1、Designation: D 5016 07aStandard 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 (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method describes a procedure using a high-
3、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. No other units of measurement are included in thissta
4、ndard.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-bility of regulatory limitations prior to use.2. Refere
5、nced 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 Test Method for Trace Elements in Coal and CokeAsh
6、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 Analy-sis Sample of Coal and Coke by Instrumental Pr
7、oceduresD 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 Elementsin Coal, Coke, and Combustion Residues from CoalU
8、tilization 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 121.4. Summary of Test Method4.1 A weighed test porti
9、on is mixed with a promoting agentand ignited in a tube furnace an operating temperature of1450C in 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 perchlor
10、ate. The gas stream is passedthrough a cell in which sulfur dioxide is measured by aninfrared absorption 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; thu
11、s, at the detector, less energyis received.All other IR energy is eliminated from reaching thedetector by a precise wavelength filter. The absorption of IRenergy 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
12、both a reference 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
13、the ash samples 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 the1This test method is under the jurisdiction of ASTM Committee D05 on
14、Coaland Coke and is the direct responsibility of Subcommittee D05.29 on MajorElements in Ash and Trace Elements of Coal.Current edition approved Oct. 1, 2007. Published October 2007. Originallyapproved in 1989. Last previous edition approved 2007 as D 5016 07.2For referenced ASTM standards, visit th
15、e 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 page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
16、United States.determination of major, minor and or trace elements in thesame ash to calculate results 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,w
17、hich form stable sulfate salts that are difficult to decompose.To minimize this interference a promoting agent shall be usedto help decompose these salts. These promoting agents canhave one or more of the following properties, (1) oxidizingagent, (2) reducing agent and (3) fluxing agent. Oxidizing a
18、ndreducing agents help decompose the metal sulfates through theoxidation or reduction of the sulfate or metal ions, or both. Thefluxing agent helps decompose the metal sulfates by fusing thesalt, which leads to the decomposition of sulfates on furtherheating. Some promoting agents may contain sulfur
19、, whichneeds to be addressed 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 dimensions can varywith design.7.2 Combustion Tube, made of mullite, porcelain, or zi
20、rcon,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 materialand of a convenient size suitable for the instrument being used.7.4 Boat Puller, r
21、od 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 reagents shall conform tothe specifications of the Committee on Analytical Reagents o
22、fthe 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 accuracy of the determination.8.2 Magnesium Perchlorate (Mg(ClO4)2)Warning: Mag-nesium
23、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 agent that is both a fluxing agentand oxidizing agent.8.4 Oxygen, 99.5 % PureCompre
24、ssed 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 grease and oil.9. Hazards9.1 The user shall ensure acceptable documented safetypro
25、cedures 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 MaterialsEmploy reference materials(RMs) for calibration and control. Reference material co
26、al,coke and ash samples can be used for calibration. A referencematerial (RM) shall be a Certified Reference Material (CRM)from recognized certifying agencies such as the NationalInstitute for Science and Technology (NIST) or the SouthAfrican Bureau of Standards (SABS), an External ReferenceMaterial
27、 (ERM) available from suppliers that provide details oftraceability to a recognized CRM with a similar matrix andcomposition, or an Internal Reference Material (IRM) that hasbeen validated to use through intercomparison with one ormore CRMs or ERMs traceable to a CRM.10.2 For total sulfur in ash det
28、ermination 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 determination oftrace elements, the ash sample is
29、 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 thecombined ash from duplicate samples of coal or coke asdetermined in accordance with that test method.NOTE 2Ashing temperature, hea
30、ting rate, and furnace ventilationhave an important influence on sulfur retention; thus, observing theprescribed ashing conditions is important. Sulfur in ash as determined bythese methods cannot be strictly related to the sulfur oxides retained in ashproduced under the conditions of combustion in b
31、oiler furnaces, or othercommercial combustion processes.NOTE 3This test method can require up to 300 mg of ash perdetermination of percent 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 a
32、sh additional coal orcoke.3Interested parties are invited to submit information regarding the identificationof alternatives to ASTM international Headquarters. Your comments will receivecareful consideration at a meeting of the responsible technical committee, whichyou may attend.4Reagent Chemicals,
33、 American Chemical Society Specifications. AmericanChemical Society, Washington, DC. For suggestions on the testing 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 Form
34、ulary. U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.5The sole source of supply of COMCAT known to the 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 H
35、eadquarters. Your comments will receive careful consideration at a meetingof the responsible technical committee,1which you may attend.D 5016 07a211. Procedure11.1 Instrument Preparation/VerificationUse of COM-CAT5requires the instrument to meet the parameters listed inTable 1. Verify the instrument
36、 meets these specifications beforeconducting instrument calibration or analysis.11.2 Calibration of the Infrared Detection SystemSelectReference Materials (RMs) with known sulfur values in therange of the samples to be analyzed. For the initial calibrationand periodic verification of instrument line
37、arity, at least threesuch RMs are recommended for each range of sulfur values 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
38、 D 4621.11.2.1 Calibration 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-b
39、asis sulfur value and residual 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 va
40、lue can be used. That quantity 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
41、summarizes these requirements.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 instrumen
42、t and its calibrationby analyzing a control sample. This control sample may be anRM used for calibration or any other reference material that iscertified for its sulfur content. The results of this determinationmust be within the certified uncertainty limits of that referencematerial. If the criteri
43、a for a successful verification of calibra-tion in accordance with Guide D 4621 are not met, thecalibration procedure of 11.2.1 shall be repeated.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 0.1mg (sample weight
44、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 thefurnace until the releas
45、e 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 4For instrumentation with a fixed furnace temperature (usually1350C), sulf
46、ur 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 percent sulfur trioxide (SO3) in the ash asfollows:SO3in a
47、sh,%5 2.5 3 ST(1)where:ST = sulfur % determined on the test sample.12.2 Calculate ash on sulfur trioxide free-basis as follows:B 5 Ax100 2 S!/100 (2)A = percent ash as determined by Test Method D 3174 orTest Method D 5142B = percent ash on a sulfur trioxide-free basisS = percent sulfur trioxide in a
48、sh from 12.113. Precision and Bias13.1 PrecisionThe precision of this test method for thedetermination of sulfur in the analysis sample of coal and cokecombustion residues is shown in Table 3. The precisioncharacterized by the repeatability (Sr, r) and reproducibility(SR, R) is described in Table A1
49、.1 in Annex A1.13.1.1 Repeatability Limit (r)the value below which theabsolute difference between two test results of separate andconsecutive test determinations, carried out on the samesample in the same laboratory by the same operator using thesame apparatus on samples taken at random from a singlequantity of homogeneous material, may be expected to occurwith a probability of approximately 95%.13.1.2 Reproducibility Limit (R) the value below whichthe absolute difference between two test results carried out indifferent laboratories using samples taken at ra
