1、Designation: D6316 09b1Standard Test Method forDetermination of Total, Combustible and Carbonate Carbonin Solid Residues from Coal and Coke1This standard is issued under the fixed designation D6316; the number immediately following the designation indicates the year oforiginal adoption or, in the ca
2、se of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1NOTETable A1.1 was editorially corrected in June 2013.1. Scope1.1 This test method covers the determi
3、nation of total,combustible, and carbonate carbon remaining in the solidbyproducts of combustion from boiler furnaces and similarreactors, including ash, flyash, char, slag, and similar materials.1.2 This test method is intended for the use of industry todetermine the performance of boiler furnaces
4、and similarcombustion reactors and aid in determining the quality of thesolid residue from combustion.1.3 This test method comprises the use of any of severalmethods to determine total carbon content combined with anyof several methods to determine carbonate carbon, and thecalculation, by difference
5、, of the combustible carbon remainingin a sample.1.4 Alternatively, this test method applies to the determina-tion of total carbon remaining in a material after acidificationwith strong acid to evolve carbonate carbon. In this case, thecombustible carbon is the total carbon measured in the sampleaft
6、er acidification.1.5 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.6 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
7、to establish appro-priate safety and health practices and to determine theapplicability of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D121 Terminology of Coal and CokeD513 Test Methods for Total and Dissolved Carbon Dioxidein WaterD1756 Test Method for Determinati
8、on as Carbon Dioxide ofCarbonate Carbon in Coal (Withdrawn 2013)3D3178 Test Methods for Carbon and Hydrogen in theAnalysis Sample of Coal and Coke (Withdrawn 2007)3D3180 Practice for Calculating Coal and Coke Analysesfrom As-Determined to Different BasesD5373 Test Methods for Instrumental Determinat
9、ion ofCarbon, Hydrogen, and Nitrogen in Laboratory Samplesof Coal and CokeE691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method2.2 Other Standards:ANSI/ASME Standard, PTC 38-1980 Determining the Con-centration of Particulate Matter in A Gas Stream and USEPA
10、 Standard CFR 60 Appendix A, Method 1743. Terminology3.1 Definitions:3.1.1 For additional definitions of terms used in this testmethod, refer to Terminology D121.3.1.2 carbonate carbon, nthe carbon content present inthe solid products derived from the combustion or reaction ofcoal, coal byproducts,
11、or coke as carbonates and which isnon-combustible in standard industry practice.1This test method is under the jurisdiction of ASTM Committee D05 on Coaland Coke and is the direct responsibility of Subcommittee D05.29 on MajorElements in Ash and Trace Elements of Coal.Current edition approved May 1,
12、 2009. Published June 2009. Originallyapproved in 1998. Last previous edition approved in 2009 as D6316 - 09a. DOI:10.1520/D6316-09BE01.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume in
13、formation, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.4Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.Copyright ASTM
14、 International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.3 combustible carbon, ncarbon content remaining inthe solid products derived from the combustion or reaction ofcoal, coal byproducts, or coke, exclusive of carbonate in anyform.3.1.4 total carbon,
15、 ncarbon content remaining in the solidproducts derived from the combustion or reaction of coal, coalbyproducts, or coke, inclusive of carbonate in any form.4. Summary of Test Method4.1 Total CarbonThe determination of total carbon ismade by the oxidative thermal decomposition of a weighedquantity o
16、f sample in a closed system and, after completeoxidation and purification of the resulting gaseous products,measurement of the carbon dioxide produced by one of severalmethods.4.1.1 Absorptive Determination of Total CarbonTheevolved carbon dioxide is fixed on an absorption train and ismeasured quant
17、itatively by weighing the absorbent (see TestMethods D3178).4.1.2 Instrumental Determination of Total CarbonThecarbon dioxide is measured quantitatively by an electronicdetection system calibrated against an appropriate referencestandard (see Test Methods D5373).4.2 Carbonate CarbonThe determination
18、 of carbonatecarbon is made by decomposing a weighed quantity of thesample with a dilute mineral acid, and after the purification ofthe evolved gases, measuring quantitatively the evolved carbondioxide.4.2.1 Absorptive Determination of Carbonate CarbonThecarbon dioxide is liberated by acidification
19、and heating. Theevolved gases are passed through a purification train and theCO2is fixed as Na2CO3on a preweighed absorption unit andis measured gravimetrically (see Test Method D1756).4.2.2 Coulometric Determination of Carbonate CarbonThe carbon dioxide is liberated by acidification and heating.The
20、 evolved gas is swept through a scrubber and into anabsorption cell where it is coulometrically titrated (see Part Bof Test Methods D513).4.2.3 Instrumental Determination of Carbonate CarbonThe carbon dioxide is liberated by acidification and heating.The evolved gases are purified and measured quant
21、itatively byan electronic detection system against an appropriate referencestream. This test method resembles that for the instrumentaldetermination of total carbon, with the provision for samplecombustion replaced by a provision for acidification. Inpractice, this test method uses an adaptation to
22、instrumentsdesigned to measure total carbon content.4.3 Combustible Carbon by Prior AcidificationThe deter-mination of combustible carbon is made directly by firstacidifying and heating to dryness a weighed sample. Allcarbonate carbon present is evolved as carbon dioxide. Thedried sample is then ana
23、lyzed for total carbon content as above.No determination of carbonate carbon is made and the carboncontent measured as total carbon is the combustible carbon.5. Significance and Use5.1 The combustible carbon content of solid residues is usedto calculate efficiency of fuel combustion in boiler furnac
24、es andsimilar combustors.5.2 Combustible carbon values are also used to determinethe residual fuel value of incompletely combusted/reacted coaland coke in other reactors that consume carbonaceous fuels(examples include fluidized bed furnaces and liquefaction,gasification and pyrolysis reactors).5.3
25、The combustible carbon content of flyash is an impor-tant parameter in the use of flyash as a cement additive.6. Interferences6.1 The interferences for the determination of total carboncontent are those specified in the referenced standard methods,Test Methods D3178 and Test Methods D5373, with thef
26、ollowing added stipulation.6.1.1 The temperature and conditions of combustion thatensure complete conversion of a residue samples total carboncontent to carbon dioxide may be different than those requiredfor conversion in coal samples. It is absolutely imperative thatthe instrumental conditions used
27、 will ensure complete conver-sion of mineral carbonate in any amount or form.6.2 The interferences for the determination of carbonatecarbon are those specified in the referenced methods, TestMethod D1756 and Part B of Test Methods D513 with thefollowing stipulation6.2.1 Some coal combustion residues
28、 contain significantamounts of reactive elements such as CaO which will absorbcarbon dioxide on exposure to open air and form mineralcarbonates. This will influence the calculated amount ofcombustible carbon in the sample only if there was carbondioxide chemisorption from the air between the time of
29、 thecarbonate determination and the total carbon determination.Therefore, it is necessary that the sample be protected from airexposure.6.3 The mineral acid and temperature required for prioracidification of the analytical sample shall not interfere withthe amount of combustible carbon present in th
30、e sample or theanalytical determination of carbon. The use of oxidizing acidssuch as concentrated nitric acid may oxidize a portion of thecombustible carbon. Other acids such as hydrochloric acid maybe incompatible with the reagents used to purify the gas streamin the instrumental determination of c
31、arbon. Sulfuric acid hasa relatively high boiling point and is difficult to remove fromthe sample by drying. A solution of 10 % nitric acid issuggested for use in this procedure.7. Apparatus7.1 The apparatus used is specified in the respective refer-enced method.7.2 Total Carbon Content:7.2.1 Absorp
32、tive Determination of Total CarbonThe ap-paratus consists of an oxygen-purifying train, combustion unit,and absorption train of the type and configuration specified inTest Methods D3178.D6316 09b127.2.2 Instrumental Determination of Total CarbonBecause a variety of instrumental components and config
33、ura-tions can be used satisfactorily for these test methods, nospecifications are presented here with respect to overall systemdesign. However, the apparatus shall be capable of completelyconverting the carbon content to carbon dioxide, and thedetection system shall determine the carbon dioxide indi
34、vidu-ally and without interference.7.3 Carbonate Carbon Content:7.3.1 Absorptive Determination of Carbonate CarbonTheapparatus shall consist of an air purifying train, reaction unit,and absorption unit of the type and configuration specified inTest Method D1756.7.3.2 Coulometric Determination of Car
35、bonate CarbonThe apparatus shall consist of an evolution unit, a carbondioxide coulometer, scrubber, and pH meter of the type andconfiguration specified in Part B of Test Methods D513.7.3.3 Instrumental Determination of Carbonate CarbonThe apparatus shall consist of a heated acidification unit that
36、isinstalled by bypassing the combustion system in a devicedesigned for the determination of total carbon content. Thegas-purifying system of such instrument shall be capable ofcompletely removing the water content and acid gases pro-duced as byproducts of the carbon dioxide evolution. Thedetection s
37、ystem shall measure the evolved carbon dioxide asan individual species and without interference.7.4 Combustible Carbon by Prior AcidificationThe cru-cibles used for this method must be free of carbonate, inert tothe mineral acid used, and compatible with the instrument usedfor measuring total carbon
38、. The acidified sample is heated todryness using a laboratory hotplate capable of maintaining thefine temperature control required to dry the sample withoutmaterial loss of sample as a result of spattering or boilover. Theinstrument used shall meet the requirements of Test MethodsD5373 and be capabl
39、e of removing the additional acid gasesthat result from the mineral acid used for evolving the carbondioxide before determining carbon content.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform
40、 to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.5Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the de
41、termination.9. Standards9.1 There are currently no standard reference materials ofcoal or coke residues that are certified for combustible carbonor carbonate carbon content. However, other types of standardmaterials can be used for both method validation and instru-ment calibration. These include:9.
42、1.1 Buffalo River Sediment (NIST 2704)Total carbon =3.348 6 0.016 %.9.1.2 Carbonate Primary Standard GradeFor example,CaCO3total carbonate carbon = 12.00 %.9.1.3 CoalBituminous (NIST 1632b) total carbon = 76.866 0.26 %.9.1.4 EDTA Primary Standard GradeTotal carbon =41.07 %.10. Sample Preparation10.1
43、 If moist or wet, the combustion residue sample6will bepredried at 107 6 3C. Drying time should be the minimumrequired to ensure complete dryness of the sample to minimizeabsorption of carbon dioxide from the air (see 6.2.1).10.2 The method of sample preparation used is specified inthe respective re
44、ferenced method.10.3 Samples in excess of 50 g should be divided by rifflingto ensure a representative analysis sample. Samples of 50 g orless should be prepared in their entirety.10.4 The analysis sample shall initially be prepared to passthrough a 250-m (# 60 U.S. standard) sieve. If required by t
45、hecharacteristics of the instrument system or analytical precisionof the resulting data or both, the analysis sample should beground to pass through a 75-m (# 200 U.S. standard) sieve.711. Instrument Preparation and Verification11.1 The preparation of equipment and instruments is speci-fied in the r
46、espective referenced methods and the manufactur-ers instructions.11.2 The proper functioning of the equipment and theoperational parameters should be verified by analyzing blanksand standard materials that contain carbonate carbon andcombustible carbon.11.2.1 The proper combustion temperature and co
47、nditionsnecessary to convert the carbonate carbon to carbon dioxidemay be determined by measuring the carbon content of acarbonate standard. Measured carbon values of less than thecertified value indicate incomplete conversion of carbonates.11.2.2 Combustion accelerants such as magnesium powder,ther
48、mite (aluminum powder and iron oxide), and tin powdercan be used to ensure the total conversion of carbonates tocarbon dioxide by significantly raising the reaction temperatureduring combustion.5Reagent Chemicals, American Chemical Society Specifications , AmericanChemical Society, Washington, DC. F
49、or suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Pool, Dorset, U.K., and the United States Pharmacopoeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.6Sample CollectionAnalysis samples are intended to originate by collectionaccording to appropriate standard industry practice suitable for the intendedpurpose. In the case of combustion boilers, it may be necessary to collect bottomash, fly ash, and slag samples for analysis. The
