1、Designation: D4530 11Standard Test Method forDetermination of Carbon Residue (Micro Method)1This standard is issued under the fixed designation D4530; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A num
2、ber in parentheses indicates the year of last reapproval. Asuperscript epsilon () 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 the determination of the amounto
3、f 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 CarbonResidue test (see Test Metho
4、d D189).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 establish operatingconditions to obt
5、ain 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 weight % (m/m) residueshould be
6、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 MethodD482, or non-volatile additives present in the sample will addto the carbon residue value and be i
7、ncluded 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 conclusions as to the coke-formingp
8、ropensity of the fuel. The presence of alkyl nitrate in the fuelmay be detected by Test Method D4046.1.6 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6.1 Exception6.4 and 6.5 include inch-pound units.1.7 WARNINGMercury has
9、been designated by manyregulatory agencies as a hazardous material that can causecentral nervous system, kidney and liver damage. Mercury, orits vapor, may be hazardous to health and corrosive tomaterials. Caution should be taken when handling mercury andmercury containing products. See the applicab
10、le product Ma-terial Safety Data Sheet (MSDS) for details and EPAswebsitehttp:/www.epa.gov/mercury/faq.htmfor addi-tional information. Users should be aware that selling mercuryand/or mercury containing products into your state or countrymay be prohibited by law.1.8 This standard does not purport to
11、 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. For specific warningstatements, see 8.2.3 and 8.4.2. Referenc
12、ed Documents2.1 ASTM Standards:3D189 Test Method for Conradson Carbon Residue of Pe-troleum ProductsD482 Test Method for Ash from Petroleum ProductsD4046 Test Method for Alkyl Nitrate in Diesel Fuels bySpectrophotometryD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practi
13、ce for Automatic Sampling of Petroleum andPetroleum ProductsE1 Specification for ASTM Liquid-in-Glass ThermometersE133 Specification for Distillation Equipment2.2 Energy Institute Standard:Specification for IP Standard Thermometers43. Terminology3.1 Definitions:3.1.1 carbon residue, nthe residue for
14、med by evaporationand thermal degradation of a carbon containing material.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 approved May 15, 2011. Publ
15、ished July 2011. Originallyapproved in 1985. Last previous edition approved in 2007 as D453007. DOI:10.1520/D4530-11.2See 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 A
16、STMStandards volume information, refer to the standards Document Summary page onthe ASTM website.4“Methods forAnalysis 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 Sum
17、mary 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.3.1.1.1 DiscussionThe residue is not composed entirelyof carbon but is a coke that can be further changed by carbonpyrolysis.4
18、. 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 swept away by thenitrogen. The carbonaceous-type residue
19、 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 residue value of the va
20、rious 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 exercised in interpreting
21、 the results.5.2 This test method offers advantages of better control oftest conditions, smaller samples, and less operator attentioncompared to Test Method D189, 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
22、.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 expected to yield re
23、sidues 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 0.5D4530 113record. Place the loaded sample vials into vial holder (up totwelve), noting position of each sample
24、 with respect to indexmark.NOTE 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 averagepercent carbon residue and standard deviation. Results for e
25、ach 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.8.2 Processing of Samples:8.2.1 With the oven at less than 1
26、00C, 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, causing loss ofsample, discard and repeat the test.NOTE 3Spa
27、ttering 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 oven to cool freely while undernitrogen purge of 600 mL/min.
28、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 cycle. The introduction ofair (oxygen) will likely cause the
29、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 flow until after the vial holderhas been removed from the oven
30、.) (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 exhaust chimney toavoid creating negative pressure in the li
31、ne.)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 vials (maintained inplace in the vial holder) to desiccator
32、 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 chamber; empty if necessary and replace.(WarningThe condensate
33、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 applicable to light distillate materials,such as ASTM No. 1
34、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 in this analysis. Fora 100-mL distillation, assemble the di
35、stillation apparatus de-scribed in Specification E133, 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 E133, using flask D (250-mL bu
36、lb 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 IP High Distilla-tion Thermometer 6C, as prescribed in the Spe
37、cification 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 13C and ambient. Maintain the con-denser bath temperature be
38、tween 0 and 60C so as to providea sufficient temperature 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 d
39、oes not touch the wall of the cylinder.The receiver 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 re
40、gulatedthat 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.After the first drop falls, move the receiving cylinder so that thetip of the condenser tube touches the wall of t
41、he 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, continue thedistillation until approximately 178 mL of distillate has beencollected, and then discontinue heating and
42、 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 mL of distillatehas been collected, and then discontinue heating and allow thecondenser to drain until 90 mL (90
43、% (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 suitable container, such as a small Erlen-meyer flask. Add to this container, while still warm, theD4530 114distillation residue left in the distilling
44、flask, and mix well. Thecontents of the container then represents 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 al
45、low a portion ofthe material to be transferred into a previously 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 pr
46、ocedure described inSection 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
47、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 thenearest 0.1% (m/m). For Micro Method carbon residue on10 % distillation residue, percent to the nearest 0.1 % (m/m).12. Precision and
48、 Bias512.1 The precision of 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
49、 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 Fig. X1.1regarding a separate 1983 correlation study6that was performed betweenTest Methods D189 and D4530.12.2 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 long run, in the normal and correct operation ofthe test method, exceed the values s
