1、Designation: D 5865 07aStandard Test Method forGross Calorific Value of Coal and Coke1This standard is issued under the fixed designation D 5865; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number i
2、n parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method pertains to the determination of thegross calorific value of coal and coke by either an isoperibol oradiabatic bomb calorime
3、ter.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 its use. It is theresponsibility of the user of this standard to establish
4、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:2D 121 Terminology of Coal and CokeD 346 Practice for Collection and Preparation of CokeSamples
5、 for Laboratory AnalysisD 388 Classification of Coals by RankD 1193 Specification for Reagent WaterD 2013 Practice for Preparing Coal Samples for AnalysisD 3173 Test Method for Moisture in theAnalysis Sample ofCoal and CokeD 3177 Test Methods for Total Sulfur in the AnalysisSample of Coal and CokeD
6、3180 Practice for Calculating Coal and Coke Analysesfrom As-Determined to Different BasesD 4239 Test Methods for Sulfur in the Analysis Sample ofCoal and Coke Using High-Temperature Tube FurnaceCombustion MethodsD 5142 Test Methods for Proximate Analysis of the Analy-sis Sample of Coal and Coke by I
7、nstrumental ProceduresE 144 Practice for Safe Use of Oxygen Combustion BombsE 178 Practice for Dealing With Outlying ObservationsE 882 Guide for Accountability and Quality Control in theChemical Analysis LaboratoryE 2251 Specification for Liquid-in-Glass ASTM Thermom-eters with Low-Hazard Precision
8、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 by the operator or the micro-processor.3.1.2 automa
9、ted 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 one pound - mass lbm ofliquid water at one atmosp
10、here 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, 1 I.T. cal = 4.1868 J. The Btu usedin modern stea
11、m 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 measuring calorific valueconsisting of a bomb, it
12、s contents, a vessel for holding thebomb, temperature measuring devices, ignition leads, water,stirrer, and a jacket maintained at specified temperature con-ditions.3.1.6 gross calorific value (gross heat of combustion atconstant volume), Qv(gross)the heat produced by completecombustion of a substan
13、ce at constant 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 mic
14、roprocssor to record theinitial and final temperatures and make the appropiate heat leak1This test method is under the jurisdiction of ASTM Committee D05 on Coaland Coke and is the direct responsibility of Subcommittee D05.21 on Methods ofAnalysis.Current edition approved Nov. 1, 2007. Published Nov
15、ember 2007. Originallyapproved in 1995. Last previous edition approved in 2007 as D 5865 07.2For 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 S
16、ummary page onthe ASTM website.1*A Summary 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.corrections during the temperature rise. It determines when thecalorimeter is in equilib
17、rium and ignites the sample anddetermines when the calorimeter has reached equilibrium afterignition.3.1.9 net calorific value (net heat 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
18、as vapor.3.2 Definitions of Terms Specific to This Standard:3.2.1 corrected temperature risethe calorimeter tempera-ture change caused 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 arbit
19、rary unit.3.2.2.1 DiscussionThe heat capacity can also be referredto as the energy equivalent or water equivalent of the calorim-eter.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 analys
20、is sample is burned under thesame conditions in the calorimeter. The calorific value of theanalysis sample is computed by multiplying 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
21、 can result in a reduction ofcalorific value. In particular, lignite and sub-bituminous rank coal samplesmay experience greater oxidation 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. Signifi
22、cance and Use5.1 The gross calorific value can be used to compute thetotal calorific content of the quantity of coal or coke repre-sented 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 m
23、eets regulatory requirements for industrial fuels.5.3 The gross calorific value can be used to evaluate theeffectiveness of beneficiation processes.5.4 The gross calorific value can be required to classifycoals according to Classification D 388.6. Apparatus and Facilities6.1 Test AreaAn area free fr
24、om drafts, shielded fromdirect sunlight and other radiation sources. Thermostatic con-trol of room temperature and controlled relative humidity aredesirable.6.2 Combustion BombConstructed of materials that arenot affected by the combustion process or the products formedto introduce measurable heat i
25、nput or alteration of end prod-ucts. The bomb shall be designed so that all liquid combustionproducts can be completely recovered by washing 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
26、 without stressing any partbeyond its specified elastic limit.6.3 BalanceAlaboratory balance capable of weighing theanalysis sample to 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 o
27、uter surfaces highly polished. Itssize shall be such that the bomb is completely immersed inwater during a determination. A stirrer shall be provided foruniform mixing of the water. The immersed portion of thestirrer shall be accessible to the outside through a coupler oflow thermal conductivity. Th
28、e stirrer speed shall remainconstant to minimize any temperature variations due to stirring.Continuous stirring for 10 min shall not raise the calorimetertemperature more than 0.01C when starting with identicaltemperatures in the calorimeter, test area and jacket. Forcalorimeters having a bucket it
29、can be a separate component orintegral component of the bomb. The vessel shall be of suchconstruction that the environment of the calorimeters entireouter boundaries can be maintained at a uniform temperature.6.5 JacketA container with the inner perimeter main-tained at constant temperature 60.1C (i
30、soperibol) or at thesame temperature 60.1C as the calorimeter vessel (adiabatic)during the test. To minimize convection, the sides, top 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
31、thermal conductivity.6.6 Thermometers:6.6.1 Automated CalorimetersPlatinum resistance or lin-ear thermistor thermometers shall be capable of measuring tothe nearest 0.0001C. Thermometer calibration shall be trace-able to a recognized certifying agency.6.6.2 Manual Calorimeters:6.6.2.1 Platinum Resis
32、tance or Linear Thermistor Ther-mometers shall be capable of measuring to the nearest0.0001C. Thermometer calibration shall be traceable to arecognized certifying agency.6.6.2.2 Liquid-in-Glass ThermometersConforming to therequirements for thermometers S56C, S116C, or S117C asprescribed in Specifica
33、tion E 2251.6.6.2.3 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 of parallax.6.7 Sample HolderAn open crucible of platinum, qu
34、artz,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 preliminary firings, theweight does not change by more than 0.0001 g.6.8 Ign
35、ition 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; andcarrying out all necessary corrections and calculations.6.11 Crucible Line
36、rQuartz fiber or alundum for lining thecrucible to promote complete combustion of samples that donot burn completely during the determination of the calorificvalue.37. Reagents7.1 Reagent WaterConforming to conductivity require-ments for Type II of Specification D 1193 for preparation ofreagents and
37、 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.47.3 Benzoic AcidStandard (C6H5COOH)Pellets madefrom benzoic acid available from the National Institut
38、e 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 OxygenManufactured from liquid air, guaranteed tobe greater than 99.5 % p
39、ure, 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, ormethyl purple for indicating the end point when titrating theacid f
40、ormed 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 sodiumcarbonate, dried for 24 h at 105C in water, and dilute to 1 L.One millilitre of
41、 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 E 144. Also consult the calorimeter equipment manu-facturers installation and operating instruct
42、ions 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 carefully after each use.Replace cracked or significantly worn parts. Replace
43、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 theneedle valve and pressure gage used in regulating the oxygenfeed to t
44、he bomb. Valves, gages, 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. Check the pressure gage annually for accuracy or afterany accidental ov
45、er pressures that reach maximum gagepressure.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 after loading.8.1.6 Do not fire the bomb if there is evidence of gasleakage
46、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 pulverized to pass250-m (No. 60) sieve, prepared in accordance with eitherPractice
47、 D 346 for coke or Method D 2013 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
48、 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 measured fuse in accordance with manu-facturers guidelines.10.2.3 Assemble the bomb. Admit oxygen to the bomb to aconsistent pressure of betw
49、een 2 and 3 MPa (20 and 30 atm).The same pressure is used for each heat capacity run. Controloxygen flow to the bomb so as not to blow material from thesample holder. If the pressure exceeds the specified pressure,detach the filling connection and exhaust the bomb. Discard thesample.10.3 Preparation of Calorimeter:10.3.1 Fill the calorimeter vessel with water at a tempera-ture not more than 2C below room temperature and place theassembled bomb in the calorimeter. Check that no oxygenbubbles are leaking from the bomb. If there is evide
