1、Designation: D4424 09 (Reapproved 2014)Standard Test Method forButylene Analysis by Gas Chromatography1This standard is issued under the fixed designation D4424; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revi
2、sion. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the gas chromatographic analy-sis of commercial butylenes, butylene concentrates, andbutane-butylene mi
3、xtures.1.2 This test method does not cover high-purity butene-1 orhigh-purity isobutene streams, or both. However, it is possiblethat one or more columns listed in Appendix X3 may becapable of the separation necessary for high-purity analyses.1.3 This test method is designed to cover the componentsl
4、isted below at about 0.05 % or greater. It is not intended fortrace hydrocarbon analysis. Components to be determined are:propane, propylene, isobutane, n-butane, butene-1, isobutene,trans-butene-2, cis-butene-2, 1,3-butadiene, isopentane,n-pentane.1.4 The values stated in SI units are to be regarde
5、d as thestandard. The values stated in inch-pound units are for infor-mation only.1.5 This standard does not purport to address all of thesafety concerns associated with its use. It is the responsibilityof the user of this standard to establish appropriate safety andhealth practices and determine th
6、e applicability of regulatorylimitations prior to use. For specific warning statements, see5.3.1.2. Referenced Documents2.1 ASTM Standards:2E260 Practice for Packed Column Gas Chromatography3. Summary of Test Method3.1 The sample is separated in a gas chromatograph systemusing a packed chromatograph
7、ic column with either helium orhydrogen as the carrier gas. The separated components of thesample are detected by either a thermal conductivity detector orby a flame ionization detector. Calibration data are obtained byusing either relative response factors or by using a standardcalibration blend.4.
8、 Significance and Use4.1 This test method could be used to determine butylenestream composition for custody transfer payments. It is alsocapable of providing data necessary to evaluate processingrequirements in an operating plant.5. Apparatus5.1 ChromatographAny chromatographic instrumenthaving eith
9、er a thermal conductivity or flame ionizationdetector with an overall sensitivity sufficient to detect at least0.05 % of each of the components listed in 1.3.5.2 DetectorEither a thermal conductivity or flame ion-ization detector may be used.5.3 Sample ValveEither a constant-volume gas samplingvalve
10、 or a liquid sampling valve may be used. If a gas samplingvalve is used, greater care must be taken to ensure that thevaporized butylenes that are injected into the chromatographare a true representation of the sample.5.3.1 If the liquid sample valve is used, the sample cylindermust be pressured up
11、to at least 1100 kPa (160 psig) with aninert gas, such as nitrogen or helium. (WarningCompressedgas under high pressure. Gas reduces oxygen available forbreathing.) Also a valve must be installed in the purge linedownstream of the liquid sample valve to ensure the butylenessample in the sampling val
12、ve is entirely in the liquid phaseprior to injection into the column. (WarningExtremelyflammable liquefied gas under pressure. Vapor reduces oxygenavailable for breathing.)5.4 ColumnAny chromatographic column may be used,providing the components listed in the scope can be separatedsufficiently for t
13、he accurate determination of component con-centration. Resolution between peaks must afford a resolutionsuch that the depth of the valleys between peaks are no lessthan 50 % of the peak height of the lesser component. A list ofsatisfactory columns is given in Appendix X3.5.5 RecorderA recorder with
14、a full-scale response of 2 sor less and a maximum rate of noise of 60.3 % of full scale.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.D0.04 on C4 Hydrocarbons.Current edition ap
15、proved May 1, 2014. Published July 2014. Originally approvedin 1984. Last previous edition approved in 2009 as D4424 09. DOI: 10.1520/D4424-09R14.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards
16、 volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States16. Preparation of Apparatus6.1 Set up the chromatograph in accordance with the manu-facturers recomme
17、ndations. Install the analytical column andadjust the carrier gas flow and column temperature so that thecomponents will elute within the time desired for the analysis.7. Calibration7.1 A standard blend containing the components to beanalyzed may be either made or purchased from a commercialsource.
18、Inject the calibration blend under identical conditionsas will be used for the samples. Record the chromatogram andcalculate the factors to be used for analysis by using the peakareas as measured by either manual, mechanical, or electronicmeans.7.2 Relative response factors may be used if they areav
19、ailable.NOTE 1Practice E260 procedures may be helpful to those using thistest method.8. Procedure8.1 If a vapor sample is to be injected using a gas samplevalve, a representative portion of the liquid butylenes must betaken and vaporized into a suitable container. As a suggestion,a small, 5 or 10 mL
20、 aliquot of liquid butylenes under pressurein a valved, 5 or 10-mL sample cylinder can be expanded intoa larger container as a vapor. Then this resultant vapor wouldbe injected into the chromatograph.8.2 If a liquid sampling valve is used, pressure the samplecylinder to at least 1100 kPa (160 psig)
21、with either helium ornitrogen.8.3 Take the sample after the proper preparation has beendone and inject it into the gas chromatographic column usingthe appropriate sampling valve. Record the chromatogramusing as low an attenuation as possible to insure all peaks areon scale and as large as possible.8
22、.4 Measure the peak areas after all peaks have eluted.Measurement may be automatic by using either mechanical orelectronic integrators or computers.9. Calculations9.1 Calculate the concentration of each component using thefollowing equation:Ci5 Ai3Fi3100/(Ai3Fi! (1)where:Ci= concentration of the i-t
23、h component,Ai= peak area of the i-th component,Fi= calibration factor for the i-th component, andAiFi= sum of all products of peak areas times calibra-tion factors.10. Report10.1 Report individual hydrocarbon compounds of the testsample using units of mass percent, rounded to the nearest 0.05mass p
24、ercent.11. Precision and Bias11.1 It is not feasible to provide a complete precisionstatement covering repeatability and reproducibility for thistest method at this time, since a sufficient quantity of repeattests and samples under the required ASTM protocol are notavailable. This information is bei
25、ng determined and will beavailable on or before May 31, 2014.11.2 The temporary repeatability standard deviation wasdetermined to be as shown in Table 1.11.3 BiasSince there is no accepted reference materialsuitable for determining bias for the procedure in this testmethod, bias cannot be determined
26、.12. Keywords12.1 butylene; C1-C4hydrocarbons; gas chromatographyD4424 09 (2014)2APPENDIXES(Nonmandatory Information)X1. GC PARAMETERS KNOWN TO WORKX1.1 GC Parameters:Column, GS Alumina50m0.53mmCarrier Gas, Heliumat 5.6 cm3/min at 60COven 60C initialfor 3 min5C/min to 105Chold 3 min5C/min to 150Chol
27、d 20 min20C/min to 180Chold 1.5 minSample Valve0.1-L liquid valveSplit Vent Flow113 cc3/minSeptum Purge2 cc3/minAuxiliary Gas, Helium33 cc3/minFID hydrogen33 cc3/minFID air375 cc3/minTABLE 1 Repeatability EstimatesPropylene Isobutane n-Butane trans-2-Butene Butene-1 Isobutylene cis-2-Butene iso-Pent
28、ane n-Pentane 1,3-Butadiene0.513 0.703 3.040 5.000 14.000 20.000 3.990 0.203 0.102 50.5500.510 0.702 3.037 4.993 13.989 19.988 3.984 0.203 0.102 50.4480.509 0.702 3.044 4.993 14.001 19.996 4.004 0.205 0.103 50.3850.509 0.698 3.025 4.982 13.943 19.920 3.974 0.201 0.102 50.3800.508 0.699 3.032 4.981 1
29、3.947 19.922 3.981 0.202 0.102 50.4510.509 0.698 3.031 4.988 13.961 19.932 3.983 0.202 0.102 50.4140.510 0.702 3.045 4.994 14.002 20.015 3.997 .0198 0.102 50.4750.508 0.697 3.025 4.978 13.937 19.897 3.973 0.202 0.102 50.3600.510 0.699 3.039 5.002 14.002 20.011 3.990 0.203 0.102 50.5510.510 0.700 3.0
30、33 4.993 13.979 19.972 3.983 0.203 0.102 50.4840.508 0.696 3.017 4.956 13.885 19.855 3.963 0.201 0.101 50.253AVERAGE 0.509 0.700 3.033 4.987 13.968 19.955 3.984 0.202 0.102 50.432STDDEV 0.001 0.002 0.009 0.013 0.037 0.053 0.011 0.002 0.000 0.087RSD 0.283 0.334 0.286 0.258 0.267 0.265 0.288 0.870 0.4
31、38 0.173D4424 09 (2014)3X2. EXAMPLE CHROMATOGRAMX2.1 See Fig. X2.1.X3. SUGGESTED COLUMNSX3.1 Column AX3.1.1 Column2.1 m by 3.2-mm (7 ft by18-in.) outsidediameter steel packed with 20 % diisopropyl phthalate on60/80 mesh NAW Chromosorb P; followed by 15.2 m by3.2-mm (50 ft by18-in.) outside diameter
32、stainless steel packedwith 20 % dimethyl sulfolane on 60/80 mesh NAW Chromo-sorb P.X3.1.2 Carrier Gashelium at 30 cm3/min.X3.1.3 Column Oven Temperatureambient.X3.1.4 Sample Valve1-L liquid valve.X3.2 Column BX3.2.1 Column12.2 m by 3.2-mm (40 ft by18-in.) outsidediameter stainless steel packed with
33、16 % sebaconitrile on80/100 meshAW Chromosorb P; followed by 1.8 m by 3.2-mm(6 ft by18-in.) outside diameter stainless steel packed with80/100 mesh OPN/Porasil C Durapak; followed by 1.2 m by3.2-mm (4 ft by18-in.) outside diameter stainless steel packedwith 80/100 mesh phenylisocyanate on Porasil C
34、Durapak.X3.2.2 Carrier Gashydrogen at 30 cm3/min.X3.2.3 Column Oven Temperature40C.X3.2.4 Sample Valve1-L liquid valve.FIG. X2.1 Example ChromatogramD4424 09 (2014)4ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this
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37、nsible 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 address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, Wes
38、t 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). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ 09 (2014)5
