1、Designation: D4746 141Standard Test Method forDetermination of Quinoline Insolubles (QI) in Tar and Pitchby Pressure Filtration1This standard is issued under the fixed designation D4746; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revisi
2、on, 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.1NOTEEditorial changes were made throughout the test method in September 2014.1. Scope*1.1 This test method covers
3、 the determination of thequinoline-insoluble matter (QI) in tar and pitch by pressurefiltration and gives results comparable to those obtained byTest Method D2318.1.2 Since this test method is empirical, strict adherence toall details of the procedure is necessary.1.3 The values stated in inch-pound
4、 units are to be regardedas standard. The values given in parentheses are mathematicalconversions to SI units that are provided for information onlyand are not considered standard.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is therespo
5、nsibility 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. Specific hazards aregiven in Section 7, 6.2, and 6.3.2. Referenced Documents2.1 ASTM Standards:2D70 Test Method for Density of Semi-So
6、lid BituminousMaterials (Pycnometer Method)D95 Test Method for Water in Petroleum Products andBituminous Materials by DistillationD329 Specification for AcetoneD850 Test Method for Distillation of Industrial AromaticHydrocarbons and Related MaterialsD2318 Test Method for Quinoline-Insoluble (QI) Con
7、tent ofTar and PitchD4296 Practice for Sampling PitchE1 Specification for ASTM Liquid-in-Glass Thermometers3. Summary of Test Method3.1 The sample is digested in hot quinoline and filteredthrough a heated pressure filter. The insoluble material iswashed with hot, fresh quinoline and with cold aceton
8、e, dried,and weighed.4. Significance and Use4.1 This test method is useful in evaluating and character-izing tar and pitch and as one element in establishing theuniformity of shipments and sources of supply.5. Apparatus5.1 Pressure Filtration VesselThe pressure filtration ves-sel3(see Fig. 1) is a s
9、tainless steel (304) jacketed block heatedby steam or cooled with water, sealed by a lid, flat gasket, andclamp. The interior of the block is designed to accept a 3A2Berlin porcelain filtration crucible (see 5.4). The crucible issealed within the block by the use of three O-rings, a cruciblesealing
10、collar, and an adjustable plunger.5.1.1 The seal is accomplished when the sealing lid isplaced on top of the block and clamped. The adjustable plungerapplies a force to the crucible sealing collar, which in turnpushes downward on the crucible and simultaneously com-presses O-ring gaskets, forming a
11、seal between surfaces of thecrucible and the wall of the block. The filtration of material isaccomplished by nitrogen (10 psig to 30 psig) introducedthrough the lid of the pressure filter. The filtrate exits from thedrain tube at the bottom of the block. The filtrate is disposedinto a Buchner flask,
12、 attached to drain tube by a No. 7 rubberstopper. A vacuum hose is attached to the Buchner flask andplaced in a 100 mL beaker containing water to indicate the exitof nitrogen when the filtration is completed.5.2 Beaker, 50 mL.1This test method is under the jurisdiction of ASTM Committee D02 onPetrol
13、eum Products, Liquid Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.05 on Properties of Fuels, Petroleum Coke and Carbon Material.Current edition approved May 1, 2014. Published May 2014. Originallyapproved in 1987. Last previous edition approved in 2013 as D4746 98 (2013)
14、.DOI: 10.1520/D4746-14E01.2For 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.3The sole source of supply of the p
15、ressure filtration vessel known to thecommittee at this time is Koppers Inc., 436 Seventh Ave., Pittsburgh, PA15219-1800. If you are aware of alternative suppliers, please provide this informa-tion to ASTM Headquarters. Your comments will receive careful consideration at ameeting of the responsible
16、technical committee,1which you may attend.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15.3 Buchner Flask, 500.5.4 Filtering Crucible, porcelain, with a medium-porosit
17、ybottom, top outer diameter 134 in. (45 mm), bottom outerdiameter 1.2 in. (30 mm), height 2 in. (50 mm).5.5 Analytical Balance.5.6 Desiccator.5.7 Thermometer, 0 F to 300 F (150 C).5.8 Drying Oven, maintained at 221 F (105 C).5.9 Mortar and Pestle.5.10 Two Wash Bottles, 500 mL.5.11 Steam Bath.6. Reag
18、ents6.1 QuinolineRefined, meeting the following require-ments:6.1.1 The quinoline shall be distilled from 5 % to 95 %within a range of 2 F (1 C) that shall include the temperatureof 459.3 F (237.4 C) after corrections for barometric pressureand emergent steam have been applied. The distillation shal
19、l becarried out in accordance with Method D850 using a total-immersion thermometer with a range from 383 F to 581F(195 C to 305C), graduated in 1 F (0.5 C) and conformingto the requirements for thermometer 69C as described inSpecification E1. Temperature measuring devices such asprecision thermocoup
20、les, resistance temperature detectors(RTDs), and liquid-in-glass thermometers with equal or betteraccuracies in the appropriate temperature range may be used.6.1.2 The quinoline shall have a specific gravity at 15.5/15.5 C of 1.092 to 1.098, as determined by Test Method D70,or other method of equiva
21、lent accuracy.6.1.3 The quinoline shall be clear and light in color and shallcontain less than 0.5 volume percent of water as determined byTest Method D95. If not, redistill the quinoline in an all-glassapparatus, discarding the first 5 % and collecting the next 90 %.If the quinoline contains suspen
22、ded matter but is clear, light incolor, and contains less than 0.5 % water, filter the quinolinethrough a crucible containing5gofcelite filter aid.6.1.4 Store the quinoline in a tightly closed, dark bottle.6.2 1 + 1 Hydrochloric Acid SolutionAdd equal volumeconcentrated hydrochloric acid to distille
23、d water. (WarningCorrosive.)6.3 Acetone, meeting Specification D329.(WarningFlammable (Health Hazard).)7. Hazards7.1 Fumes of the solvents should be removed by means ofproper hoods from all working areas. The working area shouldbe kept free of sparks and flames. Quinoline fumes should notbe inhaled,
24、 and prolonged contact with skin should be avoided.7.2 Observe proper laboratory procedures for handling anddiluting hydrochloric acid.8. Bulk Sampling8.1 Samples from shipments shall be taken in accordancewith Practice D4296 and shall be free of foreign substances.Thoroughly mix the sample immediat
25、ely before removing arepresentative portion for the determination or for dehydration.9. Dehydration of Sample9.1 Hard PitchIf the solid bulk sample contains freewater, air dry a representative portion in a forced draft oven at122 F (50 C).9.2 Soft Pitch (Softening Point 140 F (60 C)If thepresence of
26、 water is indicated by surface foam on heating,maintain a representative portion of the bulk sample at atemperature between 257 F and 302 F (125 C and 150 C)in an open container until the surface is free of foam. Take carenot to overheat, and remove the heat source immediately whenthe foam subsides.
27、9.3 TarA wet tar sample can either be dehydrated or usedas received as long as conditions stated in 9.3.1 and 9.3.2 aremet.9.3.1 Dehydrate a representative portion of the bulk sample.9.3.2 As an alternative to dehydration, the water content ofthe tar is determined by Test Method D95 and, if the wate
28、rcontent is less than 10 weight percent, the QI content iscorrected to a dry-tar basis (see 13.2). This alternative methodapplies only to stable emulsions of water in tar, that is, no waterseparates when the tar sample is left undisturbed for 24 h atroom temperature.10. Preparation of Working Sample
29、10.1 Pitch that is sufficiently hard at room temperature shallbe finely pulverized in a mortar. Crush this sample so that allFIG. 1 Pressure FilterD4746 1412of it will pass the 250 m (No. 60) sieve. Soft pitches and tarsshall be warmed and well agitated before sampling.10.2 The amount of sample to b
30、e taken for the test shall besuch that the final quantity of quinoline insoluble (QI) shall benot less than 0.1 g. As a guide, the following sample sizes arerecommended:Sample Size, gCrude coke oven tar 5.0Horizontal retort tars 2.5Fiber pitch 5.0Other pitches 2.5Distilled tars 2.5Vertical retort ta
31、rs 10.0 to 25.010.2.1 When the sample contains 15 % QI or if the softeningpoint is greater than 248 F (120 C), the amount used fortesting should be reduced, but to not less than 0.5 g.11. Crucible Preparation11.1 If the crucible, after thorough cleaning (see 11.2), hasbeen used for less than six det
32、erminations, clean it as follows.Remove the mat, wash the crucible with distilled water, dry,and ignite in a muffle furnace for1hatabout 1472 F (800 C).Cool the crucible slowly by placing it in a drying oven for 1 hafter removal from the furnace to prevent cracking and place itin a desiccator while
33、still warm.11.2 After the crucible has been used for six determinations,remove any residual ash from pores in the filtering area byboiling in1+1hydrochloric acid solution. Refer to 6.2. Thenboil the crucible in distilled water, thoroughly back wash withdistilled water, dry, and ignite as in 11.1.12.
34、 Procedure12.1 Weigh the recommended amount of sample (usually2.5 g) into a 50 mL beaker and record weight (W1).12.2 Add 2.0 mL of refined quinoline per gram of sample tobeaker.12.3 Place thermometer 0 F to 300 F (150 C) (6 in.length) into solution and heat on steam bath to 167 F 6 10 F(75 C 6 5 C)
35、for not less than 15 min nor more than 20 min.Closely inspect the thermometer and bottom of the beaker forundissolved pitch and stir so that all of the pitch is brought intosolution.12.4 Place gaskets into the pressure vessel.12.5 Start to heat block with steam (see 5.1 and Fig. 2).12.6 Weigh a 3A2
36、Berlin crucible and record mass (W2).12.7 Place the preweighed crucible in the pressure vesseland then put crucible collar on (see 5.1 and Fig. 3).12.8 When the quinoline-pitch solution has completed theheating cycle (see 12.3), pour the solution into the crucible,decanting it alongside the thermome
37、ter. Wash down the ther-mometer and beaker with 5 to 10 mL of quinoline and place onthe steam bath.12.9 Place the lid of the pressure filter with the adjustableplunger on the pressure vessel. The plunger shall be adjusted sothat there is about18 to14 in. gap between the lid and the flatgasket (see F
38、ig. 1) of block. To close, force down by hand andattach clamp.NOTE 1Sealing of the crucible is a trial-and-error process. Excessivepressure could cause the crucible to be pushed past the O-rings duringfiltration or not allow complete sealing of the lid. Insufficient pressure ofthe plunger could caus
39、e leaks around the O-rings.12.10 Add 10 psig of nitrogen using the pressure controllerto pressurize the vessel to 10 psig with nitrogen. One may seeslight bubbling from the indicator before the filtrate can be seencoming from the drain. Once the filtrate is flowing, pressurecan be increased to 30 ps
40、ig gradually. Nitrogen may bubbleslowly (caused by volume displacement in the collecting flask)through the water seal and may bubble fast when filtration iscompleted. When filtrate stops coming out of bottom, shut offnitrogen and remove lid.NOTE 2In some cases, nitrogen stops bubbling although there
41、 is nodraining of the filtrate. The filtration is actually completed, the quinolineinsolubles have compacted on the bottom (filter cake) of the crucible anddo not let nitrogen pass through. By increasing the pressure, nitrogen willeventually break through the filter cake.12.11 Continue filtering the
42、 sample as described in 12.8 to12.10 until the filtrate is clear. This usually will take aboutthree washings of the beaker. When the third or last washing ispoured into the crucible, rinse the beaker with the wash bottle,allowing the solution to run into the crucible to remove anycarbon deposits. Fi
43、lter the rinses.12.12 When the last filtration is complete, shut the steamand nitrogen off. Remove the lid and start cooling the blockwith water (it takes approximately 5 min to cool the block andcrucible).12.13 Once cool, fill the crucible to about three quarters ofits volume with acetone. Place li
44、d on and follow 12.10 to filter.Perform this step three times.12.14 When acetone rinses are complete, shut off thenitrogen, remove the lid, remove the crucible, and wipe sideswith a paper towel containing acetone to remove any traces ofquinoline. Place crucible in an oven at 221 F (105 C) for aminim
45、um of 30 min, preferably 1 h. Remove, place in adesiccator, and allow to cool for 30 min.12.15 Weigh the crucible containing quinoline insolublesand record the mass (W3).NOTE 3For pitches yielding slow-filtering quinoline insolubles, ahigher pressure may be used of up to 50 but not to exceed 75 psig
46、. Underthese conditions, a stainless steel disk with a18 in. hole is added to thebottom of the block. Under high pressure, the crucible can be forcedthrough O-rings. The stainless steel plate reduces the distance the cruciblewill travel to a minimum and thus avoids breakage and sample loss.13. Calcu
47、lation13.1 Calculate the quinoline-insoluble (QI) content as fol-lows:QI,%5 W32 W2!/W1# 3100 (1)where:W3= mass of crucible with QI, g;W2= mass of the crucible, g; andW1= mass of the sample, g.D4746 1413FIG. 2 Pressure Filter DimensionsD4746 141413.2 If the QI was determined on a wet tar sample (see9
48、.3.2), correct the QI value determined in 13.1 to a dry-tar basisas follows:QI, mass % dry basis! 5QI, mass % wet basis! from 13.1100 2 water content of tar, mass %!3100(2)14. Report14.1 Report the quinoline insoluble (QI) content to thenearest 0.1 %.FIG. 3 Pressure Filter Tension Adjuster, Collar,
49、and CapD4746 141515. Precision and Bias415.1 RepeatabilityDuplicate values by the same operatorshall not be considered suspect unless they differ by more than0.2 %.15.2 ReproducibilityThe values reported by each of twolaboratories, representing the arithmetic average of duplicatedeterminations, shall not be considered suspect unless theydiffer by more than 0.3 %.16. Keywords16.1 coal-tar insolubles; pitch; pressure filtration; QI;quinoline-insolubles; tarSUMMARY OF CHANGESSubcommittee D02.05 has identified the
