1、Designation: D5274 00 (Reapproved 2009)Standard Guide forAnalysis of 1,3Butadiene Product1This standard is issued under the fixed designation D5274; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A numbe
2、r in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This guide covers the analysis of 1,3butadiene prod-ucts produced in North America. It includes possible compo-nents and test methods, both
3、ASTM and other, either actuallyused or believed to be in use, to test for these components. Thisguide is not intended to be used or construed as a set ofspecifications for butadiene products.1.2 The values stated in SI units are to be regarded asstandard. The values given in parentheses are for info
4、rmationonly.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.
5、Referenced Documents2.1 ASTM Standards:2D1025 Test Method for Nonvolatile Residue ofPolymerization-Grade ButadieneD1157 Test Method for Total Inhibitor Content (TBC) ofLight HydrocarbonsD1550 Standard ASTM Butadiene Measurement TablesD2384 Test Methods for Traces of Volatile Chlorides inButane-Buten
6、e MixturesD2426 Test Method for Butadiene Dimer and Styrene inButadiene Concentrates by Gas ChromatographyD2593 Test Method for Butadiene Purity and HydrocarbonImpurities by Gas ChromatographyD3246 Test Method for Sulfur in Petroleum Gas by Oxida-tive MicrocoulometryD3700 Practice for Obtaining LPG
7、Samples Using a Float-ing Piston CylinderD4178 Practice for Calibrating Moisture AnalyzersD4423 Test Method for Determination of Carbonyls In C4HydrocarbonsD4468 Test Method for Total Sulfur in Gaseous Fuels byHydrogenolysis and Rateometric ColorimetryD4629 Test Method for Trace Nitrogen in Liquid P
8、etroleumHydrocarbons by Syringe/Inlet Oxidative Combustion andChemiluminescence DetectionD4864 Test Method for Determination of Traces of Metha-nol in Propylene Concentrates by Gas ChromatographyD5799 Test Method for Determination of Peroxides inButadiene3. Terminology3.1 Definitions:3.1.1 1,3-butad
9、ienehydrocarbon product containing morethan 99 % 1,3-butadiene.3.2 Symbols:3.2.1 BHTbutyl hydroxy toluene.3.2.2 GCgas chromatography.3.2.3 pTBCparatertiary butyl catechol.3.2.4 4VCH-14-vinyl cyclo hexene (1,3-butadienedimer).4. Significance and Use4.1 This guide is intended to provide information on
10、 thepossible composition of 1,3-butadiene products and possibleways to test them. Since there are currently not enough ASTMstandards for determining all components of interest, this guideprovides information on other potentially available test meth-ods.4.2 Although this guide is not to be used for s
11、pecifications,it can provide a starting point for parties to develop mutuallyagreed-upon specifications that meet their respective require-ments. It can also be used as a starting point in finding suitabletest methods for 1,3-butadiene components.5. Sampling5.1 General:5.1.1 1,3-butadiene is a very
12、reactive hydrocarbon. It reactswith oxygen to form peroxides and to polymerize. It alsodimerizes at a rate that is temperature dependent. Below 10C(50F), the dimerization rate is less than 1 mg/kg by mass/h;but, at 20C (77F), it increases to 3 to 4 mg/kg mass/h; and at40C (104F), to 14 to 20 mg/kg m
13、ass/h. 1,3-butadiene is also1This guide is under the jurisdiction of ASTM Committee D02 on PetroleumProducts and Lubricants and is the direct responsibility of Subcommittee D02.D0.04on C4 Hydrocarbons.Current edition approved July 1, 2009. Published November 2009. Originallyapproved in 1992. Last pr
14、evious edition approved in 2005 as D527400(2005).DOI: 10.1520/D5274-00R09.2For 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 page onthe
15、ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.classified as toxic and as a potential health hazard, having beenfound carcinogenic to laboratory animals. Therefore, samplingof 1,3-butadiene must adhere to the following
16、three principles:5.1.1.1 Minimize personnel exposure. See the appropriateOSHA Material Safety Data Sheet for guidance,5.1.1.2 Eliminate or keep to an absolute minimum theinclusion of oxygen during and after sampling, and5.1.1.3 Sample the product at as low a temperature aspossible, maintain the samp
17、le at a low temperature, andanalyze it as soon as possible. Do not allow it to sit outdoors inthe sun after sampling.5.1.2 In addition to 5.1.1.1-5.1.1.3, 1,3-butadiene to beanalyzed for trace components should be sampled by atechnique that minimizes or eliminates loss of light compo-nents and conce
18、ntration of heavy ones. The subsections belowlist some different sampling methods and principles. However,it is not the intent of this guide to list procedures that areapplicable to all sampling situations. It is strongly recom-mended that samples be obtained under the supervision of aperson with wi
19、de knowledge and experience in sampling1,3-butadiene.5.1.3 Also, even though this guide does not address thelocation of a sampling point in a line or vessel, the importanceof the proper sampling location cannot be overemphasized.5.2 Floating Piston CylinderPractice D3700 meets thecriterion of minimi
20、zing or eliminating loss of light componentsand concentration of heavy ones. However, some labs havesafety codes preventing use of rupture-disc piston containers.Alternative procedures must be used in these labs.5.3 Conventional “Outaging” MethodThe widely used“outaging” technique (that is, the prac
21、tice of removing aportion of the fluid contents from a conventional samplingcylinder after filling in order to provide expansion room)causes a partial loss of light components into the vapor space.Subsequent handling to recapture these light ends in the liquidphase of the sample, such as repressuriz
22、ation of the cylindercontents with an inert gas, is usually successful, since 1,3-butadiene seldom contains noncondensables. However, if per-manent gases are present and are to be determined, an alternateprocedure may be required.5.4 Vaporization MethodsVaporization of the sample, ei-ther at the sou
23、rce or in the lab prior to analysis, may cause lossof heavier components, if present, and concentration of lighterones. Also, since 1,3-butadiene is so reactive, the heat requiredto vaporize may cause undesirable changes in the compositionof the sample. For these reasons, vaporization is not recom-m
24、ended for 1,3-butadiene.5.5 Reactive ComponentsDetermination of reactive com-ponents, such as certain sulfur compounds, is generally be-lieved to require special sample containers, such as TFE-fluorocarbon-lined cylinders.6. Composition and Test Methods6.1 Table 1 indicates possible composition rang
25、es andASTM methods for 1,3-butadiene product. Table 2 lists othertest methods known or believed to be in use.7. Keywords7.1 1,3-butadiene;1,3-butadiene product;1,3-butadiene testmethodsTABLE 1 1,3-Butadiene Test Methods (ASTM)Property Units Test MethodConcentrationRangeAmines mg/kg See Table 2 1 to
26、25Ammonia mg/kg See Table 2 1 to 25Benzene mg/kg See Table 2 0.1to101,2-butadiene mg/kg D2593 1 to 1001,3-butadiene dimer(4VCH-1)mg/kg D2426 100 to 200C5hydrocarbons mg/kg D2593 1 to 1000C6+hydrocarbons mg/kg See Table 2 1 to 1000Carbonyls mg/kg D4423 1 to 100Chlorides mg/kg See Table 2 1 to 25Ethyl
27、ene glycol mg/kg See Table 2 1 to 100Inhibitor (p-TBC) mg/kg D1157See Table 21 to 500Methanol and otheralcoholsmg/kg D4864See Table 21 to 25Moisture mg/kg D4178See Table 21 to saturatedNonvolatile residue mass % D1025 0.001 to 0.2Oxygen in vapor space mass % See Table 2 0.001 to 0.3Peroxides mg/kg D
28、5799 1 to 10Propadiene mg/kg D2593 1 to 25Propane mg/kg D2593 1 to 25Propylene mg/kg D2593 1 to 25Purity of 1,3-butadiene mass % D2593 99.0 minRelative density 15.6/15.6 D1550 0.625 to 0.630Toluene mg/kg See Table 2 1 to 500Total acetylenes mg/kg D2593 1 to 100Total nitrogen mg/kg See Table 2 1 to 2
29、5Total sulfur mg/kg See Table 2 1 to 25D5274 00 (2009)2ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent
30、rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either
31、for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hear
32、ing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard
33、may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/COPYRIGHT/).TABLE 2 1,3-B
34、utadiene Test Methods (Non-ASTM Methods)AProperty Possible Test MethodAmines Adaption of Test Method D4629Ammonia Acid absorption with Nessler finishAcid absorption with specific ion finishBenzene Capillary gas chromatographyChlorides Organic chlorides by GC, with hall detector;also, Test Methods D2
35、384Ethylene glycol Capillary gas chromatographyInhibitor (BHT) Capillary gas chromatography or titrationmethodInhibitor (pTBC) Test Method D1157; also, gaschromatography and titration methods usingceric ammonium sulfateMethanol and otheralcoholsAdaption of Test Method D4864Moisture Panametrics moist
36、ure instrument; adaption ofKarl Fisher titrationOxygen Adaption of Panometric or Teledyne oxygenanalyzersToluene Capillary gas chromatographyTotal sulfur Adaption of Test Methods D3246 or D4468Total nitrogen Adaption of Test Method D4629; also, micro-coulometryAThe above are possible butadiene test
37、methods or techniques which arebelieved to be in use in the industry for testing. Inclusion of any test method in thislist is not to be construed as a recommendation by ASTM for its use. Some of thetest methods in this list are ASTM test methods that are specified for otherproducts but are being used by some labs for butadiene analysis. However, use ofASTM test methods beyond their scope is not recommended by ASTM. Precisionand bias may be adversely affected.D5274 00 (2009)3
