1、Designation: D 2426 93 (Reapproved 2004)e1An American National StandardStandard Test Method forButadiene Dimer and Styrene in Butadiene Concentrates byGas Chromatography1This standard is issued under the fixed designation D 2426; the number immediately following the designation indicates the year of
2、original 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.e1NOTEWarning notes were moved into text editorially in November 2004.
3、1. Scope1.1 This test method covers the determination of butadienedimer (4-vinylcyclohexene-1) and styrene in butadiene concen-trates, both recycle and specification grade.1.2 The values stated in SI units are to be regarded as thestandard.1.3 This standard does not purport to address all of thesafe
4、ty 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 specificprecautionary statements see Sections 6 and 8.2. Referenced Do
5、cuments2.1 ASTM Standards:2D 1657 Test Method for Density or Relative Density ofLight Hydrocarbons by Pressure ThermohydrometerD 1945 Test Method for Analysis of Natural Gas by GasChromatographyD 2593 Test Method for Butadiene Purity and HydrocarbonImpurities by Gas Chromatography2.2 Other Documents
6、:2STP 109 A , Physical Constants of Hydrocarbons C1to C103. Summary of Test Method3.1 The sample is introduced into a gas-liquid partitioncolumn. The components of interest are separated as they aretransported through the column by a carrier gas, and theirpresence in the effluent is detected and rec
7、orded as a chromato-gram. Packed columns are used, and either thermal conductiv-ity or ionization detectors are permissible. The quantity of thecomponents of interest present in the sample is determinedfrom the chromatogram by comparing their peak areas orheights with those obtained from a synthetic
8、 sample.4. Significance and Use4.1 Butadiene dimer and styrene may be present as impuri-ties in commercial butadiene. This test method is suitable foruse in internal quality control and in establishing productspecifications.5. Apparatus5.1 ChromatographAny chromatograph having either athermal conduc
9、tivity or flame ionization detector may be used.The detector system shall have sufficient sensitivity to obtain adeflection of at least 2 mm at a signal-to-noise ratio of at least5:1 for 0.01 weight % of butadiene dimer and styrene under theoperating conditions prescribed in this test method.5.2 Rec
10、orderA 0 to 1-mV, 0 to 5-mV, or 0 to 10-mVrecorder with a full-scale response time of2sorless, and withsufficient sensitivity to meet the requirements of 5.1.5.3 ColumnAny column may be used that is capable ofresolving the butadiene dimer and styrene as discrete peaks,quantitatively proportional to
11、concentration and within anelapsed time sufficiently short to be practical.5.4 Liquid Sampling ValveAny liquid sampling valve maybe used that will permit the reproducible introduction of thebutadiene concentrate as a liquid under its vapor pressure orhigher and in a quantity sufficient to meet the s
12、ensitivity andresolution requirements in 5.1 and 5.3, respectively.36. Reagents and Materials6.1 4-vinylcyclohexene-1 and Styrene, for calibration, purityof not less than 99 %.6.2 Carrier GasHelium or hydrogen for use on thermalconductivity detector units; or nitrogen, helium, or argon foruse on ion
13、ization detector units. (WarningCompressed gas.Hazardous pressure.) (WarningHydrogen gas is flammable.Hazardous pressure.)6.3 Liquid Phase, for column.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of Subcommitte
14、eD02.D0 on Hydrocarbons for Chemical and Special Uses.Current edition approved Nov. 1, 2004. Published November 2004. Originallyapproved in 1965. Last previous edition approved in 1998 as D 2426 93 (1998).2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer S
15、ervice at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Suitable valves are commercially available.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United Stat
16、es.NOTE 1The following materials have been used successfully as liquidphases (see Table 1):Carbowax 400, 1500, 1540General Electric SE-30 silicone gum rubberPolyethylene glycol 6000Barecowax 1035Dow Corning silicone oilCarbowax 20M + Dow Corning Hi Vac.6.4 Solid Support, for use in packed column, us
17、uallycrushed fire brick or diatomaceous earth. Sieve size willdepend on the diameter of the column used and support loadingand should be such as to give optimum resolution and analysistime.7. Preparation of Apparatus7.1 Column PreparationAny satisfactory method, used inthe practice of the art, that
18、will produce a column meeting therequirements of 5.3. SeeAppendix X2, Sample Calculations, ofTest Method D 1945, also see 6.1, Carrier Gas, of Test MethodD 2593.7.2 ChromatographPut in service in accordance with themanufacturers instructions. The injector temperature shall beno greater than 5C above
19、 the column oven temperature. Thecolumn oven temperature shall not exceed 185C. See Table 1for typical operating conditions.7.3 Synthetic BlendsPrepare a synthetic mixture from 99mol % minimum pure 4-vinylcyclohexene-1 and styrene in asuitable matrix in approximately the same concentration ex-pected
20、 in the sample. The matrix may be any one of the normalparaffin hydrocarbons from butane to heptane, inclusive. Inpreparing the blend, weigh each compound added with suffi-cient precision to result in a mixture accurate to 5 % relative or0.02 % absolute, whichever is greater. Transfer the blend to a
21、container of the type to be used for the sample and pressurewith a suitable gas.8. Procedure8.1 Using the liquid sampling valve, inject into the columnthe desired volume of synthetic blend and record the peaks ata sensitivity setting that allows the maximum peak height.Pressure the sample cylinder w
22、ith a suitable gas to a pressuresufficient to ensure no flashing in the line to the sampling valveor in the valve itself. Using the same sample size andinstrument conditions, inject the sample into the column andrecord the peaks. (See Table 1 for typical operating conditions.)(WarningButadiene gas i
23、s flammable under pressure.)9. Calculation9.1 Peak MeasurementMeasure the peak area or height ofeach component of interest in both the synthetic blend and thesample. Measurement may be accomplished by any methodthat meets the precision requirements of Section 10. Areamethods found to be acceptable i
24、nclude planimetering, inte-gration, and triangulation (multiplying the peak height by thewidth at the half-height). In peak area or height methods caremust be taken so that chromatograph operating parameterssuch as column temperature and carrier gas flow rate are keptat the same conditions on both t
25、he synthetic standard and thesample. Calculate the percentage by weight of each componentas follows:Concentration, weight % 5 As/Ao! 3 S 3 Go/Gs! (1)where:As= peak area or height of component in the sample,Ao= peak area or height of component in the syntheticblend,S = weight % of component in the sy
26、nthetic blend,Gs= relative density 60/60 of the sample, andGo= relative density 60/60 of the synthetic blend.NOTE 2The specific gravity of the sample may be determined inaccordance with Test Method D 1657 and the specific gravity of thesynthetic may be assumed to be equal to the gravity of solvent u
27、sed toprepare the blend. A list of such gravities is found in STP 109A.10. Precision and Bias10.1 The precision of this test method as determined bystatistical examination of interlaboratory results is as follows:10.1.1 RepeatabilityThe difference between successivetest results, obtained by the same
28、 operator with the sameapparatus under constant operating conditions on identical testmaterial would, in the long run, and in the normal and correctoperation of the test method, exceed the following values onlyin one case in twenty:Concentration RepeatabilityDimer, wt %Styrene, wt %0.151.490.0050.04
29、4TABLE 1 Columns and Conditions Used SuccessfullyDow Silicone200Carbowax1500Carbowax1540Silicone SE-30Carbowax20M + DowCorning Hi VacPolyethyleneGlycol-6000Barecowax1035Column length, m 1.5 4.6 3.7 15.2 3.1 3.7 6.1Column diameter, mm 3.2 4.8 6.4 0.5 6.4 4.8 6.4Column temperature, C 85 110 100 75 100
30、128 155 140Liquid phase, wt % 10 15 16 . 0.75 each 30 20Support material Chromosorb P TFE-fluorocarbon Chromosorb P (Coated) Silica Chromosorb P Chromosorb PMesh 80100 4060 100120 . . 3050 6080Carrier flow, mL/min 19 60 60 15 30 171 60Detector HFIAT.C.BHFI HFI T.C. T.C. T.C.Sample size, L 0.77 20 0.
31、07 1.54 1.03 8.69 3.0Peak measurement triangulation triangulation integrator triangulation triangulation peak height planimeterAHFI = hydrogen flame ionization.BT.C. = thermal conductivity.D 2426 93 (2004)e1210.1.2 ReproducibilityThe difference between two singleand independent results obtained by d
32、ifferent operators work-ing in different laboratories on identical test material would, inthe long run, and in the normal and correct operation of the testmethod, exceed the following values only in one case intwenty:Concentration ReproducibilityDimer, wt %Styrene, wt%0.151.490.0180.05110.2 BiasSinc
33、e there is no accepted reference materialsuitable for determining the bias for the procedure in this testmethod for measuring dimer and styrene, bias has not beendetermined.11. Keywords11.1 butadiene concentrate; butadiene dimer; gas chroma-tography; styreneASTM International takes no position respe
34、cting 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 responsibility.This st
35、andard 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 ASTM Internat
36、ional 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 address shown belo
37、w.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 2426 93 (2004)e13
