1、Designation: D5865 10a1Standard Test Method forGross Calorific Value of Coal and Coke1This standard is issued under the fixed designation D5865; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in
2、 parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1NOTEExtraneous section number 6.6.4 was editorially removed in January 2011.1. Scope*1.1 This test method pertains to the determination of thegross calorif
3、ic value of coal and coke by either an isoperibol oradiabatic bomb calorimeter.1.2 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.3 This standard does not purport to address all of thesafety concerns, if any, associated with
4、its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific hazardstatements are given in Section 8.2. Referenced Documents2.1 ASTM Standards:2D121 Terminology of
5、 Coal and CokeD346 Practice for Collection and Preparation of CokeSamples for Laboratory AnalysisD388 Classification of Coals by RankD1193 Specification for Reagent WaterD2013 Practice for Preparing Coal Samples for AnalysisD3173 Test Method for Moisture in the Analysis Sample ofCoal and CokeD3177 T
6、est Methods for Total Sulfur in the AnalysisSample of Coal and CokeD3180 Practice for Calculating Coal and Coke Analysesfrom As-Determined to Different BasesD4239 Test Method for Sulfur in the Analysis Sample ofCoal and Coke Using High-Temperature Tube FurnaceCombustionD5142 Test Methods for Proxima
7、teAnalysis of theAnalysisSample of Coal and Coke by Instrumental Procedures3E144 Practice for Safe Use of Oxygen Combustion BombsE178 Practice for Dealing With Outlying ObservationsE882 Guide for Accountability and Quality Control in theChemical Analysis LaboratoryE2251 Specification for Liquid-in-G
8、lass ASTM Thermom-eters with Low-Hazard Precision Liquids3. Terminology3.1 Definitions:3.1.1 adiabatic calorimetera calorimeter that operates inthe adiabatic mode and may or may not use a microprocessor.The initial temperature before initiating the combustion and thefinal temperatures are recorded b
9、y the operator or the micro-processor.3.1.2 automated calorimetera calorimeter which has amicroprocessor that takes the thermometric readings and cal-culates the Calibration Value and the Heat of CombustionValues.3.1.3 British thermal unit Btuis the amount of heatrequired to raise the temperature of
10、 one pound - mass lbm ofliquid water at one atmosphere pressure one degree Fahrenheitat a stated temperature. The results of combustion calorimetrictests of fuels for steam power plants may be expressed in termsof the 1956 International Steam Table calorie (I.T. cal) whichis defined by the relation,
11、 1 I.T. cal = 4.1868 J. The Btu usedin modern steam tables is defined by the means of the relation,1I.T.cal/g=1.8I.T.Btu/lb.Thus, 1 I.T. Btu / lb = 2.326 J/g.3.1.4 calorific valuethe heat produced by combustion of aunit quantity of a substance under specified conditions.3.1.5 calorimetera device for
12、 measuring calorific valueconsisting of a bomb, its contents, a vessel for holding thebomb, temperature measuring devices, ignition leads, water,stirrer, and a jacket maintained at specified temperature con-ditions.1This test method is under the jurisdiction of ASTM Committee D05 on Coaland Coke and
13、 is the direct responsibility of Subcommittee D05.21 on Methods ofAnalysis.Current edition approved May 1, 2010. Published July 2010. Originally approvedin 1995. Last previous edition approved in 2010 as D5865 10. DOI: 10.1520/D5865-10AE01.2For referenced ASTM standards, visit the ASTM website, www.
14、astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn. The last approved version of this historical standard is referencedon www.astm.org.1*A Summary of Changes sec
15、tion appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.3.1.6 gross calorific value (gross heat of combustion atconstant volume), Qv(gross)the heat produced by completecombustion of a substance at cons
16、tant volume with all waterformed condensed to a liquid.3.1.7 heat of formationthe change in heat content result-ing from the formation of 1 mole of a substance from itselements at constant pressure.3.1.8 isoperibol calorimetera calorimeter that operates inthe isoperibol mode and uses a microprocssor
17、 to record theinitial and final temperatures and make the appropiate heat leakcorrections during the temperature rise. It determines when thecalorimeter is in equilibrium and ignites the sample anddetermines when the calorimeter has reached equilibrium afterignition.3.1.9 net calorific value (net he
18、at of combustion at constantpressure), Qp(net)the heat produced by combustion of asubstance at a constant pressure of 0.1 MPa (1 atm), with anywater formed remaining as vapor.3.2 Definitions of Terms Specific to This Standard:3.2.1 corrected temperature risethe calorimeter tempera-ture change caused
19、 by the process that occurs inside the bombcorrected for various effects.3.2.2 heat capacitythe energy required to raise the tem-perature of the calorimeter one arbitrary unit.3.2.2.1 DiscussionThe heat capacity can also be referredto as the energy equivalent or water equivalent of the calorim-eter.
20、4. Summary of Test Method4.1 The heat capacity of the calorimeter is determined byburning a specified mass of benzoic acid in oxygen. Acomparable amount of the analysis sample is burned under thesame conditions in the calorimeter. The calorific value of theanalysis sample is computed by multiplying
21、the correctedtemperature rise, adjusted for extraneous heat effects, by theheat capacity and dividing by the mass of the sample.NOTE 1Oxidation of coal after sampling can result in a reduction ofcalorific value. In particular, lignite and sub-bituminous rank coal samplesmay experience greater oxidat
22、ion effects than samples of higher rankcoals. Unnecessary exposure of the samples to the air for the time ofsampling or delay in analysis should be avoided.5. Significance and Use5.1 The gross calorific value can be used to compute thetotal calorific content of the quantity of coal or coke repre-sen
23、ted by the sample for payment purposes.5.2 The gross calorific value can be used for computing thecalorific value versus sulfur content to determine whether thecoal meets regulatory requirements for industrial fuels.5.3 The gross calorific value can be used to evaluate theeffectiveness of beneficiat
24、ion processes.5.4 The gross calorific value can be required to classifycoals according to Classification D388.6. Apparatus and Facilities6.1 Test AreaAn area free from drafts, shielded fromdirect sunlight and other radiation sources. Thermostatic con-trol of room temperature and controlled relative
25、humidity aredesirable.6.2 Combustion BombConstructed of materials that arenot affected by the combustion process or the products formedto introduce measurable heat input or alteration of end prod-ucts. The bomb shall be designed so that all liquid combustionproducts can be completely recovered by wa
26、shing the innersurfaces. There shall be no gas leakage. The bomb shall becapable of withstanding a hydrostatic pressure test to 20 MPa(3000 psig) at room temperature without stressing any partbeyond its specified elastic limit.6.3 BalanceAlaboratory balance capable of weighing theanalysis sample to
27、the nearest 0.0001 g. The balance shall bechecked weekly, at a minimum, for accuracy.6.4 Calorimeter VesselMade of metal with a tarnish-resistant coating, with all outer surfaces highly polished. Itssize shall be such that the bomb is completely immersed inwater during a determination. A stirrer sha
28、ll be provided foruniform mixing of the water. The immersed portion of thestirrer shall be accessible to the outside through a coupler oflow thermal conductivity. The stirrer speed shall remainconstant to minimize any temperature variations due to stirring.Continuous stirring for 10 min shall not ra
29、ise the calorimetertemperature more than 0.01C when starting with identicaltemperatures in the calorimeter, test area and jacket. Forcalorimeters having a bucket it can be a separate component orintegral component of the bomb. The vessel shall be of suchconstruction that the environment of the calor
30、imeters entireouter boundaries can be maintained at a uniform temperature.6.5 JacketA container with the inner perimeter main-tained at constant temperature 60.1C (isoperibol) or at thesame temperature 60.1C as the calorimeter vessel (adiabatic)during the test. To minimize convection, the sides, top
31、 andbottom of the calorimeter vessel shall not be more than 10 mmfrom the inner surface of the jacket. Mechanical supports forthe calorimeter vessel shall be of low thermal conductivity.6.6 Thermometers:6.6.1 Platinum resistance or thermistor thermometersshall be capable of measuring to the nearest
32、0.0001C. Thesetypes of thermometers consist of two major subsystems. Thefirst and most obvious is the temperature sensing probe itself.The second and equally important aspect is the measurementsubsystem. For both subsystems, the relationship between thethermometer resistance and temperature shall be
33、 well charac-terized. The absolute temperature shall be known to 6 0.1Catthe temperature of the calorimetric measurement.6.6.2 Assessing the valid working range of the calorimeter,as outlined in 10.9, is sufficient to demonstrate that allimportant aspects of the calorimeter functionality, includingt
34、he thermometry, are in good working order. The traceability ofthe heat of combustion measurement is governed by thetraceability of the heat of combustion of the benzoic acidcalibrant in addition to meeting the aforementioned criteria.6.6.3 Liquid-in-Glass ThermometersConforming to therequirements fo
35、r thermometers S56C, S116C, or S117C asprescribed in Specification E2251.6.6.3.1 Thermometer AccessoriesA magnifier is requiredfor reading liquid-in-glass thermometers to one tenth of thesmallest scale division. The magnifier shall have a lens andholder designed so as to minimize errors as a result
36、of parallax.D5865 10a126.7 Sample HolderAn open crucible of platinum, quartz,or base metal alloy. Before use in the calorimeter, heat treatbase metal crucibles for a minimum of4hat500C to ensurethe crucible surface is completely oxidized. Base metal alloycrucibles are acceptable, if after three prel
37、iminary firings, theweight does not change by more than 0.0001 g.6.8 Ignition FuseIgnition fuse of 100-mm length and0.16-mm (No. 34 B filling the calorimeter vessel; firing theignition circuit; recording calorimeter temperatures before,during, and after the test; recording the balance weights; andca
38、rrying out all necessary corrections and calculations.6.11 Crucible LinerQuartz fiber or alundum for lining thecrucible to promote complete combustion of samples that donot burn completely during the determination of the calorificvalue.47. Reagents7.1 Reagent WaterConforming to conductivity require-
39、ments for Type II of Specification D1193 for preparation ofreagents and washing of the bomb interior.7.2 Purity of ReagentsUse reagent grade chemicals con-forming to the specification of the Committee on AnalyticalReagents of the American Chemical Society in all tests.57.3 Benzoic AcidStandard (C6H5
40、COOH)Pellets madefrom benzoic acid available from the National Institute ofStandards and Technology (NIST) or benzoic acid calibratedagainst NIST standard material. The calorific value of benzoicacid, for use in the calibration calculations, shall be traceable toa recognized certificate value.7.4 Ox
41、ygenManufactured from liquid air, guaranteed tobe greater than 99.5 % pure, and free of combustible matter.Oxygen made by the electrolytic process contains smallamounts of hydrogen rendering it unfit unless purified bypassage over copper oxide at 500C.7.5 Titration IndicatorMethyl orange, methyl red
42、, ormethyl purple for indicating the end point when titrating theacid formed during combustion. The same indicator shall beused for both calibration and calorific value determinations.7.6 Standard SolutionSodium carbonate (Na2CO3)orother suitable standard solution. Dissolve 3.757 g of sodiumcarbonat
43、e, dried for 24 h at 105C in water, and dilute to 1 L.One millilitre of this solution is equivalent to 4.2 J (1.0 calorie)in the acid titration.8. Hazards8.1 The following precautions are recommended for safecalorimeter operation. Additional precautions are noted inPractice E144. Also consult the ca
44、lorimeter equipment manu-facturers installation and operating instructions before usingthe calorimeter.8.1.1 The mass of sample and any combustion aid as well asthe pressure of the oxygen admitted to the bomb shall notexceed the bomb manufacturers specifications.8.1.2 Inspect the bomb parts carefull
45、y after each use.Replace cracked or significantly worn parts. Replace O-ringsand valve seats in accordance with manufacturers instruction.For more details, consult the manufacturer.8.1.3 Equip the oxygen supply cylinder with an approvedtype of safety device, such as a relief valve, in addition to th
46、eneedle valve and pressure gauge used in regulating the oxygenfeed to the bomb. Valves, gauges, and gaskets shall meetindustry safety codes. Suitable reducing valves and adaptersfor 3- to 4-MPa (300- to 500-psig) discharge pressure can beobtained from commercial sources of compressed gas equip-ment.
47、 Check the pressure gauge annually for accuracy or afterany accidental over pressures that reach maximum gaugepressure.8.1.4 During ignition of a sample, the operator shall notextend any portion of the body over the calorimeter.8.1.5 Do not fire the bomb if the bomb has been dropped orturned over af
48、ter loading.8.1.6 Do not fire the bomb if there is evidence of gasleakage when the bomb is submerged in the calorimeter vessel.8.1.7 For manually operated calorimeters, the ignitionswitch shall be depressed only long enough to fire the charge.9. Sample9.1 The analysis sample is the material pulveriz
49、ed to pass250-m (No. 60) sieve, prepared in accordance with eitherPractice D346 for coke or Method D2013 for coal.10. Determination of the Heat Capacity of theCalorimeter10.1 SampleWeigh 0.8 to 1.2 g of benzoic acid into asample holder. Record sample weight to the nearest 0.0001 g.10.2 Preparation of Bomb:10.2.1 Rinse the bomb with water to wet internal seals andsurface areas of the bomb or precondition the calorimeteraccording to the manufacturers instructions. Add 1.0 mL ofwater to the bomb before assembly.10.2.2 Connect a measu
