1、Designation: D4424 09Standard 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 revision. A number in
2、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 mixtures.1.2 This te
3、st 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 componentslisted below at abo
4、ut 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 regarded as thestandard.
5、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 the applicability of
6、 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 chromatographic column with eit
7、her 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. Significance and
8、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 either a thermal condu
9、ctivity 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 or a liquid sampl
10、ing 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 to at least 1100 k
11、Pa (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 valve is entirely in
12、the liquid phaseprior to injection into the column. (WarningExtremelyflammable liquefied gas under pressure. Vapor reduces oxygenavailable for breathing.)1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of Subcommi
13、tteeD02.D0.04 on C4 Hydrocarbons.Current edition approved July 15, 2009. Published November 2009. Originallyapproved in 1984. Last previous edition approved in 2001 as D442490(2001)1.DOI: 10.1520/D4424-09.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer S
14、ervice 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, United States.5.4 ColumnAny chromatographic column may
15、be used,providing the components listed in the scope can be separatedsufficiently for the 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 compon
16、ent. A list ofsatisfactory columns is given in Appendix X3.5.5 RecorderA recorder with a full-scale response of 2 sor less and a maximum rate of noise of 60.3 % of full scale.6. Preparation of Apparatus6.1 Set up the chromatograph in accordance with the manu-facturers recommendations. Install the an
17、alytical 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. Inject the calibration b
18、lend 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 areavailable.NOTE 1Practice E
19、260 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 aliquot of liquid butyl
20、enes 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) with either helium ornit
21、rogen.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.8.4 Measure the peak area
22、s 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 Ai3 Fi3 100/(Ai3 Fi! (1)where:Ci= concentration of the i-th component,Ai= peak
23、area of the i-th component,Fi= calibration factor for the i-th component, and(Ai3 Fi= sum of all products of peak areas times cali-bration factors.10. Report10.1 Report individual hydrocarbon compounds of the testsample using units of mass percent, rounded to the nearest 0.05mass percent.11. Precisi
24、on 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 being determined and
25、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.12. Keywords12.1
26、butylene; C1-C4hydrocarbons; gas chromatographyTABLE 1 Repeatability EstimatesPropylene Isobutane n-Butane trans-2-Butene Butene-1 Isobutylene cis-2-Butene iso-Pentane 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 0.2
27、03 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 13.947 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
28、 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 3.033 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
29、.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 0.438 0.173D4424 092APPENDIXES(Nonmandatory Information)X1. GC PARAMETERS KNOWN TO WORKX1.1 GC Parameters:Column, GS Alumina50 m 3 0.53 mmC
30、arrier Gas, Heliumat 5.6 cm3/min at 60COven 60C initialfor 3 min5C/min to 105Chold 3 min5C/min to 150Chold 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/minX2. EXAMPLE
31、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 stainless steel packedwith 20 % dime
32、thyl sulfolane on 60/80 mesh NAW Chro-mosorb 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 16 % sebaconitrile onFIG. X2.1 Examp
33、le ChromatogramD4424 09380/100 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
34、 C Durapak.X3.2.2 Carrier Gashydrogen at 30 cm3/min.X3.2.3 Column Oven Temperature40C.X3.2.4 Sample Valve1-L liquid valve.ASTM 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 expre
35、ssly advised that determination of the validity of any such patent 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
36、, either reapproved or withdrawn. Your comments are invited either 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 a
37、ttend. 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, 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).D4424 094
