1、Designation: D 4530 06e1An American National StandardStandard Test Method forDetermination of Carbon Residue (Micro Method)1This standard is issued under the fixed designation D 4530; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision,
2、 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 Department of Defense.e1NOTEDeleted original footnote 5 e
3、ditorially in July 2006.1. Scope*1.1 This test method covers the determination of the amountof carbon residue (see Note 1) formed after evaporation andpyrolysis of petroleum materials under certain conditions andis intended to provide some indication of the relative cokeforming tendency of such mate
4、rials.1.2 The test results are equivalent to the Conradson CarbonResidue test (see Test Method D 189).NOTE 1This procedure is a modification of the original method andapparatus for carbon residue of petroleum materials, where it has beendemonstrated that thermogravimetry is another applicable techni
5、que.2However, it is the responsibility of the operator to establish operatingconditions to obtain equivalent results when using thermogravimetry.1.3 This test method is applicable to petroleum products thatpartially decompose on distillation at atmospheric pressure andwas tested for carbon residue v
6、alues of 0.10 to 30 % (m/m).Samples expected to be below 0.10 weight % (m/m) residueshould be distilled to remove 90 % (V/V) of the flask charge(see Section 9). The 10 % bottoms remaining is then tested forcarbon residue by this test method.1.4 Ash-forming constituents, as defined by Test MethodD 48
7、2, or non-volatile additives present in the sample will addto the carbon residue value and be included as part of the totalcarbon residue value reported.1.5 Also in diesel fuel, the presence of alkyl nitrates, such asamyl nitrate, hexyl nitrate, or octyl nitrate, causes a highercarbon residue value
8、than observed in untreated fuel, whichmay lead to erroneous conclusions as to the coke-formingpropensity of the fuel. The presence of alkyl nitrate in the fuelmay be detected by Test Method D 4046.1.6 The values stated in SI units are to be regarded as thestandard. The values given in parentheses ar
9、e for informationonly.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 standard to establish appro-priate safety practices and to determine the applicability ofregulatory limitations prior to use. Fo
10、r specific warningstatements, see 8.2.3 and 8.4.2. Referenced Documents2.1 ASTM Standards:3D 189 Test Method for Conradson Carbon Residue ofPetroleum ProductsD 482 Test Method for Ash from Petroleum ProductsD 4046 Test Method for Alkyl Nitrate in Diesel Fuels bySpectrophotometryD 4057 Practice for M
11、anual Sampling of Petroleum andPetroleum ProductsD 4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsE1 Specification for ASTM Liquid-in-Glass ThermometersE 133 Specification for Distillation Equipment2.2 IP Standard:Specification for IP Standard Thermometers43. Terminology3.1 D
12、efinitions:3.1.1 carbon residue, nin petroleum products, the partremaining after a sample has been subjected to thermaldecomposition.3.1.1.1 DiscussionThe amount of residue is dependent onthe test conditions of evaporation and pyrolysis. The term maybe misleading here in that the residue may contain
13、 other thancarbon decomposition products. However, the term is retaineddue to its wide common usage.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.06 on Analysis of Lubricants.Current edition a
14、pproved Jan. 1, 2006. Published February 2006. Originallyapproved in 1985. Last previous edition approved in 2003 as D 453003.2See Fuel, Vol 63, July 1984, pp. 931934.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual
15、Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4“Methods for Analysis and Testing,” Institute of Petroleum Standard Methodsfor Petroleum and Its Products, Part I, Vol 2. Available from Energy Institute, 61New Cavendish St., London, WIM 8AR,
16、UK.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.4. Summary of Test Method4.1 A weighed quantity of sample is placed in a glass vialand heated to 500C under an inert
17、 (nitrogen) atmosphere in acontrolled manner for a specific time. The sample undergoescoking reactions, and volatiles formed are swept away by thenitrogen. The carbonaceous-type residue remaining is reportedas a percent of the original sample as “carbon residue (micro).”4.1.1 When the test result is
18、 expected to be below 0.10 %(m/m), the sample can be distilled to produce a 10 % (V/V)bottoms, prior to performing the test.5. Significance and Use5.1 The carbon residue value of the various petroleummaterials serves as an approximation of the tendency of thematerial to form carbonaceous type deposi
19、ts under degradationconditions similar to those used in the test method, and can beuseful as a guide in manufacture of certain stocks. However,care needs to be exercised in interpreting the results.5.2 This test method offers advantages of better control oftest conditions, smaller samples, and less
20、operator attentioncompared to Test Method D 189, to which it is equivalent.5.3 Up to twelve samples may be run simultaneously,including a control sample when the vial holder shown in Fig.1 is used exclusively for sample analysis.6. Apparatus6.1 Glass Sample Vials, 2-mL capacity, 12-mm outsidediamete
21、r by approximately 35-mm high.6.2 Larger 4-dram Glass Sample Vials, 15-mL capacity(20.5 to 21-mm outside diameter by 70 6 1-mm high), may beused for samples that are expected to yield residues 5 0.15 6 0.05Brown, viscous 15 0.5 6 0.1Lube oil consistency andappearance, 10 % bottoms ondistillate mater
22、ial0.11 1.5 6 0.5Large vials only 0.1 5.0 6 1.0Small vials only 0.1 1.5 6 0.5D453006e13NOTE 2A control sample can be included in each batch of samplesbeing tested. This control sample should be a typical sample that has beentested at least 20 times in the same equipment in order to define an average
23、percent carbon residue and standard deviation. Results for each batch aredeemed acceptable when results for the control sample fall within theaverage percent carbon residue 6 three standard deviations. Controlresults that are outside these limits indicate problems with the procedureor the equipment.
24、8.2 Processing of Samples:8.2.1 With the oven at less than 100C, place the vial holderinto the oven chamber and secure lid. Purge with nitrogen forat least 10 min at 600 mL/min. Then decrease the purge to 150mL/min and heat the oven slowly to 500C at 1015C/min.8.2.2 If the sample foams or spatters,
25、causing loss ofsample, discard and repeat the test.NOTE 3Spattering may be due to water that can be removed by priorgentle heating in a vacuum, followed by a nitrogen sweep. Alternatively,a smaller sample size can be used.8.2.3 Hold oven at 500 6 2C for 15 min. Then shut offfurnace power and allow o
26、ven to cool freely while undernitrogen purge of 600 mL/min. When oven temperature is lessthan 250C, remove the vial holder for further cooling indesiccator. After the samples are removed from the oven, thenitrogen purge may be shut off. (WarningDo not open ovento air at any time during the heating c
27、ycle. The introduction ofair (oxygen) will likely cause the sample to ignite and spoil thetest. (Because of the oven design and materials, such anignition is normally not a hazard to the operator.) Open theoven only after oven temperature falls below 250C during thecooling step. Maintain nitrogen fl
28、ow until after the vial holderhas been removed from the oven.) (WarningLocate thecoking oven in laboratory exhaust hood for safe venting ofsmoke and fumes. Alternatively, install vent line from MCRToven exhaust to laboratory exhaust system.) (WarningIf avent line is used, do not connect directly to
29、exhaust chimney toavoid creating negative pressure in the line.)NOTE 4To reduce oven temperature for the next run, remove the ovenlid to allow faster cooling. As required by the procedure, the subsequenttest can be started when the oven has been cooled to below 100C.8.3 Final WeighingTransfer sample
30、 vials (maintained inplace in the vial holder) to desiccator and allow vials to cool toroom temperature. Weigh the cooled vials to the nearest 0.1 mgand record. Handle the vials with forceps. Discard the usedglass sample vials.8.4 Occasionally examine the condensate trap at the bottomof the oven cha
31、mber; empty if necessary and replace.(WarningThe condensate trap residue may have somecarcinogenic materials present. Avoid contact with the trapresidue; dispose of it in accordance with local laboratorypractice.)9. Procedure for Carbon Residue on 10 % (V/V)Distillation Residue9.1 This procedure is
32、applicable to light distillate materials,such as ASTM No. 1 and No. 2 fuel oil or materials expectedto have less than 0.1 % (m/m) carbon residue.9.2 A distillation analysis using either a 100 or 200-mLstarting volume is required in order to collect a sufficientamount of the 10 % (V/V) residue needed
33、 in this analysis. Fora 100-mL distillation, assemble the distillation apparatus de-scribed in Specification E 133, using flask B (125-mL bulbvolume), flask support board with 50-mm diameter opening,and graduated cylinder B (100-mL capacity). For a 200-mLdistillation, assemble the distillation appar
34、atus described inSpecification E 133, using flask D (250-mLbulb volume), flasksupport board with 50-mm diameter opening, and graduatedcylinder C (200-mL capacity). A thermometer is not required,but the use of the ASTM High Distillation Thermometer 8F or8C, as prescribed in Specification E1, or the I
35、P High Distilla-tion Thermometer 6C, as prescribed in the Specification for IPThermometers, is recommended.9.3 Depending upon which distillation flask is used, placeeither 100 or 200 mL of sample (as measured at ambienttemperature) into a tared distillation flask that is held at atemperature between
36、 13C and ambient, and record the mass ofsample transferred (E1). Maintain the condenser bath tempera-ture between 0 and 60C so as to provide a sufficienttemperature differential for sample condensation, while avoid-ing any solidification of waxy material in the condenser tube.Use, without cleaning,
37、the cylinder from which the sample wasmeasured as the receiver, and place it so that the tip of thecondenser does not touch the wall of the cylinder. The receivertemperature is required to be maintained at the same tempera-ture (within 63C) as the sample taken at the start of the testin order to obt
38、ain an accurate volume measurement in thereceiving flask.9.4 Apply the heat to the flask at a uniform rate so regulatedthat the first drop of condensate exits from the condenserbetween 10 and 15 min (for 200-mL samples) or between 5 and15 min (for 100-mL samples) after initial application of heat.Af
39、ter the first drop falls, move the receiving cylinder so that thetip of the condenser tube touches the wall of the cylinder. Thenregulate the heat so that the distillation proceeds at a uniformrate of 8 to 10 mL/min (for 200-mL samples) or 4 to 5 mL/min(for 100-mL samples). For 200-mL samples, conti
40、nue thedistillation until approximately 178 mL of distillate has beencollected, and then discontinue heating and allow the con-denser to drain until 180 mL (90 % (V/V) of the charge to theflask) has been collected in the cylinder. For 100-mL samples,continue the distillation until approximately 88 m
41、L of distillatehas been collected, and then discontinue heating and allow thecondenser to drain until 90 mL (90 % (V/V) of the charge tothe flask) has been collected in the cylinder.9.5 Catch final drainage, if any, by immediately replacingthe cylinder with a suitably tared container, such as a smal
42、lErlenmeyer flask. Add to this container, while still warm, thedistillation residue left in the distilling flask, and mix well. Thecontents of the container then represents a 10 % (V/V) distil-lation residue from the original product. Allow the contents ofthe container to cool to ambient temperature
43、 before weighingthe container and its contents in order to obtain an accuratemeasurement.9.6 If the distillation residue is too viscous to flow freely atambient temperature, it is necessary to warm the distillationresidue to a sufficient temperature that will allow a portion ofthe material to be tra
44、nsferred into a previously weighted vialD453006e14for analysis (see Table 1). After allowing the material in thevial to cool to ambient temperature, determine the mass of thetest specimen to the nearest 0.1 mg and carry out the carbonresidue test in accordance with the procedure described inSection
45、8.10. Calculation10.1 Calculate the mass % carbon residue in the originalsample, or in the 10 % distillation bottoms as follows:10.1.1 Calculate percent residue as follows:% carbon residue 5A 3 100!W(1)where:A = carbon residue, g, andW = sample used, g.11. Report11.1 For values up to 10 %, report th
46、e value obtained asMicro Method carbon residue, percent to the nearest 0.01 %(m/m). For values above 10 %, report the value obtained to thenearest 0.1% (m/m). For Micro Method carbon residue on10 % distillation residue, percent to the nearest 0.1 % (m/m).12. Precision and Bias512.1 The precision of
47、this test method as determined by (seeNote 5) statistical examination of interlaboratory results is asfollows:NOTE 5Precision data were generated by a task force in 2004. Theround robin involved nine laboratories and six petroleum materials induplicate analysis. The range for values samples was from
48、 0.1 % to 25 %(m/m). No precision data or correlation data exists for results obtainedusing 10 % bottoms or 15-mL vials, or both. See X1.1 and Fig. X1.1regarding a separate 1983 correlation study6that was performed betweenTest Methods D 189 and D 4530.12.2 RepeatabilityThe difference between two tes
49、t re-sults, obtained by the same operator with the same apparatusunder constant operating conditions on identical test material,would, in the long run, in the normal and correct operation ofthe test method, exceed the values shown in Fig. 3 in only onecase in twenty.12.3 ReproducibilityThe difference between two singleand independent results, obtained by different operators work-ing in different laboratories on identical test material, would, inthe long run, in the normal and correct operation of the testmethod, exceed the values shown in Fig. 3 in only
