1、Designation: D 4530 07An 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, t
2、he 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.1. Scope*1.1 This test method covers
3、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 materials.1.2 The test results are equivalent to the Conradson Ca
4、rbonResidue 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 technique.2However, it is the responsibility of the operator to est
5、ablish 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 values of 0.10 to 30 % (m/m).Samples expected to be below 0.10
6、 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 482, or non-volatile additives present in the sample will addto
7、 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 than observed in untreated fuel, whichmay lead to erroneous c
8、onclusions 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 are for informationonly.1.7 This standard does not purport to a
9、ddress 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. For specific warningstatements, see 8.2.3 and 8.4.2. Referenced
10、 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 Manual Sampling of Petroleum andPetroleum ProductsD 4177 Pract
11、ice for Automatic Sampling of Petroleum andPetroleum ProductsE1 Specification for ASTM Liquid-in-Glass ThermometersE 133 Specification for Distillation Equipment2.2 Energy Institute Standard:Specification for IP Standard Thermometers43. Terminology3.1 Definitions:3.1.1 carbon residue, nin petroleum
12、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 other thancarbon decomposition products. Howev
13、er, the term is retaineddue to its wide common usage.4. Summary of Test Method4.1 A weighed quantity of sample is placed in a glass vialand heated to 500C under an inert (nitrogen) atmosphere in acontrolled manner for a specific time. The sample undergoescoking reactions, and volatiles formed are sw
14、ept away by the1This 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 approved Nov. 1, 2007. Published December 2007. Originallyapproved in 1985. Last previ
15、ous edition approved in 2006 as D 453006e1.2See 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 Book of ASTMStandards volume information, refer to the standards Document Summary p
16、age 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, UK.1*A Summary of Changes section appears at the end of this standard.Copyright AST
17、M International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Copyright by ASTM Intl (all rights reserved); Mon Apr 21 02:18:11 EDT 2008Downloaded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No further reproductions authorized.nitrogen. The carbon
18、aceous-type residue remaining is reportedas a percent of the original sample as “carbon residue (micro).”4.1.1 When the test result is 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 resi
19、due value of the various petroleummaterials serves as an approximation of the tendency of thematerial to form carbonaceous type deposits 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 exerci
20、sed in interpreting the results.5.2 This test method offers advantages of better control oftest conditions, smaller samples, and less 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
21、 holder shown in Fig.1 is used exclusively for sample analysis.6. Apparatus6.1 Glass Sample Vials, 2-mL capacity, 12-mm outsidediameter 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
22、expected to yield residues 5 0.15 6 0.05Brown, viscous 15 0.5 6 0.1Lube oil consistency andappearance, 10 % bottoms ondistillate material0.11 1.5 6 0.5Large vials only 0.1 5.0 6 1.0Small vials only 0.1 1.5 6 0.5D4530073Copyright by ASTM Intl (all rights reserved); Mon Apr 21 02:18:11 EDT 2008Downloa
23、ded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No further reproductions authorized.results that are outside these limits indicate problems with the procedureor the equipment.8.2 Processing of Samples:8.2.1 With the oven at less than 100C, place the vial holderinto the oven chamber and
24、 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, causing loss ofsample, discard and repeat the test.NOTE 3Spattering may be due to water that can be removed by
25、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 oven to cool freely while undernitrogen purge of 600 mL/min. When oven temperature is lessthan 250C, remove the
26、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 cycle. The introduction ofair (oxygen) will likely cause the sample to ignite and spoil thetest. (Because of the
27、 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 flow until after the vial holderhas been removed from the oven.) (WarningLocate thecoking oven in laboratory exha
28、ust 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 exhaust chimney toavoid creating negative pressure in the line.)NOTE 4To reduce oven temperature for the next r
29、un, 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 vials (maintained inplace in the vial holder) to desiccator and allow vials to cool toroom temperature. Weigh
30、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 chamber; empty if necessary and replace.(WarningThe condensate trap residue may have somecarcinogenic materials pr
31、esent. 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 applicable to light distillate materials,such as ASTM No. 1 and No. 2 fuel oil or materials expectedto have les
32、s 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 in this analysis. Fora 100-mL distillation, assemble the distillation apparatus de-scribed in Specification E
33、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 apparatus described inSpecification E 133, using flask D (250-mLbulb volume), flasksupport board with 50-mm diameter
34、 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 IP High Distilla-tion Thermometer 6C, as prescribed in the Specification for IPThermometers, is recommended.9.3
35、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 13C and ambient. Maintain the con-denser bath temperature between 0 and 60C so as to providea sufficient tempe
36、rature differential for sample condensation,while avoiding any solidification of waxy material in thecondenser tube. Use, without cleaning, the cylinder from whichthe sample was measured as the receiver, and place it so thatthe tip of the condenser does not touch the wall of the cylinder.The receive
37、r temperature is required to be maintained at thesame temperature (within 63C) as the sample taken at thestart of the test in order to obtain an accurate volumemeasurement in the receiving flask.9.4 Apply the heat to the flask at a uniform rate so regulatedthat the first drop of condensate exits fro
38、m the condenserbetween 10 and 15 min (for 200-mL samples) or between 5 and15 min (for 100-mL samples) after initial application of heat.After 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 dis
39、tillation 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, continue thedistillation until approximately 178 mL of distillate has beencollected, and then discontinue heating and allow the con-denser to drain until 180 mL (90 %
40、(V/V) of the charge to theflask) has been collected in the cylinder. For 100-mL samples,continue the distillation until approximately 88 mL 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 collec
41、ted in the cylinder.9.5 Catch final drainage, if any, by immediately replacingthe cylinder with a suitable container, such as a small Erlen-meyer flask. Add to this container, while still warm, thedistillation residue left in the distilling flask, and mix well. Thecontents of the container then repr
42、esents a 10 % (V/V) distil-lation residue from the original product.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 transferred into a previ
43、ously weighted vialfor 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 8.10. Calculation10.1 Calculate
44、 the mass % carbon residue in the originalsample, or in the 10 % distillation bottoms as follows:10.1.1 Calculate percent residue as follows:D4530074Copyright by ASTM Intl (all rights reserved); Mon Apr 21 02:18:11 EDT 2008Downloaded/printed byGuo Dehua (CNIS) pursuant to License Agreement. No furth
45、er reproductions authorized.% 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 the value obtained asMicro Method carbon residue, percent to the nearest 0.01 %(m/m). For values above 10 %, report the value obtained to theneare
46、st 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 this test method as determined by (seeNote 5) statistical examination of interlaboratory results is asfollows:NOTE 5Precision data were generate
47、d by a task force in 2004. Theround robin involved nine laboratories and six petroleum materials induplicate analysis. The range for values samples was from 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 F
48、ig. X1.1regarding a separate 1983 correlation study6that was performed betweenTest Methods D 189 and D 4530.12.2 RepeatabilityThe difference between two test re-sults, obtained by the same operator with the same apparatusunder constant operating conditions on identical test material,would, in the lo
49、ng 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 one case intwenty.12.4 BiasThe procedure in Test Method D 4530 for mea-suring carbon residue of petroleum by the carbon residuemethod has no
