1、Designation: D 5016 081Standard Test Method forTotal Sulfur in Coal and Coke Combustion Residues Using aHigh-Temperature Tube Furnace Combustion Method withInfrared Absorption1This standard is issued under the fixed designation D 5016; the number immediately following the designation indicates the y
2、ear oforiginal adoption or, in the case 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 revised in July 2009.1. Scope1.1
3、This test method describes a procedure using a high-temperature tube furnace and infrared detection for the deter-mination of sulfur in coal and coke combustion residues,including lab ashes and residues from coal and coke combus-tion.1.2 The values stated in SI units are to be regarded asstandard. N
4、o 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 appro-priate safety and health practices and determine the applica-bil
5、ity of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 121 Terminology of Coal and CokeD 3174 Test Method forAsh in theAnalysis Sample of Coaland Coke from CoalD 3682 Test Method for Major and Minor Elements inCombustion Residues from Coal Utilization ProcessesD 3683
6、 Test Method for Trace Elements in Coal and CokeAsh by Atomic AbsorptionD 4326 Test Method for Major and Minor Elements in Coaland Coke Ash By X-Ray FluorescenceD 4621 Guide for Quality Management in an OrganizationThat Samples or Tests Coal and CokeD 5142 Test Methods for Proximate Analysis of the
7、Analy-sis Sample of Coal and Coke by Instrumental ProceduresD 6349 Test Method for Determination of Major and MinorElements in Coal, Coke, and Solid Residues from Com-bustion of Coal and Coke by Inductively CoupledPlasmaAtomic Emission SpectrometryD 6357 Test Methods for Determination of Trace Eleme
8、ntsin Coal, Coke, and Combustion Residues from CoalUtilization Processes by Inductively Coupled PlasmaAtomic Emission Spectrometry, Inductively CoupledPlasma Mass Spectrometry, and Graphite Furnace AtomicAb3. Terminology3.1 For definitions of terms used in these test methods, referto Terminology D 1
9、21.3.2 Throughout this test method the term ash is used todescribe the sample being analyzed. The term ash is to beinterpreted as a combustion residue.4. Summary of Test Method4.1 A weighed test portion is mixed with a promoting agentand ignited in a tube furnace an operating temperature of1450C in
10、a stream of oxygen. The combustible sulfur con-tained in the test portion is oxidized to gaseous oxides of sulfur.Moisture and particulates are removed by traps filled withanhydrous magnesium perchlorate. The gas stream is passedthrough a cell in which sulfur dioxide is measured by aninfrared absorp
11、tion detector. Sulfur dioxide absorbs IR energyat a precise wavelength within the IR spectrum. Energy isabsorbed as the gas passes through the cell body in which theIR energy is being transmitted; thus, at the detector, less energyis received.All other IR energy is eliminated from reaching thedetect
12、or by a precise wavelength filter. The absorption of IR1This 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 Feb. 1, 2008. Published Februar
13、y 2008. Originallyapproved in 1989. Last previous edition approved 2007 as D 5016 07a.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 Summary
14、 page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.energy can be attributed only to sulfur dioxide whose concen-tration is proportional to the change in energy at the detector.One cell is used as both a referenc
15、e and a measurementchamber. Total sulfur as sulfur dioxide is detected on acontinuous basis.4.2 This test method is applicable for use with sulfuranalyzers equipped to carry out the operations in 4.1 and mustbe calibrated using reference materials (RMs) covering therange of sulfur in the ash samples
16、 being analyzed.5. Significance and Use5.1 The percent sulfur content of the ash derived from coalor coke can be calculated to sulfur trioxide content. Thisinformation can be used in combination with results from thedetermination of major, minor and or trace elements in thesame ash to calculate resu
17、lts on a sulfur trioxide free-basis orto calculate total recovered analyte.6. Interferences6.1 Known interferences in this test method are somealkaline earth metal ions, including barium and strontium,which form stable sulfate salts that are difficult to decompose.In order to have an accurate analys
18、is of the material all mineralsulfates must be decomposed to yield sulfur dioxide, which isthen presented to the IR detection system for measurement. Tominimize interferences a promoting agent shall be used to helpdecompose these salts. These promoting agents can have oneor more of the following pro
19、perties, (1) oxidizing agent, (2)reducing agent and (3) fluxing agent. Oxidizing and reducingagents help decompose the metal sulfates through the oxidationor reduction of the sulfate or metal ions, or both. The fluxingagent helps decompose the metal sulfates by fusing the salt,which leads to the dec
20、omposition of sulfates on further heating.Some promoting agents may contain sulfur, which needs to beaddressed with their use.7. Apparatus7.1 Tube Furnace, electrically heated, capable of heating150 to 165-mm length of the hot zone area of the combustiontube (see 7.2) to at least 1350C. Specific dim
21、ensions can varywith design.7.2 Combustion Tube, made of mullite, porcelain, or zircon,approximately 23-mm inside diameter with a 3-mm thick wall,at least 450 mm long with means to route the gases producedby combustion through the infrared cell.7.3 Sample Combustion Boats, made of iron-free material
22、and of a convenient size suitable for the instrument being used.7.4 Boat Puller, rod of a heat resistant material with a bentor disk end used to insert and remove boats from the combus-tion tube.8. Reagents8.1 Purity of ReagentsReagent grade chemicals shall beused unless otherwise specified. All rea
23、gents shall conform tothe specifications of the Committee on Analytical Reagents ofthe American Chemical Society, where such specificationsexist.3,4Other grades may be used, provided it is first ascer-tained that the reagent is of sufficiently high purity to permit itsuse without affecting the accur
24、acy of the determination.8.2 Magnesium Perchlorate (Mg(ClO4)2)Warning: Mag-nesium perchlorate is a strong oxidizing agent. Do not attemptto regenerate the absorbent. Do not permit contact with organicmaterials or reducing agents.8.3 PromotorCOM-CAT Combustion promoter5.NOTE 1COM-CAT5is a promoting a
25、gent that is both a fluxing agentand oxidizing agent.8.4 Oxygen, 99.5 % PureCompressed gas contained in acylinder equipped with a suitable pressure regulator and needlevalve to control gas flow. Warning: Pure oxygen vigorouslyaccelerates combustion. All regulators, lines, and valves shallbe free of
26、grease and oil.9. Hazards9.1 The user shall ensure acceptable documented safetyprocedures are in place for the handling of all reagents and testmaterials and for the operation of laboratory equipment speci-fied for this test method.10. Calibration Materials and Test Samples10.1 Calibration Materials
27、Employ RMs for calibrationand control. Reference material coal, coke and ash samples canbe used for calibration. A RM shall be a Certified ReferenceMaterial (CRM) from recognized certifying agencies such asthe National Institute for Science and Technology (NIST) orthe South African Bureau of Standar
28、ds (SABS), an ExternalReference Material (ERM) available from suppliers that pro-vide details of traceability to a recognized CRM with a similarmatrix and composition, or an Internal Reference Material(IRM) that has been validated to use through intercomparisonwith one or more CRMs or ERMs traceable
29、 to a CRM.10.2 For total sulfur in ash determination to complementmajor and minor elements in ash analysis, the ash sample isprepared in accordance with Test Methods D 3682, D 4326,orD 6349.10.3 For total sulfur in ash determination to calculate totalrecovered analyte in conjunction with the determi
30、nation oftrace elements, the ash sample is prepared in accordance withTest Methods D 3683 or D 6357.10.4 For sulfur correction of ash as determined by TestMethods D 3174 or D 5142, the sample shall consist of the3Interested parties are invited to submit information regarding the identificationof alt
31、ernatives to ASTM international Headquarters. Your comments will receivecareful consideration at a meeting of the responsible technical committee, whichyou may attend.4Reagent Chemicals, American Chemical Society Specifications. AmericanChemical Society, Washington, DC. For suggestions on the testin
32、g of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary. U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.5The sole source of supply of COMCAT known to the
33、 committee at this timeis LECO Corporation, 3000 Lakeview Ave. St Joseph, MI 49085 USA. If you areaware of alternative suppliers, please provide this information to ASTM Interna-tional Headquarters. Your comments will receive careful consideration at a meetingof the responsible technical committee,1
34、which you may attend.D 5016 0812combined ash from duplicate samples of coal or coke asdetermined in accordance with that test method.NOTE 2Ashing temperature, heating rate, and furnace ventilationhave an important influence on sulfur retention; thus, observing theprescribed ashing conditions is impo
35、rtant. Sulfur in ash as determined bythese methods cannot be strictly related to the sulfur oxides retained in ashproduced under the conditions of combustion in boiler furnaces, or othercommercial combustion processes.NOTE 3This test method can require up to 300 mg of ash perdetermination of percent
36、 sulfur with reference to Test Method D 3174,Test Method D 3682, Test Method D 4326, Test Method D 5142, or TestMethod D 6349; therefore, it can be necessary to ash additional coal orcoke.11. Procedure11.1 Instrument Preparation/VerificationUse of COM-CAT5requires the instrument to meet the paramete
37、rs listed inTable 1. Verify the instrument meets these specifications beforeconducting instrument calibration or analysis (see Note 4).11.2 Calibration of the Infrared Detection SystemCalibration of the infrared detector system is accomplishedwhen a measurable amount of sulfur dioxide is presented f
38、ordetection using the conditions outlined in Table 1. SelectReference Materials (RMs) with known sulfur values in therange of the samples to be analyzed. For the initial calibrationand periodic verification of instrument linearity, at least threesuch RMs are recommended for each range of sulfur valu
39、es tobe determined. Two of the RMs should bracket the range ofsulfur values to be tested and the third should be near themid-point of the expected range. Records for all calibrationswill be maintained in accordance with Guide D 4621.NOTE 4The use of a combustion promoter is required for the analysis
40、of ash and combustion residues (6.1). Calibration of the sulfur analyzermay be done with coal or coke RMs. The use of a combustion promoteris not necessary for coal or coke RMs, since the materials themselves areexcellent reducing agents that decompose mineral sulfates in the RMs.11.2.1 Calibration
41、ProcedureMake a minimum of sixdeterminations to condition the equipment prior to beginningthe calibration procedure. The as-determined sulfur value ofthe RM shall be used for calibration of the system. This valuemust have been previously calculated from the certified dry-basis sulfur value and resid
42、ual moisture determined usingeither Test Methods D 3173, D 5142, or the procedure recom-mended by the vendor of the RM. Alternatively, a quantity ofthe RM can be dried using the previously mentioned proce-dures for determining moisture, in which case the dry basissulfur value can be used. That quant
43、ity of RM dried forcalibration of the system must be stored in a desiccator and anyportion remaining at the end of the normal working periodmust be discarded. The number of RMs used for calibrationshall not be less than the degree of the calibration curve plustwo. Table 2 summarizes these requiremen
44、ts.11.2.2 Verify proper calibration by analyzing RMs thatbracket the range of sulfur values to be tested. These resultsmust also be within the RMs certified uncertainty limits.11.2.3 Periodic Calibration VerificationOn a periodicbasis, verify the stability of the instrument and its calibrationby ana
45、lyzing a control sample. This control sample may be anRM used for calibration or any other reference material that iscertified for its sulfur content (see Note 5). The results of thisdetermination must be within the certified uncertainty limits ofthat reference material. If the criteria for a succes
46、sful verifica-tion of calibration in accordance with Guide D 4621 are notmet, the calibration procedure of 11.2.1 shall be repeated.NOTE 5Some RMs, especially ashes with very low sulfur contents,may not be acceptable for use as periodic calibration verifications. This isdue to the difficulty of deco
47、mposing the mineral sulfates in the ash and thelow sulfur contents. The infrared detection system only functions tomeasure the sulfur dioxide presented for measurement.11.3 Analysis Procedure:11.3.1 Stabilize and calibrate the analyzer (see 11.2).11.3.2 Weigh 250 mg of the test sample to the nearest
48、 0.1mg (sample weight may have to be adjusted in order for thesulfur concentration to land within the calibration range).Carefully blend the weighed test portion with approximately1.0 g COM-CAT5. Spread the mixture evenly in the combus-tion boat. Position the combustion boat in the hot zone of thefu
49、rnace until the release of sulfur dioxide is completed asindicated by the instruments return to baseline.11.3.3 When the analysis is complete, the instrument shouldindicate the percent sulfur. Refer to the manufacturers recom-mended procedure.NOTE 6For instrumentation with a fixed furnace temperature (usually1350C), sulfur dioxide may not be completely released from the testsample. Annex A2 describes alternate procedures using extended analysistimes and/or alternative promoting agents that can be employed underthese conditions.12. Calculations12.1 Calculate
