1、Designation: D 2593 93 (Reapproved 2004)e1Designation: 194/74 (81)An American National StandardStandard Test Method forButadiene Purity and Hydrocarbon Impurities by GasChromatography1This standard is issued under the fixed designation D 2593; the number immediately following the designation indicat
2、es the year 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.This test method was adopted as a joint ASTM-IP Standard
3、 in 1972.e1NOTEWarning notes were editorially moved into text in November 2004.1. Scope1.1 This test method covers the determination of butadiene-1,3 purity and impurities such as propane, propylene, isobu-tane, n-butane, butene-1, isobutylene, propadiene, trans-butene-2, cis-butene-2, butadiene-1,2
4、, pentadiene-1,4, and,methyl, dimethyl, ethyl, and vinyl acetylene in polymerizationgrade butadiene by gas chromatography. Impurities includingbutadiene dimer, carbonyls, inhibitor, and residue are measuredby appropriate ASTM procedures and the results used tonormalize the component distribution obt
5、ained by chromatog-raphy.NOTE 1Other impurities present in commercial butadiene must becalibrated and analyzed. Other impurities were not tested in the coopera-tive work on this test method.NOTE 2This test method can be used to check for pentadiene-1,4 andother C5s instead of Test Method D 1088.1.2
6、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. For specific hazar
7、dstatements, see 6.1 and 9.3.2. Referenced Documents2.1 ASTM Standards:2D 1088 Test Method for Boiling Point Range ofPolymerization-Grade Butadiene32.2 Energy Institute Standards:4Test Method IP 194, Analysis of Butadiene-1,3 Polymer-ization Grade.3. Summary of Test Method3.1 A representative sample
8、 is introduced into a gas-liquidpartition column. The butadiene and other components areseparated as they are transported through the column by aninert carrier gas. Their presence in the effluent is measured bya detector and recorded as a chromatogram. The chromatogramof the sample is interpreted by
9、 applying component attenuationand detector response factors to the peak areas or peak heightsand the relative concentration determined by relating indi-vidual peak response to total peak response. Impurities includ-ing butadiene dimer, carbonyls, inhibitor, and residue aremeasured by appropriate AS
10、TM procedures and the resultsused to normalize the distribution obtained by gas chromatog-raphy.4. Significance and Use4.1 The trace hydrocarbon compounds listed can have aneffect in the commercial use of butadiene. This test method issuitable for use in process quality control and in settingspecifi
11、cations.5. Apparatus5.1 ChromatographAny chromatograph having either athermal-conductivity or flame ionization detector can be used1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.D0 on Hydrocarb
12、ons for Chemical and Special Uses.Current edition approved Nov. 1, 2004. Published November 2004. Originallyapproved in 1967. Last previous edition approved in 1998 as D 2593 93 (1998).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceast
13、m.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn.4Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR,U.K.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA
14、19428-2959, United States.provided the system has sufficient sensitivity and stability toobtain a recorder deflection of at least 2 mm at signal-to-noiseratio of at least 5:1 for 0.01 weight % of impurity.5.2 ColumnAny column can be used that is capable ofresolving the components listed in 1.1 with
15、the exception ofbutene-1 and isobutylene, which can be eluted together. Thecomponents should be resolved into distinct peaks such that theratio A/B will not be less than 0.5 where A is the depth of thevalley on either side of peak B and B is the height above thebaseline of the smaller of any two adj
16、acent peaks. In the casewhere the small component peak is adjacent to a large one, itcan be necessary to construct a baseline of the small peaktangent to the curve as shown in Fig. 1.5.2.1 A description of columns that meet the requirementsof this test method is tabulated in the Appendix. Persons us
17、ingother column materials must establish that the column givesresults that meet the precision requirements of Section 11.5.3 Sample Inlet SystemMeans shall be provided forintroducing a measured quantity of representative sample intothe column. Pressure-sampling devices can be used to inject asmall a
18、mount of liquid directly into the carrier gas. Introduc-tion can also be accomplished by use of a gas valve to chargethe vaporized liquid.5.4 RecorderA recording potentiometer with a full-scaledeflection of 10 mV or less is suitable for obtaining thechromatographic data. Full-scale response time sho
19、uld be 2 sor less, and with sufficient sensitivity to meet the requirementsof 5.1.NOTE 3Other methods of recording detector output such as computer-teletype systems can be used instead of a recorder, provided precisionrequirements of Section 11 are met.6. Reagents and Materials6.1 Carrier GasA carri
20、er gas appropriate to the type ofdetector used should be employed. Helium or hydrogen may beused with thermal conductivity detectors. Nitrogen, helium, orargon may be used with ionization detectors. The minimumpurity of any carrier should be 99.95 mol %. (WarningCompressed gas. Hazardous pressure.)
21、(WarningHydrogenflammable gas. Hazardous pressure.)6.1.1 If hydrogen is used, special safety precautions must betaken to ensure that the system is free from leaks and that theeffluent is properly vented.6.2 Column Materials:6.2.1 Liquid PhaseThe materials that have been usedsuccessfully in cooperati
22、ve work as liquid phases are listed inTable X1.1.6.2.2 Solid SupportThe support for use in the packedcolumn is usually crushed firebrick or diatomaceous earth.Sieve size will depend on the diameter of the column used andliquid-phase loading, and should be such as would giveoptimum resolution and ana
23、lysis time. Optimum size rangescannot be predicted on purely theoretical grounds. For somesystems it has been found that a ratio of average particlediameter to column inside diameter of 1:25 will result inminimum retention time and minimum band widths.6.2.3 Tubing MaterialCopper, stainless steel, Mo
24、nel, alu-minum, and various plastic materials have been found to besatisfactory for column tubing. The material must be nonreac-tive with respect to substrate, sample, and carrier gas and ofuniform internal diameter.6.3 Hydrocarbons for Calibration and IdentificationHydrocarbon standards for all com
25、ponents present are neededfor identification by retention time and for calibration forquantitative measurements.NOTE 4Mixtures of hydrocarbons can be used provided there is nouncertainty as to the identity or concentration of the compounds involved.7. Preparation of Apparatus7.1 Column PreparationTh
26、e technique used to preparethe column is not critical as long as the finished columnproduces the desired separation. Preparation of the packing isnot difficult once the support, partitioning liquid, and loadinglevel have been determined. The following general directionshave been found to produce col
27、umns of acceptable character-istics.7.1.1 Weigh out the desired quantity of support, usuallytwice that required to fill the column.7.1.2 Calculate and weigh out the required quantity ofpartitioning agent. Dissolve the partitioning agent in a volumeof chemically inert, low-boiling solvent equal to ap
28、proximatelytwice the volume of support.7.1.3 Gradually add the support material to the solution withgentle stirring.7.1.4 Slowly evaporate the solvent while gently agitatingthe mixture until the packing is nearly dry and no free liquid isapparent.7.1.4.1 Some stationary phases such as benzyl cyanide
29、silver nitrate are susceptible to oxidation and must be protectedfrom excessive exposure to air during the evaporation anddrying steps.7.1.5 Spread the packing in thin layers on a nonabsorbentsurface and air- or oven-dry as required to remove all traces ofsolvent.7.1.6 Resieve the packing to remove
30、fines and agglomeratesproduced in the impregnation step.7.1.7 Fill the column tubing with packing by plugging oneend with glass wool and pouring the packing into the other endFIG. 1 Illustration of A/B Ratio for Small-Component PeakD 2593 93 (2004)e12through a small funnel. Vibrate the tubing contin
31、uously over itsentire length while filling. When the packing ceases to flow, tapthe column gently on the floor or bench-top while vibrating iscontinued. Add packing as necessary until no further settlingoccurs during a 2-min period. Remove a small amount ofpacking from the open end, plug with glass
32、wool, and shape thecolumn to fit the chromatograph.7.2 ChromatographMount the column in the chromato-graph and establish the operating conditions required to givethe desired separation (Appendix X1).Allow sufficient time forthe instrument to reach equilibrium as indicated by a stablebase line. Contr
33、ol the oven temperature so that it is constant towithin 0.5C without thermostat cycling which causes anuneven base line. Set the carrier-gas flow rate, measured witha soap film meter, so that it is constant to within 1 mL/min ofthe selected value.8. Calibration8.1 IdentificationSelect the conditions
34、 of column tem-perature and carrier gas flow that will give the necessaryseparation. Determine the retention time for each compound byinjecting small amounts of the compound either separately orin mixtures. Recommended sample sizes for retention data are1 L for liquids and 1 cm3or less for gases.8.2
35、 StandardizationThe area under the peak of the chro-matogram is considered a quantitative measure of the amountof the corresponding compound. The relative area is propor-tional to the concentration if the detector responses of thesample components are equal. The recommended procedurefor quantitative
36、 calibration is as follows: with all equipment atequilibrium at operating conditions, inject constant volumesamples of high-purity components. Each compound should beinjected at least three times. The areas of the correspondingpeaks should agree within 1 %. When a recorder is used, adjustthe attenua
37、tion in all cases to keep the peak on-scale and witha height of at least 50 % of full scale. Measure the area of thepeaks by any reliable method (Note 7). To obtain componentweight % response data from the area response of the volumeinjections, it is necessary to consider the density and purity ofth
38、e compounds used for calibration. The average volume arearesponse of each component is divided by the density multi-plied by the weight percent purity of the component as follows:Weight percent response of component5average component peak areadensity 3 weight percent purity of component(1)Component
39、weight percent detector correction factors arethen obtained by selecting a reference component such asbutadiene, and dividing the individual component weightresponses into the reference weight response.8.2.1 Factors derived on a thermal-conductivity detectorusing helium-carrier gas are as follows:Co
40、mponent Mol wt ThermalResponseWeight Factor Weight Fac-tor,Butadiene-1,3=1.00Butadiene-1,3 54 80 0.68 1.00Propane 44 65 0.68 1.00Propylene 42 63 0.67 0.98Isobutane 58 82 0.71 1.04Component Mol wt ThermalResponseWeight Factor Weight Fac-tor,Butadiene-1,3=1.00n-Butane 58 85 0.68 1.00Butene-1 56 81 0.6
41、9 1.01Isobutylene 56 82 0.68 1.00trans-Butene-2 56 85 0.66 0.97cis-Butene-2 56 87 0.64 0.94Propadiene 40 53 0.75 1.10Methyl acetylene 40 58 0.69 1.01NOTE 5Response based on data represented by Messner,A. E., Rosie,D. M., and Argabright, P. A., Analytical Chemistry, Vol 31, 1959, pp.230233, and Dietz
42、, W. A., Journal of Gas Chromatography, Vol 5, No.2, 1967, pp. 6871.8.2.1.1 Although not determined with standards, weightfactors of 1.00 (compared to butadiene 1,3 as 1.00) were usedfor pentadiene-1,4 butadiene-1,2, dimethyl acetylene, ethyl andvinyl acetylene in this study to obtain the precision
43、listed inSection 11. It is permissible to use the above establishedresponse factors instead of calibration when using thermal-conductivity detectors with helium-carrier gas. With otherdetectors or carrier gas, or both, it is necessary to calibrate(Note 5).8.2.2 Measurements can be made using peak he
44、ights ascriteria for calculations instead of peak areas. If peak heightsare used, care must be taken so that chromatograph-operatingparameters such as column temperature and carrier-gas flowrate are kept at the same conditions as when the unit wascalibrated. The chromatograph can be calibrated using
45、 knownblends or by establishing relative-response data using peakheights in the same manner as listed above.NOTE 6Use of a hydrogen-flame detector gives essentially equalrelative response to hydrocarbons. On a weight basis, the sensitivity of theflame detector for hydrocarbons is essentially indepen
46、dent of the hydro-carbons structure. On a molar basis, the sensitivity appears to be a functionof the carbon content, giving essentially equal relative response tohydrocarbons containing the same number of carbon atoms.8.2.3 Because detector or amplifier output need not be linearwith component conce
47、ntration, this must be checked by inject-ing constant volumes of pure butadiene at a series of decreas-ing pressures from ambient down to 20 mm Hg (torr) or byusing synthetic standards with vapor sample valves at ambientor at decreasing pressures or by using synthetic standards withliquid sample val
48、ves. If on plotting the results the response islinear, then the calibration procedure given above is satisfac-tory. If not, the relative responses of the minor componentsmust be determined in the linear response region.9. Procedure9.1 Attach the sample cylinder to the instrument-samplingvalve so tha
49、t the sample is obtained from the liquid phase. Ifintroduction is through a liquid valve the sample cylindersshould be pressured with a suitable gas, such as helium, to apressure sufficient to ensure that sample flashing does not occurin the line to the sampling valve or in the valve itself. If a vaporvalve is used, care must be taken to completely vaporize asmall liquid sample, allowing the vapor to flow through thesample loop at a flow rate of 5 to 10 mL/min until at least tentimes the volume of the sample loop has been flushed through.If a vacuum-sampling
