waxy substances, and inorganic material are collected ona filter paper. The waxy substances are removed by washingwith hot heptane in an extractor.4.2 After removal
10、of the waxy substances, the asphaltenesare separated from the inorganic material by dissolution in hottoluene, the extraction solvent is evaporated, and the asphalt-enes weighed.5. Significance and Use5.1 Asphaltenes are the organic molecules of highest mo-lecular mass and carbon-hydrogen ratio norm
11、ally occurring incrude petroleum and petroleum products containing residualmaterial. They may give problems during storage and handlingif the suspension of asphaltene molecules is disturbed through1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants a
12、nd is the direct responsibility of SubcommitteeD02.14 on Stability and Cleanliness of Liquid Fuels.Current edition approved Nov. 1, 2005. Published November 2005. Originallyapproved in 2000. Last previous edition approved in 2000 as D 6560 00.2This standard is based on material published in the IP S
13、tandard methods forAnalysis 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 A
14、STM Customer Service at serviceastm.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.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700,
15、West Conshohocken, PA 19428-2959, United States.excess 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 compositionnormally includes a disproportionately high quantity of thesulfur, nitrogen
16、, 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 suitable, and for someapplications, the diameter itself can be one of two . H
17、owever,it is critical that the male and female parts of each joint arefrom the 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 bottom to fit the top ofthe extractor. Minimum length is 300 mm.6.3 Reflux
18、 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 otherdimensions. The female ground-glass joint at the top shallmatch the male at the bottom of the condenser, and the maleground-glass joint at
19、the bottom shall match the female of theconical 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 2Sizes 24/39, 24/29, 29/43, or 29/32 are suitable.6.5 Stopper, of borosilicate glass of a siz
20、e 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 3A rotovapor in conjunction with a nitrogen atmospherereduces the hazard of toluene evaporation (
21、see 11.7).6.7 Filter Funnel, of borosilicate glass, approximately100 mm diameter.6.8 Filter Papers, Whatman5Grade 42, 110 or 125-mmdiameter.6.9 Analytical Balance, capable of weighing with an accu-racy of 0.1 mg.6.10 Forceps, of stainless steel, spade ended.6.11 Timing Device, electronic or manual,
22、accurate to 1.0 s.6.12 Oven, capable of maintaining a temperature from 100to 110C.6.13 Graduated Cylinders, of 50 and 100 mL capacity.6.14 Stirring Rods, of glass or polytetrafluoroethylene(PTFE), 150 by 3-mm diameter.6.15 Cooling Vessel, consisting of either a dessicator with-out desiccant, or anot
23、her suitable tightly-stoppered vessel.6.16 Mixer, high-speed, nonaerating.7. Reagents7.1 Toluene (methylbenzene) C6H5CH3, analytical 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
24、D 4057 or D 4177.9. Test Portion Preparation9.1 Test portions from the laboratory samples shall bedrawn after thorough mixing and subdivision. Heat viscoussamples of residual fuels to a temperature that renders thesample liquid, but not above 80C, and homogenize, using themixer (see 6.16) as necessa
25、ry.9.2 Heat samples of penetration grade bitumens to a tem-perature not exceeding 120C, and stir well before taking analiquot.9.3 Samples of hard bitumens shall be ground to a powderbefore an aliquot is taken.5The sole source of supply of the filter papers known to the committee at thistime is Whatm
26、an Int. Ltd., Maidstone, UK. If you are aware of alternative suppliers,please provide 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 S
27、ize, Flask, and Heptane VolumesEstimated AsphalteneContent%m/mTest PortionSizegFlask VolumemLHeptane VolumemLLess than 0.5 10 6 2 1000 300 6 600.5to2.0 86 2 500 240 6 60Over 2.0 to 5.0 4 6 1 250 120 6 30Over 5.0 to 10.0 2 6 1 150 60 6 15Over 10.0 to 25.0 0.8 6 0.2 100 25 to 30Over 25.0 0.5 6 0.2 100
28、 25 6 1D 6560 00 (2005)29.4 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 80C.10. Apparatus Preparation10.1 Clean all glass flasks (see 6.4
29、) and dishes (see 6.6)bya means that matches the cleanliness obtained by the use of astrongly oxidizing agent, such as chromosulfuric acid, ammo-nium peroxydisulfate in concentrated sulfuric acid at approxi-mately 8 g/L, or sulfuric acid itself, soaking for at least 12 h,followed by rinses in tap wa
30、ter, distilled water, and thenacetone, using forceps only for handling. (WarningChromosulfuric acid is a health hazard. It is toxic, a recognizedcarcinogen as it contains Cr (VI) compounds, which are highlycorrosive and potentially hazardous in contact with organicmaterials. When using chromosulfuri
31、c acid cleaning solution,eye protection and protective clothing are essential. Neverpipette the cleaning solution by mouth. After use, do not pourcleaning solution down the drain, but neutralize it with greatcare, owing to the concentrated sulfuric acid present, anddispose of it in accordance with s
32、tandard procedures for toxiclaboratory waste (chromium is highly dangerous to the envi-ronment). Nonchromium containing, strongly oxidizing acidcleaning solutions are also highly corrosive and potentiallyhazardous in contact with organic materials, but do not containchromium, which has its own speci
33、al disposal problems.)10.2 For routine analysis, use a proprietary laboratorydetergent to clean the 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, pl
34、ace the glassware in the oven (see6.12) for 30 min, and cool in the cooling vessel (see 6.15) for30 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
35、and tothe nearest 0.1 mg for masses of 1 g and below (see Table 1),into a flask (see 6.4) of appropriate capacity (see Table 1).11.2 Add heptane (see 7.2) to the test portion in the flask ata ratio of 30 mL to each1gofsample if the expectedasphaltene content is below 25 % m/m. For samples with anexp
36、ected asphaltene content of above 25 % m/m, a minimumheptane volume of 25 mL shall be used (see Table 1).11.3 Boil the mixture under reflux for 60 6 5 min. Removethe flask and contents at the end of this period, cool, close witha stopper (see 6.5), and store in a dark cupboard for 90 to150 min, calc
37、ulated from the time of removal from reflux.11.4 Place the filter paper, folded as shown in 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, a
38、nd then transfer the the residue in the flask ascompletely as possible with successive quantities of hotheptane, using the stirring rod (see 6.14) as necessary. Give theflask a final rinse with hot heptane, and pour the rinsingsthrough the filter. Set the flask aside, without washing, for useas spec
39、ified in 11.6.11.5 Remove the filter paper and contents from the funnel,and place in the reflux extractor (see 6.3). Using a flaskdifferent from that used initially, reflux with heptane (see 7.2)at a rate of 2 drops/s to 4 drops/s from the end of the condenserfor an extraction period of not less tha
40、n 60 min, or until a fewdrops of heptane from the bottom of the extractor leave noresidue on evaporation on a glass slide.11.6 Replace the flask by the one used initially, and to whichhas been added 30 to 60 mL of toluene (see 7.1), and continuerefluxing until all the asphaltenes have been dissolved
41、 from thepaper.11.7 Transfer the contents of the flask to a clean and dry (seeSection 10) evaporating 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 evap
42、oration on a boiling waterbath, or by evaporation in a rotovapor under an atmosphere ofnitrogen. (WarningPerform the evaporation in a fumehood.)11.8 Dry the dish and contents in the oven (see 6.12)at100to 110C for 30 min. Cool in the cooling vessel (see 6.15) for30 to 60 min and reweigh by tare agai
43、nst the dish usedpreviously for this purpose, and which has been subjected tothe same heating and cooling procedure as was the dishcontaining asphaltenes.NOTE 4Asphaltenes are very susceptible to oxidation, and it isimportant that the procedure specified in the final drying stage is adheredto exactl
44、y as regards to temperature and time 61 min.12. Calculation12.1 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
45、/m, ofcrude petroleum prepared in the manner described in theAnnex, as follows:C 5 100 MR/GD! (2)FIG. 2 Filter PaperD 6560 00 (2005)3where: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 t
46、he mass of crude petroleum sample distilled, ingrams.13. Report13.1 Report the following information:13.1.1 The heptane insoluble asphaltene content of valuesless than 1.00 % m/m, to the nearest 0.05 % m/m, by TestMethod D 6560.13.1.2 The heptane insoluble asphaltene content of valuesof 1.0 % m/m an
47、d greater, to the nearest 0.1 % m/m, by TestMethod D 6560.14. Precision and Bias14.1 PrecisionThe precision values were determined inan interlaboratory program, using benzene as solvent, in 1956.A second interlaboratory program, using toluene as solvent,was carried out in 1975 to confirm the precisi
48、on. No data fromthe 1956 evaluation program can be found.NOTE 5A recent (1998) interlaboratory program in France on foursamples with asphaltene contents in the range from 0.50 to 22.0 % m/mresulted in estimated precision values very similar to those given in 14.2and 14.3, except for the reproducibil
49、ity 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 the value below in only 1 case in 20.r 5 0.1 A (3)where A is the average result, in % m/m.14.3 ReproducibilityThe difference between two singleand independent results obtained by different operators work-ing in different laboratories on nominally
