1、Designation: D 2007 03An American National StandardStandard Test Method forCharacteristic Groups in Rubber Extender and ProcessingOils and Other Petroleum-Derived Oils by the Clay-GelAbsorption Chromatographic Method1This standard is issued under the fixed designation D 2007; the number immediately
2、following the designation indicates 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.1. Scope*1.1 This test
3、method covers a procedure for classifying oilsamples of initial boiling point of at least 260C (500F) intothe hydrocarbon types of polar compounds, aromatics andsaturates, and recovery of representative fractions of thesetypes. This classification is used for specification purposes inrubber extender
4、 and processing oils.NOTE 1See Test Method D 2226.1.2 This test method is not directly applicable to oils ofgreater than 0.1 mass % pentane insolubles. Such oils can beanalyzed after removal of these materials, but precision isdegraded (see Appendix X1).1.3 The values stated in SI units are to be re
5、garded as thestandard. The values given in parentheses are for informationonly.1.4 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 dete
6、rmine the applica-bility of regulatory limitations prior to use. Specific warningstatements are given in 6.1, Section 7, A1.4.1, and A1.5.5.2. Referenced Documents2.1 ASTM Standards:D 86 Test Method for Distillation of Petroleum Products atAtmospheric Pressure2D 323 Test Method for Vapor Pressure of
7、 Petroleum Prod-ucts (Reid Method)2D 1159 Test Method for Bromine Numbers of PetroleumDistillates and Commercial Aliphatic Olefins by Electro-metric Titration2D 2226 Classification for Various Types of Petroleum Oilsfor Rubber Compounding Use3D 5309 Specification for Cyclohexane 9994E 691 Practice f
8、or Conducting an Interlaboratory Study toDetermine the Precision of a Test Method53. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 The following terms refer to the hydrocarbon typesand structural groups as measured by this test method:3.1.2 aromaticsmaterial that, on percolatio
9、n, passesthrough a column of adsorbent clay in a n-pentane eluent butadsorbs on silica gel under the conditions specified.3.1.3 asphaltenes, or n-pentane insolublesinsoluble mat-ter that precipitates from a solution of oil in n-pentane underthe specified conditions.3.1.4 polar aromaticssynonym for p
10、olar compounds.3.1.5 polar compoundsmaterial retained on adsorbentclay after percolation of the sample in n-pentane eluent underthe conditions specified.3.1.6 saturatesmaterial that, on percolation in a n-pentaneeluent, is not adsorbed on either the clay or silica gel under theconditions specified.4
11、. Summary of Test Method4.1 The sample is diluted with solvent and charged to aglass percolation column containing clay in the upper sectionand silica gel plus clay in the lower section. n-pentane is thencharged to the double column until a definite quantity ofeffluent has been collected. The upper
12、(clay) section is removedfrom the lower section and washed further with n-pentane. Atoluene-acetone mixture 50 to 50 by volume is then charged tothe clay section for desorption and a specified volume ofeffluent collected. The lower (gel) column may be desorbed byrecirculation of toluene.4.2 The solv
13、ents are completely removed from the recov-ered n-pentane and the toluene-acetone fractions and theresidues are weighed and calculated as saturate and polarcompounds contents. Aromatics may be calculated by differ-ence, or measured following evaporation of the toluene usedfor desorption of the gel c
14、olumn.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and is the direct responsibility of SubcommitteeD02.04 on Hydrocarbon Analysis.Current edition approved May 10, 2003. Published June 2003. Originallyapproved in 1968. Last previous edition app
15、roved in 2002 as D 200702.2Annual Book of ASTM Standards, Vol 05.01.3Annual Book of ASTM Standards, Vol 09.01.4Annual Book of ASTM Standards, Vol 06.04.5Annual Book of ASTM Standards, Vol 14.02.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr
16、Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.4.3 When the sample contains more than 0.1 mass % ofn-pentane insolubles, this test method cannot be used directly.The insoluble matter must be removed from the sample prior tocharging to the column. A method for this removal
17、 is given asan appendix.4.4 Alternative methods are provided (1) for recovery ofaromatics from the gel column, and (2) for analysis of oil withhigh-polar content.5. Significance and Use5.1 The composition of the oil included in rubber com-pounds has a large effect on the characteristics and uses of
18、thecompounds. The determination of the saturates, aromatics, andpolar compounds is a key analysis of this composition.5.2 The determination of the saturates, aromatics, and polarcompounds and further analysis of the fractions produced isoften used as a research method to aid understanding of oileffe
19、cts in rubber and other uses.6. Apparatus6.1 Beakers, Anticreep, 150-mL capacity, as illustrated inFig. 1.(WarningBeakers should be examined for sharpedges and fire polished, if necessary.)6.2 Clay-Gel Column, constructed as illustrated in Fig. 2.6.3 Conical Flasks, (Erlenmeyer), 250-mL capacity.6.4
20、 Solvent Receiver, capable of collecting solvent, withoutsplashing or loss of material during the analysis. A wide-mouth, graduated, 500-mL capacity Erlenmeyer flask is onesuch example that has been found suitable to use.6.5 Filter Funnel, long stem, 125-mm diameter; for use with185 mm ready folded,
21、 fine-texture, rapid filter paper.6.6 Separatory Funnel, 500 mL.6.7 Hot Plate, explosion proof, controlled to a surfacetemperature of 100 to 105C.NOTE 2Temperatures should be uniform on the top of the hot plate.Some laboratory hot plates benefit by the inclusion of an aluminum plate,approximately 6-
22、mm thick, included under or on top of regular plate top.6.8 Round Bottom Flask, 3-necked, borosilicate, 500-mLcapacity (Fig. 3).6.9 Condenser, borosilicate (Fig. 3).6.10 Adapter Tube with Vigreux column (Fig. 3).6,76.11 Flexible Joint, TFE-fluorocarbon and borosilicate,24/40 TSground glass joints on
23、 each end.7,87. Reagents and Materials7.1 Purity of Reagents, Reagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the commit-tee on Analytical Reagents of the American Chemical Society,where such specif
24、ications are available.9Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.7.2 Acetone, reagent grade, minimum purity. (WarningAcetone is extremely flammable.)7.3 Calcium Chlori
25、de, anhydrous granules.7.4 Clay Adsorbent, 500 to 250 m (30 to 60 mesh)Attapulgus.7,10Clay quality may be determined using theazobenzene equivalence test shown in Annex A1. The azoben-zene activity test measures the adsorptive characteristics of theclay. Azobenzene equivalence value should be 30 to
26、35. Clayoutside of these limits should be discarded.7.5 Cyclohexane, conforming to Specification D 5309. (Op-tional, see 8.1.9.) (WarningCyclohexane is extremely flam-mable. Harmful if inhaled.)7.6 Pentane,7,11reagent grade minimum purity.(Warningn-Pentane is extremely flammable. Harmful ifinhaled.)
27、7.7 Silica Gel, activated, conforming to the following in-spections:7,126The sole source of supply of the adapter tube known to the committee at thistime is Owens Glass Apparatus, Inc., 128 River Road, Channelview, TX 77530This item can be fabricated at any scientific glassblowing shop.7If you are a
28、ware of alternative suppliers, please provide this information toASTM International Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee1, which you may attend.8Cole Parmer No. 6675-40 has been found suitable for this purpose.9Reagent Ch
29、emicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand Natio
30、nal Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.10The sole source of supply of clay adsorbent known to the committee at thistime is Forcoven Products, 22010 East Martin Dr., Porter, TX 77365. Packaged inmoisture resistant twinned packets of 50 and 100 g (sufficient for one de
31、termina-tion). These packets are packed 50 sets per case. It is important that extremes oftemperature be avoided on stored clay samples.11The sole source of supply of pentane known to the committee at this time isSpecial Products Div., Phillips Petroleum Co., Bartlesville, OK.12The sole source of su
32、pply of silica gel meeting these specifications known tothe committee at this time is Forcoven Products, 22010 East Martin Dr., Porter, TX77365, packaged in 200 g moisture resistant packets. Sieve analysis should bechecked on other sources of gel.FIG. 1 Anticreep BeakerD2007032Sieve analysis 30 siev
33、e size, 5 % (mass) maximum;50 sieve size, 45 % (mass) min100 sieve size, 80 % (mass) min200 sieve size, 94 % (mass) min7.7.1 Gel should be activated for4hinanairoven at 190Cin a shallow pan.7.8 Toluene, reagent grade minimum purity. (WarningToluene is flammable. Vapor harmful.)7.9 Toluene-Acetone Mi
34、xture (50 to 50 by volume), mixequal volumes of toluene and acetone.7.10 In order to obtain results that are consistent with thoseobtained elsewhere, it is very important that only the reagentsand materials described in this section be used.8. Procedure8.1 Fractionation:8.1.1 Prepare the adsorption
35、column (Fig. 2) by placing 100g of clay adsorbent in the upper section of the column and 200g of silica gel plus 50 g of clay on top of the gel in the lowersection (Note 4). Place a piece of glass wool (of about 25-mmloose thickness) over the top surface of the clay in the uppercolumn to prevent agi
36、tation of the clay while charging theeluent solvents. Join the columns (clay over gel) after lubri-cating the joint with hydrocarbon-insoluble grease. It is impor-tant that the adsorbents in each column be packed to a constantlevel. A minimum of ten taps with a soft rubber hammer atdifferent points
37、up and down and 25 taps on top of each columnshould be employed to achieve constant level. A suitablerubber hammer may be assembled by fastening two No. 7 or 8rubber stoppers on one end of a small rod about 200-mm long.Use fresh adsorbents for each determination.8.1.2 If n-pentane insolubles were no
38、t determined, select theappropriate sample size in accordance with the following polarcontent ranges, if the proper range can be anticipated; other-wise, use a 10 6 0.5 g sample.Polar Content Range,mass percent Sample Size, g020 10 6 0.5Above 20 5 6 0.28.1.3 Dilute with 25 mL of n-pentane solvent an
39、d mix wellto ensure a uniform solution of the sample. The sample shouldnot display precipitate or flocculate at this point. If a precipitateis present asphaltenes may be removed by the procedure ofAppendix X1, however, the precision statement no longerNOTECheck to ascertain ID is 44 mm.FIG. 2 Clay-G
40、el Percolating ColumnD2007033applies. It is important that the polar content result obtained benot greater than that for the sample size as specified above,since the capacity of the clay for retaining polar constituentsbecomes limited at these concentrations. If results exceed thisspecification, rep
41、eat the test using a smaller sample. Partition-ing between aromatics and polar compounds is affected bysample size. Results using different sample size may not beequivalent.NOTE 3For viscous oils, dilutions of the sample with 25 mL ofcyclohexane is more convenient and does not affect the results. Cy
42、clo-hexane used in this manner will not detect small quantities of asphaltenes,however.8.1.4 Add 25 mL of n-pentane to the top of the clay portionof the assembled column and allow to percolate into the clay.As soon as nearly all of the n-pentane has entered the clay,charge to the column the diluted
43、sample of 8.1.3. Wash thesample beaker (or flask) with n-pentane and add the washingsto the column. After nearly all of this material has entered theclay, wash the walls of the column above the clay free ofsample with n-pentane. The sample and eluent solvent can beadded to the column through a 65-mm
44、 diameter, wide-stemfunnel (the funnel can be left on top of the column). At no timeduring the run should air be allowed to enter the clay bed.8.1.5 When nearly all of the washings have entered the clay,charge n-pentane to the column and maintain a head level wellabove the clay beds (Note 4) to wash
45、 the saturate portion of thesample from the adsorbents. Recover 280 6 10 mL of the firstn-pentane effluent from the column in a graduated, 500-mLwide-mouth conical flask.NOTE 4Columns may be briefly separated, if necessary, to give asolvent head 5- to 10-mm deep in the second (lower) column. Loss of
46、 thehead will give channeling in the lower column, with inaccurate results.NOTE 5With long use, the frits in the absorption columns becomeprogressively less porous. If the time for percolation doubles over that fora new column, the slow columns are to be discarded.NOTE 6If only saturates are to be d
47、etermined, proceed to 8.3 andsubsequent calculation of saturates.8.1.6 Disconnect the two sections. Allow the lower sectionto drain into a receiver. Continue washing the upper claysection with n-pentane. Maintain a moderate liquid head levelabove the clay during this wash and adjust n-pentane additi
48、onsso that the level is about 25 mm when 150 mL have beencollected in the receiver. Discontinue additions at this point andallow the liquid to essentially drain from the column. Thequantity in the receiver should then be about 200 mL. Then-pentane from this step and from the draining of the lowerFIG
49、. 3 Extraction ApparatusD2007034column should be discarded if aromatics are to be determinedby difference. This n-pentane should be added to the aromaticssolution from the gel column during solvent evaporation (8.3)if aromatics are to be recovered.NOTE 7This extra n-pentane washing of the clay section is necessaryin order to ensure complete removal of aromatics from the clay.8.1.7 After n-pentane effluent has essentially drained fromthe column, charge a 50 to 50 volume mixture of tolueneac-etone. Collect the effluent in a 500-mL separatory funnel.Collect 250 mL
