1、Designation: D 2505 88 (Reapproved 2004)e1An American National StandardStandard Test Method forEthylene, Other Hydrocarbons, and Carbon Dioxide in High-Purity Ethylene by Gas Chromatography1This standard is issued under the fixed designation D 2505; the number immediately following the designation i
2、ndicates 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.e1NOTEWarning notes were moved into text editorial
3、ly in November 2004.1. Scope1.1 This test method covers the determination of carbondioxide, methane, ethane, acetylene, and other hydrocarbons inhigh-purity ethylene. Hydrogen, nitrogen, oxygen, and carbonmonoxide are determined in accordance with Test MethodD 2504. The percent ethylene is obtained
4、by subtracting thesum of the percentages of the hydrocarbon and nonhydrocar-bon impurities from 100. The method is applicable over therange of impurities from 1 to 500 parts per million volume(ppmV).1.2 This standard does not purport to address all of thesafety concerns, if any, associated with its
5、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 some specifichazard statements, see Section 6.1.3 The values stated in acceptable metric units are to beregarde
6、d as the standard. The values in parentheses are forinformation only.2. Referenced Documents2.1 ASTM Standards:2D 2504 Test Method for Noncondensable Gases in C2andLighter Hydrocarbon Products by Gas ChromatographyD 4051 Practice for Preparation of Low-Pressure GasBlendsE 260 Practice for Packed Col
7、umn Gas ChromatographyF 307 Practice for Sampling Pressurized Gas for GasAnaly-sis3. Summary of Test Method3.1 The sample is separated in a gas chromatograph systemutilizing four different packed chromatographic columns withhelium as the carrier gas. Methane and ethane are determinedby using a silic
8、a gel column. Propylene and heavier hydrocar-bons are determined using a hexamethylphosphoramide(HMPA) column. Acetylene is determined by using, in series,a hexadecane column and a squalane column. Carbon dioxideis determined using a column packed with activated charcoalimpregnated with a solution o
9、f silver nitrate in b,b8-oxydipropionitrile. Columns other than those mentioned abovemay be satisfactory (see 5.3). Calibration data are obtainedusing standard samples containing the impurities, carbondioxide, methane, and ethane in the range expected to beencountered. Calibration data for acetylene
10、 are obtained as-suming that acetylene has the same peak area response on aweight basis as methane. The acetylene content in a sample iscalculated on the basis of the ratio of peak area of the acetylenepeak to the peak area of a known amount of methane.Calculations for carbon dioxide, methane, and e
11、thane arecarried out by the peak-height measurement method.4. Significance and Use4.1 High-purity ethylene is required as a feedstock for somemanufacturing processes, and the presence of trace amounts ofcarbon dioxide and some hydrocarbons can have deleteriouseffects. This method is suitable for set
12、ting specifications, foruse as an internal quality control tool and for use in develop-ment or research work.5. Apparatus5.1 Any chromatographic instrument with an overall sensi-tivity sufficient to detect 2 ppmV or less of the compoundslisted with a peak height of at least 2 mm without loss ofresol
13、ution.5.2 DetectorsThermal ConductivityIf a methanation re-actor is used, a flame ionization detector is also required. Todetermine carbon dioxide with a flame ionization detector, amethanation reactor must be inserted between the column and1This test method is under the jurisdiction of ASTM Committ
14、ee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.D0 on Hydrocarbons for Chemical and Special Uses.Current edition approved Nov. 1, 2004. Published November 2004. Originallyapproved in 1966. Last previous edition approved in 1998 as D 2505 88 (1998).2For
15、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 Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700,
16、 West Conshohocken, PA 19428-2959, United States.the detector and hydrogen added as a reduction gas (see TestMethod D 2504, Appendix X1, Preparation of MethanationReactor).5.3 ColumnAny column or set of columns can be usedthat separates carbon dioxide, methane, acetylene and C3andheavier compounds.
17、There may be tailing of the ethylene peakbut do not use any condition such that the depth of the valleysahead of the trace peak is less than 50 % of the trace peakheight. (See Fig. 1 for example.)5.4 RecorderA recorder with a full-scale response of 2 sor less and a maximum rate of noise of 60.3 % of
18、 full scale.5.5 Gas-Blending ApparatusA typical gas-blending appa-ratus is shown in Fig. 2. A high-pressure manifold equippedwith a gage capable of accurately measuring ethylene pressuresup to 3.4 MN/m2gage (500 psig) is required. Other types ofgas-blending equipment, such as described in Practice D
19、 4051,can be used.NOTE 1 Practice E 260 contains information that will be helpful tothose using this method.6. Reagents and Materials6.1 Copper or Aluminum, or Stainless Steel Tubing, 6.4-mm(14-in. ) outside diameter, and nylon tubing, 3.2-mm (18-in.)outside diameter.6.2 Solid SupportsCrushed firebr
20、ick or calcined diatoma-ceous earth, such as Chromosorb P,335 to 80-mesh and 80 to100-mesh. Other supporting materials or mesh sieves can besatisfactory.6.3 Active SolidsActivated carbon, 30 to 40-mesh,4silicagel, 100 to 200-mesh.5Other sizes may be satisfactory.6.4 Liquid PhasesHexamethylphosphoram
21、ide (HMPA6),hexadecane.6Squalene,6silver nitrate, and b,b8-oxydipropionitrile.7Other liquid phases may be satisfactory.(WarningCombustible solvents. See A1.7.) (WarningHMPAmay be harmful if inhaled. Causes irritation.Apotentialcarcinogen (lungs). See A1.5.)6.5 Helium.(WarningCompressed Gas, Hazardou
22、s Pres-sure. See A1.2.)6.6 Hydrogen.(WarningFlammable Gas, HazardousPressure. See A1.6.)6.7 Acetone.(WarningExtremely Flammable. See A1.1.)6.8 Gases for CalibrationPure or research grade carbondioxide, methane, ethane, acetylene, ethylene, propane, andpropylene. Certified calibration blends are comm
23、ercially avail-able from numerous sources and may be used. (WarningFlammable Gases, Hazardous Pressure. See A1.2 and A1.3.)6.9 Methanol.(WarningFlammable. Vapor Harmful. SeeA1.4.)3The sole source of supply of the apparatus is available from the Celite Division,Johns Mansville Co., New York, NY. f yo
24、u are aware of alternative suppliers, pleaseprovide this information to ASTM International Headquarters. Your comments willreceive careful consideration at a meeting of the responsible technical committee1,which you may attend.4A fraction sieved in the laboratory to 30 to 40 mesh from medium activit
25、ycharcoal, 20 to 60 mesh, sold by Central Scientific Co., 1700 Irving Park Road,Chicago, IL 60613, has been found satisfactory for this purpose. If you are aware ofalternative suppliers, please provide this information to ASTM InternationalHeadquarters. Your comments will receive careful considerati
26、on at a meeting of theresponsible technical committee1, which you may attend.5The sole source of supply of the apparatus known to the committee at this timeis Silica gel Code 923 available from the Davison Chemical Co., Baltimore,Md. 21203. If you are aware of alternative suppliers, please provide t
27、his informationto ASTM International Headquarters. Your comments will receive careful consid-eration at a meeting of the responsible technical committee1, which you may attend.6The sole source of supply of the apparatus known to the committee at this timeis available from the Fisher Scientific Co.,
28、St. Louis, MO. If you are aware ofalternative suppliers, please provide this information to ASTM InternationalHeadquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee1, which you may attend.7b,b8-oxydipropionitrile, sold by Distillation Produc
29、ts Industries, Division ofEastman Kodak Co., Rochester, NY, has been found to be satisfactory. If you areaware of alternative suppliers, please provide this information to ASTM Interna-tional Headquarters. Your comments will receive careful consideration at a meetingof the responsible technical comm
30、ittee1, which you may attend.FIG. 1 Typical Chromatogram for PropyleneFIG. 2 Gas-Blending ManifoldD 2505 88 (2004)e12NOTE 2The use of copper tubing is not recommended with samplescontaining acetylene as this could lead to the formation of potentiallyexplosive copper acetylide.7. Sampling7.1 Samples
31、should be supplied to the laboratory in highpressure sample cylinders, obtained using the proceduresdescribed in Practice F 307, or similar methods.8. Preparation of Apparatus8.1 Silica Gel ColumnDry the silica gel in an oven at204C (400F) for 3 h, cool in a desiccator, and store inscrew-cap bottles
32、. Pour the activated silica gel into a 0.9-m(3-ft) length of 6.4-mm (14-in.) outside diameter copper oraluminum tubing plugged with glass wool at one end. Tap orvibrate the tube while adding the silica gel to ensure uniformpacking and plug the top end with glass wool. Shape thecolumn to fit into the
33、 chromatograph.8.2 Silver Nitrateb,b8-OxydipropionitrileActivatedCarbon ColumnWeigh 10 g of b,b8-oxydipropionitrile into abrown 125-mL (4-oz) bottle. Add5gofsilver nitrate (AgNO3)crystals. With occasional shaking, dissolve as much AgNO3aspossible, and allow the bottle to stand overnight to ensuresat
34、uration. Prepare this solution fresh, as required. Withoutdisturbing the crystals at the bottom of the bottle, weigh 2.5 gof supernatant AgNO3solution into a 250-mL beaker and add50 mL of methanol. While stirring this mixture, slowly add22.5 g of activated carbon. Place the beaker on a steam bath to
35、evaporate the methanol. When the impregnated activatedcarbon appears to be dry, remove the beaker from the steambath and finish drying in an oven at 100 to 110C for 2 h. Plugone end of a 4-ft (1.2-m) length of 6.4-mm (14-in.) outsidediameter aluminum or stainless steel tubing with glass wool.Hold th
36、e tubing vertically with the plugged end down and pourfreshly dried column packing into it, vibrating the columnduring filling to ensure uniform packing. Plug the top end withglass wool and shape the tubing so that it may be mountedconveniently in the chromatograph.8.3 Hexamethylphosphoramide Column
37、 (HMPA)Dry the35 to 80-mesh inert support at 204C (400F). Weigh 75 g intoa wide-mouth 500-mL (16-oz) bottle.Add 15 g of HMPAto theinert support and shake and roll the mixture until the supportappears to be uniformly wet with the HMPA. Pour the packinginto a 6-m (20-ft) length of 6.4-mm (14-in.) outs
38、ide diametercopper of aluminum tubing plugged at one end with glasswool. Vibrate the tubing while filling to ensure more uniformpacking. Plug the top end of the column with glass wool andshape the column to fit into the chromatograph.8.4 Hexadecane-Squalane ColumnDissolve 30 g of hexa-decane into ap
39、proximately 100 mL of acetone. Add 70 g of 80to 100-mesh inert support. Mix thoroughly and pour themixture into an open pan for drying. The slurry should bestirred during drying to ensure uniform distribution. When theacetone has evaporated, add a portion of the packing to a 7-m(25-ft) length of 3.2
40、-mm (18-in.) outside diameter nylon tubingwhich has been plugged at one end with glass wool. Vibrate thecolumn while filling to ensure more uniform packing. Fill thecolumn with packing to only 4 m (15 ft) of the length of thecolumn. Fill the remainder of the column with squalanepacking prepared in t
41、he same manner as the hexadecanepacking. Plug the open end of the tubing with glass wool andshape the column to fit into the chromatograph with thehexadecane portion of the column at the front end of thecolumn. The column shall be purged under test conditions (nosample added) until a constant baseli
42、ne is obtained.NOTE 3Columns made with liquid phases listed above were usedsatisfactorily in cooperative work. Other columns may be used (see 5.3).9. Calibration9.1 Preparation of Standard Mixtures:9.1.1 Preparation of ConcentratePrepare a concentrate ofthe impurities expected to be encountered. A c
43、ertified calibra-tion blend containing the expected impurities can be obtainedand used as the concentrate. An example of a satisfactoryconcentrate is given in Table 1. The concentrate can beprepared using the gas blending manifold as shown in Fig. 2 orusing a similar apparatus as follows: Evacuate t
44、he apparatusand add the components in the order of increasing vaporpressure; that is, propylene, carbon dioxide, ethane and meth-ane. Record the increase in pressure on the manometer as eachcomponent is added. Close the reservoir and evacuate themanometer after each addition.9.1.2 Dilution of Concen
45、trateDilute the concentrate withhigh-purity ethylene in a ratio of approximately 1:4000. Thiscan be done by adding the calculated amount of the concentrateand high purity ethylene to an evacuated cyclinder using thegas-blending apparatus (Fig. 2). Use a source of high-pressure,high-purity ethylene e
46、quipped with a needle valve and apressure gage capable of accurately measuring the pressure ofthe blend as the ethylene is added to the cylinder containing theconcentrate. Add the calculated amount of ethylene; warm oneend of the cylinder to ensure mixing of the blend. Allow thetemperature to reach
47、equilibrium before recording the finalpressure on the cylinder. Prepare at least three calibrationsamples containing the compounds to be determined over therange of concentration desired in the products to be analyzed.9.2 Calculation of Composition of Standard MixturesCalculate the exact ratio of th
48、e concentrate dilution withethylene by correcting the pressure of the ethylene added forthe compressibility of ethylene (Table 2). Multiply the dilutionratio or factor by the percentage of each component present inthe original concentrate (Table 1). These calculations give theamount of each componen
49、t that has been added to thehigh-purity ethylene blend stock. The actual composition of thefinal blend must be ascertained by making corrections for theimpurities present in the high-purity ethylene used for theblend stock. The amount of correction is determined by makingchromatograph runs on the high-purity ethylene and measuringthe peak heights of the impurities. These peak heights will beTABLE 1 Suggested Composition of a Concentrate of ImpuritiesUsed in Preparing Standard Mixtures for Calibration PurposesComponent PercentCarbon dioxide 10Me
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