Designation:D4530–07An American National Standard Standard Test Method for
Determination of Carbon Residue(Micro Method)1
This standard is issued under thefixed designation D4530;the number immediately following the designation indicates the year of
original adoption or,in the case of revision,the year of last revision.A number in parentheses indicates the year of last reapproval.A
superscript 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*
1.1This test method covers the determination of the amount of carbon residue(see Note1)formed after evaporation and pyrolysis of petroleum materials under certain conditions and is intended to provide some indication of the relative coke forming tendency of such materials.
1.2The test results are equivalent to the Conradson Carbon Residue test(see Test Method D189).
N OTE1—This procedure is a modification of the original method and apparatus for carbon residue of petroleum materials,where it has been demonstrated that thermogravimetry is another applicable technique.2 However,it is the responsibility of the operator to establish operating conditions to obtain equivalent results when using thermogravimetry. 1.3This test method is applicable to petroleum products that partially decompose on distillation at atmospheric pressure and was tested for carbon residue values of0.10to30%(m/m). Samples expected to be below0.10weight%(m/m)residue should be distilled to remove90%(V/V)of theflask charge (see Section9).The10%bottoms remaining is then tested for carbon residue by this test method.
1.4Ash-forming constituents,as defined by Test Method D482,or non-volatile additives present in the sample will add to the carbon residue value and be included as part of the total carbon residue value
reported.
1.5Also in diesel fuel,the presence of alkyl nitrates,such as amyl nitrate,hexyl nitrate,or octyl nitrate,causes a higher carbon residue value than observed in untreated fuel,which may lead to erroneous conclusions as to the coke-forming propensity of the fuel.The presence of alkyl nitrate in the fuel may be detected by Test Method D4046.北京新世界
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1.6The values stated in SI units are to be regarded as the standard.The values given in parentheses are for information only.
1.7This standard does not purport to address all of the safety concerns,if any,associated with its use.It is the responsibility of the user of this standard to establish appro-priate safety practices and to determine the applicability of regulatory limitations prior to use.For specific warning statements,see8.
2.3and8.4.
2.Referenced Documents
2.1ASTM Standards:3
D189Test Method for Conradson Carbon Residue of Petroleum Products
D482Test Method for Ash from Petroleum Products
D4046Test Method for Alkyl Nitrate in Diesel Fuels by Spectrophotometry
D4057Practice for Manual Sampling of Petroleum and Petroleum Products
D4177Practice for Automatic Sampling of Petroleum and Petroleum Products
E1Specification for ASTM Liquid-in-Glass Thermometers E133Specification for Distillation Equipment
2.2Energy Institute Standard:
Specification for IP Standard Thermometers4
3.Terminology
3.1Definitions:
3.1.1carbon residue,n—in petroleum products,the part remaining after a sample has been subjected to thermal decomposition.
3.1.1.1Discussion—The amount of residue is dependent on the test conditions of evaporation and pyrolysis.The term may be misleading here in that the residue may contain other than carbon decomposition products.However,the term is retained due to its wide common usage.
4.Summary of Test Method
4.1A weighed quantity of sample is placed in a glass vial and heated to500°C under an inert(nitrogen)atmosphere in a controlled manner for a specific time.The sample undergoes coking reactions,and volatiles formed are swept away by the
1This test method is under the jurisdiction of ASTM Committee D02on Petroleum Products and Lubricants and is the direct responsibility of Subcommittee D02.06on Analysis of Lubricants.
Current edition approved Nov.1,2007.Published December2007.Originally approved in1985.Last previous edition approved in2006as D4530–06e1.
2See Fuel,V ol63,July1984,pp.931–934.
3For referenced ASTM standards,visit the ASTM website,,or contact ASTM Customer Service at For Annual Book of ASTM Standards volume information,refer to the standard’s Document Summary page on the ASTM website.
4“Methods for Analysis and Testing,”Institute of Petroleum Standard Methods for Petroleum and Its Products,Part I,V ol2.Available from Energy Institute,61 New Cavendish St.,London,WIM8AR,UK.
*A Summary of Changes section appears at the end of this standard. Copyright©ASTM International,100Barr Harbor Drive,PO Box C700,West Conshohocken,PA19428-2959,United States.
nitrogen.The carbonaceous-type residue remaining is reported as a percent of the original sample as “carbon residue (micro).”4.1.1When 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 Use
5.1The carbon residue value of the various petroleum materials serves as an approximation of the tendency of the material to form carbonaceous type deposits under degradation conditions similar to
those used in the test method,and can be useful as a guide in manufacture of certain stocks.However,care needs to be exercised in interpreting the results.
5.2This test method offers advantages of better control of test conditions,smaller samples,and less operator attention compared to Test Method D 189,to which it is equivalent.5.3Up to twelve samples may be run simultaneously,including a control sample when the vial holder shown in Fig.1is used exclusively for sample analysis.
6.Apparatus
6.1Glass Sample Vials ,2-mL capacity,12-mm outside diameter by approximately 35-mm high.
6.2Larger 4-dram Glass Sample Vials ,15-mL capacity (20.5to 21-mm outside diameter by 7061-mm high),may be used for samples that are expected to yield residues <0.10%(m/m)so that a more appreciable mass difference can be determined.It should be noted the precision statements for the test method were determined using the 2-mL capacity vials only (with sample residues between 0.3and 26%(m/m)and that the precision associated with using the larger sample vials has not been determined.
6.3Eyedropper,Syringe,or Small Rod ,for sample transfer.6.4Coking Oven with circular heating chamber approxi-mately 85mm (33⁄8in.)in diameter by 100-mm (4-in.)deep,for top loading,with heating capability from 10to 40°C/min rate to 500°C,with exhaust port 13-mm (1⁄2-in.)inside diameter for nitrogen purge of oven chamber (inlet near top,exhaust at bottom center)with thermocouple sensor located in oven chamber next to but not touching sample vials,with lid capable of sealing out air,and with removable condensate trap located at the oven chamber base.A schematic diagram is given in Fig.2.
6.5Sample Vial Holder —Cylindrical aluminum block,ap-proximately 76mm (3in.)in diameter by 16-mm (5⁄8-in.)thick,with twelve evenly spaced holes (for vials)each 13mm (1⁄2in.)in diameter by 13-mm (1⁄2-in.)deep.The holes are arranged in a circular pattern approximately 3mm (1⁄8in.)from the perimeter.The holder has legs 6-mm (1⁄4-in.)long,with guides to center in oven chamber,and an index mark on the side to use as position reference.The sample vial holder is shown in Fig.1.
6.6A modified version of the standard sample vial holder (see Fig.1)is required when larger glass sample vials (see 6.2)are used.The modified sample vial holder is similar in nature to the twelve hole vial holder,except that there are six evenly spaced holes (for vials)each 21.260.1mm in diameter by approximately 16-mm deep,arranged in a circular pattern.6.7Thermocouple ,suitable for controller an
d temperature range of interest,with exterior temperature readout,degrees Celsius.
6.8Analytical Balance ,with 60.1mg sensitivity to 20g minimum weighing
capacity.
FIG.1Sample Vial Holder and
Vial
6.9Nitrogen ,minimum 99.998%purity with suitable means of delivering a pressure of 0to 200kPa (0to 30psig).Cylinders of zero grade nitrogen have been found suitable to use.
7.Sampling
7.1Using the practices outlined in Practice D 4057(manual sampling)or Practice D 4177(automatic sampling),ensure that a representative sample of material to be tested is obtained.8.Procedure
8.1Sample Preparation :
8.1.1Determine the mass of each clean sample vial being used in the sample analysis,and record the mass to nearest 0.1mg.
8.1.2During weighing and filling,handle vials with forceps to help minimize weighing errors.Discard the sample vials after use.
8.1.3It is assumed that a representative sample of the stock or process has been obtained for laboratory use following Practice D 4057or similar standard.Stir the sample to be tested,first warming if necessary to reduce its viscosity.Samples that are homogeneous liquids can be transferred directly to vials using a rod,syringe,or eyedropper.Solid
materials may also be heated;or frozen with liquid nitrogen,and then shattered to provide manageable pieces.
8.1.4Transfer an appropriate mass of the sample (see Table 1)into a tared-sample vial,reweigh to nearest 0.1mg,and record.Place the loaded sample vials into vial holder (up to twelve),noting position of each sample with respect to index mark.
N OTE 2—A control sample can be included in each batch of samples being tested.This control sample should be a typical sample that has been tested at least 20times in the same equipment in order to define an average percent carbon residue and standard deviation.Results for each batch are deemed acceptable when results for the control sample fall within the average percent carbon re
sidue 6three standard deviations.
Control
FIG.2Coking Oven and Lid
TABLE 1Guide for Sample Size
Sample Description
Expected Carbon Residue,(m/m)%
Recommended Sample Size,g Black,viscous or solid >50.1560.05Brown,viscous
1–50.560.1Lube oil consistency and
appearance,10%bottoms on distillate material 0.1–<1
1.560.5
Large vials only <0.1 5.061.0Small vials only
<0.1 1.56
0.5
results that are outside these limits indicate problems with the procedure or the equipment.
8.2Processing of Samples:
8.2.1With the oven at less than100°C,place the vial holder into the oven chamber and secure lid.Purge with nitrogen for at least10min at600mL/min.Then decrease the purge to150 mL/min and heat the oven slowly to500°C at10°–15°C/min.
8.2.2If the sample foams or spatters,causing loss of sample,discard and repeat the test.
N OTE3—Spattering may be due to water that can be removed by prior gentle heating in a vacuum,followed by a nitrogen sweep.Alternatively,
a smaller sample size can be used.
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8.2.3Hold oven at50062°C for15min.Then shut off furnace power and allow oven to cool freely while under nitrogen purge of600mL/min.When oven temperature is less than250°C,remove the vial holder for further cooling in desiccator.After the samples are removed from the oven,the nitrogen purge may be shut off.(Warning—Do not open oven to air at any time during the heating cycle.The introduction of air(oxygen)will likely cause the sample to ignite and spoil the test.(Because of the oven design and materials,such an ignition is normally not a hazard to the operator.)Open the oven only after oven temperature falls below250°C during the cooling step.Maintain nitrogenflow until after the vial holder has been removed from the oven.)(Warning—Locate the coking oven in laboratory exhaust hood for safe venting of smoke and fumes.Alternatively,install vent line from MCRT oven exhaust to laboratory exhaust system.)(Warning—If a vent line is used,do not connect directly to exhaust chimney to avoid creating negative pressure in the line.)
N OTE4—To reduce oven temperature for the next run,remove the oven lid to allow faster cooling.As required by the procedure,the subsequent test can be started when the oven has been cooled to below100°C. 8.3Final Weighing—Transfer sample vials(maintained in place in the vial holder)to desiccator and allow vials to cool to room temperature.Weigh the cooled vials to the nearest0.1mg and record.Handle the vials with forceps.Discard the used glass sample vials.
kernelfaultcheck8.4Occasionally examine the condensate trap at the bottom of the oven chamber;empty if necessary and replace. (Warning—The condensate trap residue may have some carcinogenic materials present.Avoid contact with the trap residue;dispose of it in accordance with local laboratory practice.)
9.Procedure for Carbon Residue on10%(V/V)
Distillation Residue
9.1This procedure is applicable to light distillate materials, such as ASTM No.1and No.2fuel oil or materials expected to have less than0.1%(m/m)carbon residue.
9.2A distillation analysis using either a100or200-mL starting volume is required in order to collect a sufficient amount of the10%(V/V)residue needed in this analysis.For a100-mL distillation,assemble the distillation apparatus de-scribed in Specification E133,usingflask B(125-mL bulb volume),flask support board with50-mm diameter opening, and graduated cylinder B(100-mL capacity).For a200-mL distillation,assemble the distillation apparatus described in Specification E133,usingflask D(250-mL bulb volume),flask support board with50-mm diameter opening,and graduated cylinder C(200-mL capacity).A thermometer is not required, but the use of the ASTM High Distillation Thermometer8F or 8C,as prescribed in Specification E1,or the IP High Distilla-tion Thermometer6C,as prescribed in the
Specification for IP Thermometers,is recommended.
9.3Depending upon which distillationflask is used,place either100or200mL of sample(as measured at ambient temperature)into a tared distillationflask that is held at a temperature between13°C and ambient.Maintain the con-denser bath temperature between0and60°C so as to provide a sufficient temperature differential for sample condensation, while avoiding any solidification of waxy material in the condenser tube.Use,without cleaning,the cylinder from which the sample was measured as the receiver,and place it so that the tip of the condenser does not touch the wall of the cylinder. The receiver temperature is required to be maintained at the same temperature(within63°C)as the sample taken at the start of the test in order to obtain an accurate volume measurement in the receivingflask.
9.4Apply the heat to theflask at a uniform rate so regulated that thefirst drop of condensate exits from the condenser between10and15min(for200-mL samples)or between5and 15min(for100-mL samples)after initial application of heat. After thefirst drop falls,move the receiving cylinder so that the tip of the condenser tube touches the wall of the cylinder.Then regulate the heat so that the distillation proceeds at a uniform rate of8to10mL/min(for200-mL samples)or4to5mL/min (for100-mL samples).For200-mL samples,continue the distillation until approximately178mL of distillate has bee
n collected,and then discontinue heating and allow the con-denser to drain until180mL(90%(V/V)of the charge to the flask)has been collected in the cylinder.For100-mL samples, continue the distillation until approximately88mL of distillate has been collected,and then discontinue heating and allow the condenser to drain until90mL(90%(V/V)of the charge to theflask)has been collected in the cylinder.
9.5Catchfinal drainage,if any,by immediately replacing the cylinder with a suitable container,such as a small Erlen-meyerflask.Add to this container,while still warm,the distillation residue left in the distillingflask,and mix well.The contents of the container then represents a10%(V/V)distil-lation residue from the original product.
9.6If the distillation residue is too viscous toflow freely at ambient temperature,it is necessary to warm the distillation residue to a sufficient temperature that will allow a portion of the material to be transferred into a previously weighted vial for analysis(see Table1).After allowing the material in the vial to cool to ambient temperature,determine the mass of the test specimen to the nearest0.1mg and carry out the carbon residue test in accordance with the procedure described in Section8.直言命题
10.Calculation
10.1Calculate the mass%carbon residue in the original sample,or in the10%distillation bottoms as follows:
10.1.1Calculate percent residue as
follows:
丁晓兵老婆%carbon residue 5
~A 3100!
W
(1)
where:
A =carbon residue,g,and W =sample used,g.
11.Report
11.1For values up to 10%,report the value obtained as Micro Method carbon residue,percent to the nearest 0.01%(m/m).For values above 10%,report the value obtained to the nearest 0.1%(m/m).For Micro Method carbon residue on 10%distillation residue,percent to the nearest 0.1%(m/m).12.Precision and Bias 5
12.1The precision of this test method as determined by (see Note 5)statistical examination of interlaboratory results is as follows:
N OTE 5—Precision data were generated by a task force in 2004.The round robin involved nine laboratories and six petroleum materials in duplicate analysis.The range for values samples was from 0.1%to 25%(m/m).No precision data or correlation data exists for results obtained
using 10%bottoms or 15-mL vials,or both.See X1.1and Fig.X1.1regarding a separate 1983correlation study 6that was performed between Test Methods D 189and D 4530.
12.2Repeatability —The difference between two test re-sults,obtained by the same operator with the same apparatus under constant operating conditions on identical test material,would,in the long run,i
n the normal and correct operation of the test method,exceed the values shown in Fig.3in only one case in twenty.
12.3Reproducibility —The difference between two single and independent results,obtained by different operators work-ing in different laboratories on identical test material,would,in the long run,in the normal and correct operation of the test method,exceed the values shown in Fig.3in only one case in twenty.
12.4Bias —The procedure in Test Method D 4530for mea-suring carbon residue of petroleum by the carbon residue method has no bias because the mass %of carbon residue can be defined only in terms of the test method.
13.Keywords
13.1carbon residue;carbon residue (micro method);diesel fuel;lubricating oil;petroleum products
5
Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:D02-1589.
6
Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR:
FIG.3Carbon Residue (Micro)Precision
Data
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