1、Designation: D4746 14Standard 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 revisio
2、n, 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. Scope*1.1 This test method covers the determination of thequinoline-insoluble matter (QI) in tar and pitch by pr
3、essurefiltration 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 units are to be regardedas standard. The values given in parentheses are mathe
4、maticalconversions 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 theresponsibility of the user of this standard to establish appro-priate safety and hea
5、lth 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-Solid BituminousMaterials (Pycnometer Method)D95 Test Method for Water in Petrole
6、um Products andBituminous Materials by DistillationD329 Specification for AcetoneD850 Test Method for Distillation of Industrial AromaticHydrocarbons and Related MaterialsD2318 Test Method for Quinoline-Insoluble (QI) Content ofTar and PitchD4296 Practice for Sampling PitchE1 Specification for ASTM
7、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 acetone, dried,and weighed.4. Significance and Use4.1 This test method is useful in e
8、valuating 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 stainless steel (304) jacketed block heatedby steam or cooled with water, sealed
9、 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 collar, and an adjustable plunger.5.1.1 The seal is accomplished when the seali
10、ng 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 seal between surfaces of thecrucible and the wall of the block. The filtration
11、of material isaccomplished by nitrogen (10 to 30 psig) introduced throughthe lid of the pressure filter. The filtrate exits from the draintube at the bottom of the block. The filtrate is disposed into aBuchner flask, attached to drain tube by a No. 7 rubber stopper.A vacuum hose is attached to the B
12、uchner flask and placed ina 100-mL beaker containing water to indicate the exit ofnitrogen when the filtration is completed.5.2 Beaker, 50 mL.5.3 Buchner Flask, 500.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liquid Fuels, and Lubricants and is the direct
13、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).DOI: 10.1520/D4746-14.2For referenced ASTM standards, visit
14、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 pressure filtration vessel known to thecommittee at this time is
15、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 technical committee,1which you may attend.*A Summary of Changes
16、section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States15.4 Filtering Crucible, porcelain, with a medium-porositybottom, top outer diameter 134 in. (45 mm), bottom outerdiameter 1.2 in. (30 mm), heig
17、ht 2 in. (50 mm).5.5 Analytical Balance.5.6 Desiccator.5.7 Thermometer, 0 to 300F (150C).5.8 Drying Oven, maintained at 221F (105C).5.9 Mortar and Pestle.5.10 Two Wash Bottles, 500 mL.5.11 Steam Bath.6. Reagents6.1 QuinolineRefined, meeting the following require-ments:6.1.1 The quinoline shall be di
18、stilled from 5 to 95 % withina range of 2F (1C) that shall include the temperature of459.3F (237.4C) after corrections for barometric pressureand emergent steam have been applied. The distillation shall becarried out in accordance with Method D850 using a total-immersion thermometer with a range fro
19、m 383 to 581F (195to 305C), graduated in 1F (0.5C) and conforming to therequirements for thermometer 69C as described in Specifica-tion E1. Temperature measuring devices such as precisionthermocouples, resistance temperature detectors (RTDs), andliquid-in-glass thermometers with equal or better accu
20、racies inthe appropriate temperature range may be used.6.1.2 The quinoline shall have a specific gravity at 15.5/15.5C of 1.092 to 1.098, as determined by Test Method D70,or other method of equivalent accuracy.6.1.3 The quinoline shall be clear and light in color and shallcontain less than 0.5 volum
21、e % of water as determined by TestMethod D95. If not, redistill the quinoline in an all-glassapparatus, discarding the first 5 % and collecting the next 90 %.If the quinoline contains suspended matter but is clear, light incolor, and contains less than 0.5 % water, filter the quinolinethrough a cruc
22、ible 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 distilled water. (WarningCorrosive.)6.3 Acetone, meeting Specification D329.(WarningFlammable (Health Hazard).)7. Haza
23、rds7.1 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, and prolonged contact with skin should be avoided.7.2 Observe proper laboratory procedures for handling anddi
24、luting 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 immediately before removing arepresentative portion for the determination or for dehydration.9. Dehydration of Sample9
25、.1 Hard PitchIf the solid bulk sample contains freewater, air dry a representative portion in a forced draft oven at122F (50C).9.2 Soft Pitch (Softening Point 140F (60C)If thepresence of water is indicated by surface foam on heating,maintain a representative portion of the bulk sample at atemperatur
26、e between 257 and 302F (125 and 150C) in anopen container until the surface is free of foam. Take care notto overheat, and remove the heat source immediately when thefoam subsides.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 arem
27、et.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 watercontent is less than 10 weight %, the QI content is corrected toa dry-tar basis (see 13.2). This alternative method app
28、lies onlyto stable emulsions of water in tar, that is, no water separateswhen the tar sample is left undisturbed for 24 h at roomtemperature.10. Preparation of Working Sample10.1 Pitch that is sufficiently hard at room temperature shallbe finely pulverized in a mortar. Crush this sample so that allF
29、IG. 1 Pressure FilterD4746 142of 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 be taken for the test shall besuch that the final quantity of quinoline insoluble (QI) shall benot less than 0.1 g. As a guide,
30、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 tars 10.0 to 25.010.2.1 When the sample contains 15 % QI or if the softeningpoint is greater than 248F (120C), the amount used fo
31、rtesting 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 determinations, clean it as follows.Remove the mat, wash the crucible with distilled water, dry,and ignite in a muffle furnace for1h
32、atabout 1472F (800C).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 still warm.11.2 After the crucible has been used for six determinations,remove any residual ash from pores in the filtering area by
33、boiling 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. 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
34、refined quinoline per gram of sample tobeaker.12.3 Place thermometer 0 to 300F (150C) (6 in. length)into solution and heat on steam bath to 167 6 10F (75 6 5C)for not less than 15 nor more than 20 min. Closely inspect thethermometer and bottom of the beaker for undissolved pitchand stir so that all
35、of the pitch is brought into solution.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 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.
36、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 thermometer. 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 wit
37、h 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 Fig. 1) of block. To close, force down by hand andattach clamp.NOTE 1Sealing of the crucible is a trial-and-error process. Excessivepressure coul
38、d cause the crucible to be pushed past the O-rings duringfiltration or not allow complete sealing of the lid. Insufficient pressure ofthe plunger could cause 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
39、 seeslight bubbling from the indicator before the filtrate can be seencoming from the drain. Once the filtrate is flowing, pressurecan be increased to 30 psig gradually. Nitrogen may bubbleslowly (caused by volume displacement in the collecting flask)through the water seal and may bubble fast when f
40、iltration iscompleted. When filtrate stops coming out of bottom, shut offnitrogen and remove lid.NOTE 2In some cases, nitrogen stops bubbling although there is nodraining of the filtrate. The filtration is actually completed, the quinolineinsolubles have compacted on the bottom (filter cake) of the
41、crucible anddo not let nitrogen pass through. By increasing the pressure, nitrogen willeventually break through the filter cake.12.11 Continue filtering the 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 la
42、st washing ispoured into the crucible, rinse the beaker with the wash bottle,allowing the solution to run into the crucible to remove anycarbon deposits. Filter the rinses.12.12 When the last filtration is complete, shut the steamand nitrogen off. Remove the lid and start cooling the blockwith water
43、 (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 lid 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, remo
44、ve the crucible, and wipe sideswith a paper towel containing acetone to remove any traces ofquinoline. Place crucible in an oven at 221F (105C) for aminimum of 30 min, preferably 1 h. Remove, place in adesiccator, and allow to cool for 30 min.12.15 Weigh the crucible containing quinoline insolublesa
45、nd 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. Underthese conditions, a stainless steel disk with a18-in. hole is added to thebottom of the block. Under high pressure, the crucible can be for
46、cedthrough O-rings. The stainless steel plate reduces the distance the cruciblewill travel to a minimum and thus avoids breakage and sample loss.13. Calculation13.1 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
47、the crucible, g; andW1= mass of the sample, g.D4746 143FIG. 2 Pressure Filter DimensionsD4746 14413.2 If the QI was determined on a wet tar sample (see9.3.2), 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 conten
48、t 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, and CapD4746 14515. Precision and Bias415.1 RepeatabilityDuplicate values by the same operatorshall not be considered suspect unless they differ by
49、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 location of selected changes to this standard since the last issue(D4746 98 (2013) that may impact the use of this standard. (Approved May 1, 2014.)(1) Revised
