1、Designation: D5016 081D5016 16Standard 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 D5016; the number immediately following the designation indicates
2、 the year 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.1 NOTETable A1.1 was editorially revised in July 2009.1. Sc
3、ope1.1 This test method describes a procedure using a high-temperature tube furnace and infrared detection for the determinationof sulfur in coal and coke combustion residues, including lab ashes and residues from coal and coke combustion.1.2 The values stated in SI units are to be regarded as stand
4、ard. No other units of measurement are included in this standard.1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the appl
5、icability of regulatorylimitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D121 Terminology of Coal and CokeD3174 Test Method for Ash in the Analysis Sample of Coal and Coke from CoalD3682 Test Method for Major and Minor Elements in Combustion Residues from Coal Utilization Processes
6、D3683 Test Method for Trace Elements in Coal and Coke Ash by Atomic AbsorptionD4326 Test Method for Major and Minor Elements in Coal and Coke Ash By X-Ray FluorescenceD4621 Guide for Quality Management in an Organization That Samples or Tests Coal and Coke (Withdrawn 2010)3D5142 Test Methods for Pro
7、ximate Analysis of the Analysis Sample of Coal and Coke by Instrumental Procedures (Withdrawn2010)3D6349 Test Method for Determination of Major and Minor Elements in Coal, Coke, and Solid Residues from Combustion ofCoal and Coke by Inductively Coupled PlasmaAtomic Emission SpectrometryD6357 Test Met
8、hods for Determination of Trace Elements in Coal, Coke, and Combustion Residues from Coal UtilizationProcesses by Inductively Coupled Plasma Atomic Emission Spectrometry, Inductively Coupled Plasma Mass Spectrometry,and Graphite Furnace Atomic Ab3. Terminology3.1 For definitions of terms used in the
9、se test methods, refer to Terminology D121.3.2 Throughout this test method the term ash is used to describe the sample being analyzed. The term ash is to be interpretedas a combustion residue.4. Summary of Test Method4.1 A weighed test portion is mixed with a promoting agent and ignited in a tube fu
10、rnace an operating temperature of1450C1450 C in a stream of oxygen. The combustible sulfur contained in the test portion is oxidized to gaseous oxides of sulfur.1 This test method is under the jurisdiction of ASTM Committee D05 on Coal and Coke and is the direct responsibility of Subcommittee D05.29
11、 on Major Elements inAsh and Trace Elements of Coal.Current edition approved Feb. 1, 2008Sept. 1, 2016. Published February 2008September 2016. Originally approved in 1989. Last previous edition approved 20072008as D5016 07a.D5016 081. DOI: 10.1520/D5016-08E01.10.1520/D5016-16.2 For referencedASTM st
12、andards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.3 The last approved version of this historical standard is referenced on www.astm.or
13、g.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior e
14、ditions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1Moisture and particulates are removed by traps
15、 filled with anhydrous magnesium perchlorate. The gas stream is passed througha cell in which sulfur dioxide is measured by an infrared absorption detector. Sulfur dioxide absorbs IR energy at a precisewavelength within the IR spectrum. Energy is absorbed as the gas passes through the cell body in w
16、hich the IR energy is beingtransmitted; thus, at the detector, less energy is received. All other IR energy is eliminated from reaching the detector by a precisewavelength filter. The absorption of IR energy can be attributed only to sulfur dioxide whose concentration is proportional to thechange in
17、 energy at the detector. One cell is used as both a reference and a measurement chamber. Total sulfur as sulfur dioxideis detected on a continuous basis.4.2 This test method is applicable for use with sulfur analyzers equipped to carry out the operations in 4.1 and must be calibratedusing reference
18、materials (RMs) covering the range of sulfur in the ash samples being analyzed.5. Significance and Use5.1 The percent sulfur content of the ash derived from coal or coke can be calculated to sulfur trioxide content. This informationcan be used in combination with results from the determination of ma
19、jor, minor and or trace elements in the same ash to calculateresults on a sulfur trioxide free-basis or to calculate total recovered analyte.6. Interferences6.1 Known interferences in this test method are some alkaline earth metal ions, including barium and strontium, which formstable sulfate salts
20、that are difficult to decompose. In order to have an accurate analysis of the material all mineral sulfates mustbe decomposed to yield sulfur dioxide, which is then presented to the IR detection system for measurement. To minimizeinterferences a promoting agent shall be used to help decompose these
21、salts. These promoting agents can have one or more of thefollowing properties, (1) oxidizing agent, (2) reducing agent and (3) fluxing agent. Oxidizing and reducing agents help decomposethe metal sulfates through the oxidation or reduction of the sulfate or metal ions, or both. The fluxing agent hel
22、ps decompose themetal sulfates by fusing the salt, which leads to the decomposition of sulfates on further heating. Some promoting agents maycontain sulfur, which needs to be addressed with their use.7. Apparatus7.1 Tube Furnace, electrically heated, capable of heating 150 to 165-mm 165 mm length of
23、 the hot zone area of the combustiontube (see 7.2) to at least 1350C.1350 C. Specific dimensions can vary with design.7.2 Combustion Tube, made of mullite, porcelain, or zircon, approximately 23-mm23 mm inside diameter with a 3-mm3 mmthick wall, at least 450 mm long with means to route the gases pro
24、duced by combustion through the infrared cell.7.3 Sample Combustion Boats, made of iron-free material and of a convenient size suitable for the instrument being used.7.4 Boat Puller, rod of a heat resistant material with a bent or disk end used to insert and remove boats from the combustiontube.8. R
25、eagents8.1 Purity of ReagentsReagent grade chemicals shall be used unless otherwise specified. All reagents shall conform to thespecifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications exist.4,5Other grades may be used, provided it is first a
26、scertained that the reagent is of sufficiently high purity to permit its use withoutaffecting the accuracy of the determination.8.2 Magnesium Perchlorate (Mg(ClO4)2) Warning: Magnesium perchlorate is a strong oxidizing agent. Do not attempt toregenerate the absorbent. Do not permit contact with orga
27、nic materials or reducing agents.8.3 PromotorCOM-CAT Combustion promoterpromoterNOTE 1COM-CAT is a promoting agent that is both a fluxing agent and oxidizing agent.8.4 Oxygen, 99.5 % PureCompressed gas contained in a cylinder equipped with a suitable pressure regulator and needle valveto control gas
28、 flow. Warning: Pure oxygen vigorously accelerates combustion. All regulators, lines, and valves shall be free ofgrease and oil.9. Hazards9.1 The user shall ensure acceptable documented safety procedures are in place for the handling of all reagents and test materialsand for the operation of laborat
29、ory equipment specified for this test method.4 Interested parties are invited to submit information regarding the identification of alternatives to ASTM international Headquarters. Your comments will receive carefulconsideration at a meeting of the responsible technical committee, which you may atte
30、nd.5 Reagent Chemicals, American Chemical Society Specifications. American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed bythe American Chemical Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Phar
31、macopeia and NationalFormulary. U.S. Pharmaceutical Convention, Inc. (USPC), Rockville, MD.D5016 16210. Calibration Materials and Test Samples10.1 Calibration MaterialsEmploy RMs for calibration and control. Reference material coal, coke and ash samples can beused for calibration. AAn RM shall be a
32、Certified Reference Material (CRM) from recognized certifying agencies such as theNational Institute for Science and Technology (NIST) or the South African Bureau of Standards (SABS), an External ReferenceMaterial (ERM) available from suppliers that provide details of traceability to a recognized CR
33、M with a similar matrix andcomposition, or an Internal Reference Material (IRM) that has been validated to use through intercomparison with one or moreCRMs or ERMs traceable to a CRM.10.2 For total sulfur in ash determination to complement major and minor elements in ash analysis, the ash sample is
34、preparedin accordance with Test Methods D3682, D4326, or D6349.10.3 For total sulfur in ash determination to calculate total recovered analyte in conjunction with the determination of traceelements, the ash sample is prepared in accordance with Test Methods D3683 or D6357.10.4 For sulfur correction
35、of ash as determined by Test Methods D3174 or D5142, the sample shall consist of the combined ashfrom duplicate samples of coal or coke as determined in accordance with that test method.NOTE 2Ashing temperature, heating rate, and furnace ventilation have an important influence on sulfur retention; t
36、hus, observing the prescribedashing conditions is important. Sulfur in ash as determined by these methods cannot be strictly related to the sulfur oxides retained in ash produced underthe conditions of combustion in boiler furnaces, or other commercial combustion processes.NOTE 3This test method can
37、 require up to 300 mg of ash per determination of percent sulfur with reference to Test Method D3174, Test MethodD3682, Test Method D4326, Test Method D5142, or Test Method D6349; therefore, it can be necessary to ash additional coal or coke.11. Procedure11.1 Instrument Preparation/VerificationUse o
38、f COM-CAT requires the instrument to meet the parameters listed in Table 1.Verify the instrument meets these specifications before conducting instrument calibration or analysis (see Note 4).11.2 Calibration of the Infrared Detection SystemCalibration of the infrared detector system is accomplished w
39、hen ameasurable amount of sulfur dioxide is presented for detection using the conditions outlined in Table 1. Select Reference Materials(RMs) with known sulfur values in the range of the samples to be analyzed. For the initial calibration and periodic verification ofinstrument linearity, at least th
40、ree such RMs are recommended for each range of sulfur values to be determined. Two of the RMsshould bracket the range of sulfur values to be tested and the third should be near the mid-point of the expected range. Recordsfor all calibrations will be maintained in accordance with Guide D4621.NOTE 4Th
41、e use of a combustion promoter is required for the analysis of ash and combustion residues (6.1). Calibration of the sulfur analyzer maybe done with coal or coke RMs. The use of a combustion promoter is not necessary for coal or coke RMs, since the materials themselves are excellentreducing agents t
42、hat decompose mineral sulfates in the RMs.11.2.1 Calibration ProcedureMake a minimum of six determinations to condition the equipment prior to beginning thecalibration procedure. The as-determined sulfur value of the RM shall be used for calibration of the system. This value must havebeen previously
43、 calculated from the certified dry-basis sulfur value and residual moisture determined using either Test MethodsD3174, D5142, or the procedure recommended by the vendor of the RM. Alternatively, a quantity of the RM can be dried usingthe previously mentioned procedures for determining moisture, in w
44、hich case the dry basis sulfur value can be used. That quantityof RM dried for calibration of the system must be stored in a desiccator and any portion remaining at the end of the normal workingperiod must be discarded. The number of RMs used for calibration shall not be less than the degree of the
45、calibration curve plustwo. Table 2 summarizes these requirements.11.2.2 Verify proper calibration by analyzing RMs that bracket the range of sulfur values to be tested. These results must alsobe within the RMs certified uncertainty limits.11.2.3 Periodic Calibration VerificationOn a periodic basis,
46、verify the stability of the instrument and its calibration byanalyzing a control sample. This control sample may be an RM used for calibration or any other reference material that is certifiedfor its sulfur content (see Note 5). The results of this determination must be within the certified uncertai
47、nty limits of that referencematerial. If the criteria for a successful verification of calibration in accordance with Guide D4621 are not met, the calibrationprocedure of 11.2.1 shall be repeated.NOTE 5Some RMs, especially ashes with very low sulfur contents, may not be acceptable for use as periodi
48、c calibration verifications. This is dueTABLE 1 Instrument ParametersFurnace Temperature 1450CFurnace Temperature 1450 CComparator Level 0.3Lance Delay 10Minimum Run Time 120 secondsMinimum Run Time 120 sMaximum Run Time 300 secondsMaximum Run Time 300 sD5016 163to the difficulty of decomposing the
49、mineral sulfates in the ash and the low sulfur contents. The infrared detection system only functions to measure thesulfur 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 0.1 mg 0.1 mg (sample weightmass may have to be adjusted in order forthe sulfur concentration mass fraction to land within the calibration range). Carefully blend the weighed test portion withapproximately 1.0 g COM-CATCOM-CAT Spread the mixture evenly in the combusti
