1、Designation: D 5274 00 (Reapproved 2005)An American National StandardStandard Guide forAnalysis of 1,3Butadiene Product1This standard is issued under the fixed designation D 5274; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the
2、 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 guide covers the analysis of 1,3butadiene prod-ucts produced in North America. It includes possible com
3、po-nents and test methods, both 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 as thestandard. The valu
4、es given in parentheses are for informationonly.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 reg
5、ulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1025 Test Method for Nonvolatile Residue of Polymer-ization Grade ButadieneD 1157 Test Method for Total Inhibitor Content (TBC) ofLight HydrocarbonsD 1550 ASTM Butadiene Measurement TablesD 2384 Test Methods for Traces of
6、Volatile Chlorides inButane-Butene MixturesD 2426 Test Method for Butadiene Dimer and Styrene inButadiene Concentrates by Gas ChromatographyD 2593 Test Method for Butadiene Purity and HydrocarbonImpurities by Gas ChromatographyD 3246 Test Method for Sulfur in Petroleum Gas by Oxi-dative Microcoulome
7、tryD 3700 Practice for Obtaining LPG Samples Using a Float-ing Piston CylinderD 4178 Practice for Calibrating Moisture AnalyzersD 4423 Test Method for Determination of Carbonyls in C4HydrocarbonsD 4468 Test Method for Total Sulfur in Gaseous Fuels byHydrogenolysis and Rateometric ColorimetryD 4629 T
8、est Method for Trace Nitrogen in Liquid Petro-leum Hydrocarbons by Syringe/Inlet Oxidative Combus-tion and Chemiluminescence DetectionD 4864 Test Method for Determination of Traces of Metha-nol in Propylene Concentrates by Gas ChromatographyD 5799 Test Method for Determination of Peroxides inButadie
9、ne3. Terminology3.1 Definitions:3.1.1 1,3-butadienehydrocarbon 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 T
10、his guide is intended to provide information on 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.
11、4.2 Although this guide is not to be used for specifications,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. Sam
12、pling5.1 General:5.1.1 1,3-butadiene is a very 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/k
13、g mass/h; and at40C (104F), to 14 to 20 mg/kg mass/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 C4Hydrocarbons.Current edition approved Nov. 1, 2005. Published Nove
14、mber 2005. Originallyapproved in 1992. Last previous edition approved in 2000 as D 5274 00.2For 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 Su
15、mmary page onthe 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
16、to the following 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,
17、maintain the sample 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 comp
18、o-nents and concentration 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 o
19、f aperson with wide 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 D 3700 meets thec
20、riterion of minimizing 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
21、(that is, the practice 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, s
22、uch as repressurization 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,
23、ei-ther at the source 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, vaporizat
24、ion is not recom-mended 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 possibl
25、e composition ranges 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
26、 See Table 2 1 to 25Ammonia mg/kg See Table 2 1 to 25Benzene mg/kg See Table 2 0.1to101,2-butadiene mg/kg D 2593 1 to 1001,3-butadiene dimer(4VCH-1)mg/kg D 2426 100 to 200C5hydrocarbons mg/kg D 2593 1 to 1000C6+hydrocarbons mg/kg See Table 2 1 to 1000Carbonyls mg/kg D 4423 1 to 100Chlorides mg/kg Se
27、e Table 2 1 to 25Ethylene glycol mg/kg See Table 2 1 to 100Inhibitor (p-TBC) mg/kg D 1157See Table 21 to 500Methanol and otheralcoholsmg/kg D 4864See Table 21 to 25Moisture mg/kg D 4178See Table 21 to saturatedNonvolatile residue mass % D 1025 0.001 to 0.2Oxygen in vapor space mass % See Table 2 0.0
28、01 to 0.3Peroxides mg/kg D 5799 1 to 10Propadiene mg/kg D 2593 1 to 25Propane mg/kg D 2593 1 to 25Propylene mg/kg D 2593 1 to 25Purity of 1,3-butadiene mass % D 2593 99.0 minRelative density 15.6/15.6 D 1550 0.625 to 0.630Toluene mg/kg See Table 2 1 to 500Total acetylenes mg/kg D 2593 1 to 100Total
29、nitrogen mg/kg See Table 2 1 to 25Total sulfur mg/kg See Table 2 1 to 25TABLE 2 1,3-Butadiene Test Methods (Non-ASTM Methods)AProperty Possible Test MethodAmines Adaption of Test Method D 4629Ammonia Acid absorption with Nessler finishAcid absorption with specific ion finishBenzene Capillary gas chr
30、omatographyChlorides Organic chlorides by GC, with hall detector;also, Test Methods D 2384Ethylene glycol Capillary gas chromatographyInhibitor (BHT) Capillary gas chromatography or titrationmethodInhibitor (pTBC) Test Method D 1157; also, gaschromatography and titration methods usingceric ammonium
31、sulfateMethanol and otheralcoholsAdaption of Test Method D 4864Moisture Panametrics moisture instrument; adaption ofKarl Fisher titrationOxygen Adaption of Panometric or Teledyne oxygenanalyzersToluene Capillary gas chromatographyTotal sulfur Adaption of Test Methods D 3246 or D 4468Total nitrogen A
32、daption of Test Method D 4629; also, micro-coulometryAThe above are possible butadiene test 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 metho
33、ds 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.D 5274 00 (2005)2ASTM International takes no
34、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 rights, and the riskof infringement of such rights, are entirely their own responsi
35、bility.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 for revision of this standard or for additional standardsand should be addressed to
36、 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 hearing you shouldmake your views known to the ASTM Committee on Standards, at the addr
37、ess 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 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).D 5274 00 (2005)3
