1、Designation: D2007 11 (Reapproved 2016)Standard 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 D2007; the number immediately following the
2、 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 () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers a
3、 procedure for classifying oilsamples of initial boiling point of at least 260 C (500 F) intothe hydrocarbon types of polar compounds, aromatics andsaturates, and recovery of representative fractions of thesetypes. This classification is used for specification purposes inrubber extender and processi
4、ng oils.NOTE 1See Test Method D2226.1.2 This test method is not directly applicable to oils ofgreater than 0.1 % by mass pentane insolubles. Such oils canbe analyzed after removal of these materials, but precision isdegraded (see Appendix X1).1.3 The values stated in SI units are to be regarded as t
5、hestandard. 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 determine the a
6、pplica-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:2D2226 Classification for Various Types of Petroleum Oilsfor Rubber Compounding UseD5309 Specification for Cyclohexane 999E691 Pr
7、actice for Conducting an Interlaboratory Study toDetermine the Precision of a Test Method3. 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 per
8、colation, 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 aromaticssynony
9、m for polar 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 spec
10、ified.4. 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
11、 upper (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 T
12、he solvents 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 bydifference, or measured following evaporation of the tolueneused for desorption of the
13、gel column.4.3 When the sample contains more than 0.1 % by 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 is given asan appendix.1This test method is under the jurisd
14、iction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.04.0C on Liquid Chromatography.Current edition approved Oct. 1, 2016. Published November 2016. Originallyapproved in 1968. Last previous edition approved in 2011 as D20
15、07 11. DOI:10.1520/D2007-11R16.2For 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.*A Summary of Changes section
16、appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States14.4 Alternative methods are provided (1) for recovery ofaromatics from the gel column, and (2) for analysis of oil withhigh-polar content.5. Significan
17、ce and Use5.1 The composition of the oil included in rubber com-pounds has a large effect on the characteristics and uses of 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 po
18、larcompounds and further analysis of the fractions produced isoften used as a research method to aid understanding of oileffects 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,
19、if necessary.)6.2 Clay-Gel Column, constructed as illustrated in Fig. 2.6.3 Conical Flasks, (Erlenmeyer), 250 mL capacity.6.4 Solvent Receiver, capable of collecting solvent, withoutsplashing or loss of material during the analysis. A wide-mouth, graduated, 500 mL capacity Erlenmeyer flask is onesuc
20、h example that has been found suitable to use.6.5 Filter Funnel, long stem, 125 mm diameter; for use with185 mm ready folded, fine-texture, rapid filter paper.6.6 Separatory Funnel, 500 mL.6.7 Hot Plate, explosion proof, controlled to a surfacetemperature of 100 C to 105 C.NOTE 2Temperatures should
21、be uniform on the top of the hot plate.Some laboratory hot plates benefit by the inclusion of an aluminum plate,approximately 6 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 Ad
22、apter Tube with Vigreux column (Fig. 3).3,46.11 Flexible Joint, TFE-fluorocarbon and borosilicate,24/40 TSground glass joints on each end.4,57. Reagents and Materials7.1 Purity of Reagents, Reagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents
23、 shall conform to the specifications of the commit-tee on Analytical Reagents of the American Chemical Society,where such specifications are available.6Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccu
24、racy of the determination.7.2 Acetone, reagent grade, minimum purity. (WarningAcetone is extremely flammable.)7.3 Calcium Chloride, anhydrous granules.7.4 Clay Adsorbent, 500 m to 250 m (30 mesh to 60mesh) Attapulgus.4,7Clay quality may be determined using theazobenzene equivalence test shown in Ann
25、ex A1. The azoben-zene activity test measures the adsorptive characteristics of theclay. Azobenzene equivalence value should be 30 to 35. Clayoutside of these limits should be discarded.7.5 Cyclohexane, conforming to Specification D5309.(Optional, see 8.1.9.) (WarningCyclohexane is extremelyflammabl
26、e. Harmful if inhaled.)7.6 Pentane,4,8reagent grade minimum purity. (Warningn-Pentane is extremely flammable. Harmful if inhaled.)7.7 Silica Gel, activated, conforming to the followinginspections:4,93The sole source of supply of the adapter tube known to the committee at thistime is Owens GlassAppar
27、atus, Inc., 128 River Road, Channelview, TX 77530. Thisitem can be fabricated at any scientific glassblowing shop.4If you are aware of alternative suppliers, please provide this information toASTM International Headquarters. Your comments will receive careful consider-ation at a meeting of the respo
28、nsible technical committee,1which you may attend.5Cole Parmer No. 6675-40 has been found suitable for this purpose.6Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Soc
29、iety, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.7The sole source of supply of clay adsorbent known to the committee at this timeis Forcoven Products,
30、22010 East Martin Dr., Porter, TX 77365. Packaged inmoisture resistant twinned packets of 50 and 100 g (sufficient for one determina-tion). These packets are packed 50 sets per case. It is important that extremes oftemperature be avoided on stored clay samples.8The sole source of supply of pentane k
31、nown to the committee at this time isSpecial Products Div., Phillips Petroleum Co., Bartlesville, OK.9The sole source of supply 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 resis
32、tant packets. Sieve analysis should bechecked on other sources of gel.FIG. 1 Anticreep BeakerD2007 11 (2016)2Sieve analysis 30 sieve 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 for 4 h in an air ov
33、en at190 C in a shallow pan.7.8 Toluene, reagent grade minimum purity. (WarningToluene is flammable. Vapor harmful.)7.9 Toluene-Acetone Mixture (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 i
34、mportant that only the reagentsand materials described in this section be used.8. Procedure8.1 Fractionation:8.1.1 Prepare the adsorption column (Fig. 2) by placing100 g of clay adsorbent in the upper section of the column and200 g of silica gel plus 50 g of clay on top of the gel in thelower sectio
35、n (Note 5). Place a piece of glass wool (of about25 mm loose thickness) over the top surface of the clay in theupper column to prevent agitation of the clay while chargingthe eluent solvents. Join the columns (clay over gel) afterlubricating the joint with hydrocarbon-insoluble grease. It isimportan
36、t that the adsorbents in each column be packed to aconstant level. A minimum of ten taps with a soft rubberhammer at different points up and down and 25 taps on top ofeach column should be employed to achieve constant level. Asuitable rubber hammer may be assembled by fastening twoNo. 7 or 8 rubber
37、stoppers on one end of a small rod about200 mm long. Use fresh adsorbents for each determination.8.1.2 If n-pentane insolubles were not determined, select theappropriate sample size in accordance with the following polarcontent ranges, if the proper range can be anticipated;otherwise, use a 10 g 6 0
38、.5 g sample.Polar Content Range,mass percent Sample Size, g020 10 0.5Above 20 5 0.28.1.3 Dilute with 25 mL of n-pentane solvent and 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
39、removed by the procedure ofAppendix X1, however, the precision statement no longerapplies. It is important that the polar content result obtained beNOTE 1Check to ascertain ID is 44 mm.FIG. 2 Clay-Gel Percolating ColumnD2007 11 (2016)3not greater than that for the sample size as specified above,sinc
40、e the capacity of the clay for retaining polar constituentsbecomes limited at these concentrations. If results exceed thisspecification, repeat the test using a smaller sample. Partition-ing between aromatics and polar compounds is affected bysample size. Results using different sample size may not
41、beequivalent.NOTE 3For viscous oils, dilutions of the sample with 25 mL ofcyclohexane is more convenient and does not affect the results. Cyclo-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 assembl
42、ed 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 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
43、 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 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 nearl
44、y 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 the saturate portion of thesample from the adsorbents. Recover 280 mL 6 10 mL of thefirst n-pentane effluent from the column in a graduated, 500 mLwide-mouth
45、conical flask.NOTE 4Columns may be briefly separated, if necessary, to give asolvent head 5 mm to 10 mm deep in the second (lower) column. Loss ofthe head will give channeling in the lower column, with inaccurate results.NOTE 5With long use, the frits in the absorption columns becomeprogressively le
46、ss 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 determined, proceed to 8.3 andsubsequent calculation of saturates.8.1.6 Disconnect the two sections. Allow the lower sectionto drain into a receiver. Conti
47、nue washing the upper claysection with n-pentane. Maintain a moderate liquid head levelabove the clay during this wash and adjust n-pentane additionsso 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
48、 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 lowercolumn should be discarded if aromatics are to be determinedby difference. This n-pentane should be added to the aromaticssolution from the gel column during
49、 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 mLof the toluene-acetone (plus n-pentane) effluentor until the effluent is practically colorless (only in exceptionalcases will more than 300 mL of effluent be required).8.1.8 Stop
