Designation: D 4530 - 07 Standard Test Method for faq: tay 1S0 10390 Determination of Carbon Residue (Micro Method)’ “hd sel mdr he il sition 450 he mb ella owing he iain nents ye Te sdyuny ov te eerie yo ean h unpre ics ea pe ‘Seger an tol ge neh nt vn Rena "Wi sadn se pane or se br gee he Dare Dee, 1, Scope [LI This test method coves the determination ofthe amount of carbon residue (See Note |) formed after evaporation and pyrolysis of petroleum materials under certain conditions and is intended (© provide tome indication of the weative coke Forming tendeney of such materials. 1L2 The test results are equivalent tthe Conradson Carbon Residue tex (see Test Method D189). Nore 1—Thisprcadne is 4 modication of the gil med nt appre for erbon rue of pales) mata here hs Boe momired Hat emogroviery is another apleale leas Fomever si the reapomsiy of he perc To exalsh esting centione i in quale resus wher using themegavisry 1.3. This ext mosh is applicable to peuroleum preducs that, partially decompose on disillation at atmosphere pressure and ‘vas tested for carbon reside values of 0.10 t0 30 % (rn) Samples expected to be below 0.10 weight % (sum) residue should be distilled to remove 90 % (V/V) of the Nask charge (see Section 9). The 10 % bottoms remaining is then ested for ‘atbon residue by this nt wei 1.4 Asteforming constuens, a8 defined by Test Method 1D 482, or non-volatile actives present in the sample will add to the carbon residue value and be included as par of the total ceubon residue value reported, LS Also in diesel fel, he presence of alkyl mirates, suchas amyl meat, hexyl aitate, oF octyl nitrate, causes a higher tatbon residue value than observed i untvented fuel, which may lead to erroneous conclusions as to the coke-forming propensity ofthe fuel. The presence of ulkyl nitrate in the fue] ‘may be detected by Test Method D Ib, 116 The values sated in SI units are to be regarded as dhe standard, The values given in parentheses are for information aly TT This stondant does not purport to address all of the safery concerns, if any. associated with is use. ft és the responsibilty ofthe user ofthis standard to establish appr olan dicta abe ane as dec rp a Sebeneme DiEDS on Auta! be ‘ur csi apes Rw, 207. Pah Dsante 00-OFealy appre 195 La ei elon posed 20 NDA ‘Se a Wl 6 ly 98 pp. 98 priate safesy practices and w determine the applicability of regulators limitations prior 10 use. For specific warning statements, see 8.2.3 and 8.4 2, Referenced Documents 2.1 AST Standards: * D 189 Test Method for Conradson Carbon Residue of Petroleum Produess D482 Test Method for Ash from Petroleum Products [D404 Test Method for Alky! Nitrate in Diesel Puels by Spectrophotometry 4NS? Proetce for Manual Sampling of Pewoleum and Peiroloum Products 14177 Proctce for Awomatie Sampling of Petroleum and Peirolevn Produess Specification for ASTM Liquid-in-Glass Thermometers E 1A Specification for Distillation Equipment 22. Energy hnvitnte Slender Spocitioatin for HP Standars Thermometers © 3. Terminoiogy 3 Definitions 3.11 carbon residue, ain petroleum products, the pa Femaining.alier_a sample his. been subjected 19 thermal decomposition, BALL Discussion —The amount of reside is dependent on the test conditions of evaporation and pyrolysis. The erm may be imisteading bere in thatthe residue may contain other than carbon decomposition products. However, tbe term is etained de Wo is wide common usage. 4. Summary of Test Method 4.1 A weighed quantity of sample is placed in glas vist and heated wo SOOPC under an inert (nitrogen) atmosphere in a controlled manner fora specific time. The sample undergoes coking reactions, and volatiles formed are swept away by the Tor eed AST wa, vik te ASTM web wat ot engin noe Stat or A Teka of Pr Sod! Ms Jor Pot on Po a 83. Re ty aie “A Summary of Changes etn appre ee ond oft nara ‘comp @ #874 Moai 0 a ve 20x Cea, AEoF nitrogen. The carbonaceous-ype reside remaining is reported «sa percent ofthe original sample as “carbon residue (micro).” 4.1.1 When the test result is expected to be below 0.10 % (ini), the sample can be distilled to produce a 10% (VIV) bottoms, priar to performing the test 5B ificanee and Use 5.1 The catbon residue value of the vatious petroleum materials serves as an approximation of the tendeney of the ‘material to form carbonsceous type deposits under degradation cconcitions similar to those used in the test method, and can be sell as a guide in manufacture of cersin stocks. However, care needs io be exercised i interpreting th result, ‘52 This test method offers advantages of beer contol of test conditions, smaller samples, and less operator atention compared to Test Method D 19, 10 which ics equivalent 5.3 Up 10 weve samples may be run simulkoncously. inluging a conto sample wher the vial holder shown is used exelasively for sample analysis, 6. Apparatus 6.1 Glass Semple Vals, 2-mil- capacity, 12-mm ouside diameter by approximstely 35-:im high, 62 Larger 4edram Glass Sample Vials. \S-nL. capacity (20.5 wo 21-1nm ouside diameter by 70 = 1-inm high), may be used for samples that are expected 1o yield eesidues 20.10 % (ow) s0 that a moe appreciable mass difference can be determined. I should be ned the precision statements forthe test method were determined using the 2-mL eapocity vials ‘nly (with sample residues between 0.3 and 26 % (min) and thatthe precision associated with using the larger sample Vals hhas not been determined 1G, Y Sample Vat Holder ana Vist, 63 Bvedropper Syringe, or Smal Rod, Yor sample wanser 64 Coking Oven with circular heating chamber approxi- imately 85 mem (3% in) in diameter by 100-mm (in) deep. for top loading, with heating capabiiy From 10 10 40°Ciin ‘ate to 300°C. with exhaust port 13-mm tin. inside diameter For sivogen purge of oven enamiber inlt near top, exhaust at ‘boston emer) with thermocouple sensor located in oven ‘chamber nex! but aot touching sample vials, with lid capable ‘of sealing ou air, and wth removable condensate tap located at the oven chamber base. schematic diagram is piven in Fis, 65 Sample Vial Hofder—Cylindreal aluminum block, 29- proximately 76 mm (3 in.) in diameter by 16mm Ain. tick, with weve evenly spaced holes (Yor vials) each 13 men (3 in.) in diameter by 13-mm (/-in.) deep, The holes are arranged in 4 circular pattem approximately 3 mm (4 in.) from the perimeter The holder has legs G-nom (Vin. Hong, sith gues to-center in oven chamber, ad an index mark onthe side o use 138 positon reference, The sample val holder is shown ia Yi. H 64 A modified version of the standard sample vial holder (see Fig. 1) is required when larger glass sample vials (see 6.2) fre used. The modified sample wal holder is simi in nature to the owelve hole vial holder except that there are sis evealy spaced holes (for vials) each 21.2 + 0.1 mm in diameter by approximately 16-mm deep, aranged in a cireuar pater. 6.2 Thermocouple, suitable for controller and temperature range of interest, with exterior temperature readout. degrees Celsius. 68 Analytical Balance, with 0.1 mg sensitivity to 20 minimum weighing capacityiy 0 4500-07 wo cenwoe nue EZ oa srameess see, | ‘em OUTER ErLIMOMGAL SHELL sal = vara vaste (ee atau suone ae? Se counennare FIG. 2 Coking Oven and Lid 69 Mirogen, minimum 99.998 % purity with suitable ‘means of delivering a pressure of 0 10 200 KPa (0 to 30 psig) Cylinders of zero grade mitogen have been found suitable to 7. Sampling 7.1. Using the practices ourtined ia Practice 1 3087 (manual saraping) or Practice D 4177 (automatic sampling) eure that a representative sample of mati 1o be tested is.siaine. 8, Procedure 8.1 Sample Preparation: 8111 Determine the mass of each clean sample val being ‘sed inthe sample analysis, and record the mass to nearest 0.1 mg. 8.1.2 During weighing and filling, hanele vials with forceps to help minimize weighing enrrs. Discard the sample vials aller use 3 8.1.3 Its assumed that a representative sample ofthe stock (oF provess has been obtained for laboratory use following Practice D 4057 or similar standard. Sti the sample to b2 tested, frst warming iT necessary (0 reduce its viscosity. Samples thar ave homogencous liquids can be wansTered dicetly 1 vials using a rod, syringe. or eyedropper. Solid raterals may also be heated; oF frozen with liquid nitsogen, ‘ad then shatered to provide manageable pieces. 8.14 Transfer an appropriate mass ofthe sample (se Table 1) into @ ared-sample vial, reweigh to nearest 0.1 mg, and cco, Place the loaded sample vials imo vial holdes (op 0 twelve), noting postion of each sample with respect io index mark Nove 2 coal spe an be aca i ec ba oF sales teing stl Thc contol spe sol! be pial tht is Pe ese a eas 20 is ine se euipent in ore dee wera Breet carbon reside al andar devon, Resi or euch bch re feoma aceite when ree for the control sap Fl within the tvenge percent carbo resive = hee Sandan devin Cota “TABLE 1 Guide fr Sample Size Teipesss aon Faconenser Senge Deserotan Foveve tums —_Sangie See 9 ‘Back rovers > Bis 005Ay 04500-07 rer hat ue od hee Lis aca problems wi the rocee ‘ihe cqipment 82 Processing of Samples 8.2.1, With the oven a ess chan 100°C, place the val holder imo the oven chamber and sectre Hid, Purge with nitrogen for at east 10 min a 600 mLfni, Then decrease the purge to 150 mL/min and heat the oven slowly to 500°C at 10°=15°C/nin 82.2 If the sample foams oF spatiers, causing loss of sample, diseard and repeat the test Nowe 3~Spateing may be de o water dha ean be removed by pie ule Hens aa veto, followed by a wivogen sweep. Aleratel. Smale sal ae cun be ws 8.23 Hold oven at $00 ++ 2°C for 15 min. Then shut off furnace power and allow oven to cool Feely while under nitrogen purge of 600 mLoxin. When aven temperature is less than 280°C, remove the vial holder for funder cooling in esiceator After the samples are removed fiom the oven, the nitrogen purge may be shutoff. (Warning —Do not open oven ‘sir at any lime during the heating eycle, The introduction of air (oxygen) will likely cause the sample to ignite and spoil dhe test. (Because of the oven design and materials, such an ‘nition is notmally not a hazard co the operator) Open the ‘oven only afer oven temperaure falls below 250°C during the cooling step. Maintain nitogen Mow until ater tbe vial holder hhas been removed from the oven.) (Warning—Locate the coking oven in laboratory exhaust hood for safe venting of smoke and fumes. Altematively, install vent Tne from MCRT ‘oven exhaust to laboratory exhaust system) (Waraing—Il a ‘vent line is used, do not conneet dirty to exaust chimney 10 avoid creating neyative pressur inthe Tine.) ti tow fst eolng As equi bythe posed te socom ‘Sean ated when eon hs bea cold low 10D 83 Final Weighing—Trasfer sample vials kmsiained in place inte val hold) desiccator and alow vials cool 0 oom temperature, Weigh the cooled vials othe nearest 0.1 mg fang record. Handle the vials with frzeps. Discard the uscd sass sample vals 84 Occasionally examine the condensate rp ashe bot of the oven ehatiber: emply if necessary and replace {Warning The condensate trap residue may have some ‘areinogenie materials present Avoid contact withthe trap residue dispose of it 4m aeconlance with local laboratory practice) 9, Procedure for Carbon Residue on 10 4 (V/V) Distillation Residue 9.1 This procedure is applicable to light distlate materials, such a8 ASTM No’ | and No, 2 fast oil or materials expected tw have Tess than .1 4 (n/n) carbon residue. 92 A disilaion analysis using either 2 100 oF 200-mL. staring volume is requited in order to collect a suificient amount of the 10 % (V/V residue needed in this analysis. Por 4 100-mL disillation, assemble the distlaion apparatus de- sevibed in Specitication £133, using Mase B (125-mL bulb volume), flask suppon board with $O-mm diameter opening, and graduated eylinder B (100-mL capacity). For a 200mL Gisllnion, assemble the disilation aparacas, described in Specification E153, using Mask D (250-mL bub volume), Mask Sppor bosrd with S0-mm diameter opeaing, and graduated cylinder C (209-ml. capacity). thermometer is not requte. but the use of the ASTM High Distillation Thermometer 8F or [8C, as prescribes in Specification E 1, or the IP High Distila. tion Thermomeir 6C, as prescribed in the Specification fou IP “Thermomowee, is ecommended. 9.3 Depending upon Which distillation Mas is used, place either 100 oF 200 mL of sample (as measured at ambient (emperature) into a tared distillation Ask that is held at a Temperature between 13°C and ambient. Maintain the eon- ‘denser bath temperature between 0 and 60°C 50 a5 19 provide ‘8 saficient temperature diferenial for sample condensation, ‘while avoiding any solidification of waxy material an tho condenser tube. Use, without elesning, the cylinder from which ‘e sample was measured as the receiver, and pee it so that the tp of the condenser does no touch the wal ofthe eylinde. ‘The receiver lemperature is required to be maintained at the same temperature (within =3°C) as the sample taken at the art of the test in onder to obtain an accurate volume Ieasufement in the receiving Mas, ‘944 ply the eat to the flask at uniform reso egulate thatthe Tist drop of condensate exits from the condenser between 10 and 15 min (for 200-mL. samples) or between 3 and 15 min (for 100-mL samples) after inital application of heat Altes the first diop Falls, move the eceivingeyliner so that the tip ofthe condenser tube tues she wal of the eylinder. Then regulate the heal so thatthe distiatien proceeds ata uniform fate of 819 14) mL/min oe 200-7 samples or wo $ mL/s (far 100-mL samples). For 200ml. samples, continue the istlaton vil approximately 178 ml. of dsillae has bese ‘collected, end thon diosontinus hang and allow the 20 denser to drain until 180 ml. (90 % (VV) of the charge to the Nas) has been collected in she eylindes, For 100-m. samples, continue the distillation unl approximately 88 mL of dislate has beon collected, and then diseontinue heating and allow the condenser 10 drain until 99 mL. (90 5 (VV) ofthe charge to the Nask) has been collected in the eying 9.5 Catch final drvinage, Hf aay, by immediately replacing the eylindse with a suitable container, sueh as a small Exien myer Mask, Add (0 this container. while sill warm. the Aistlation residue let inthe distiing flask, and mix wel, The contents of the container then represents & 10 % (V/V) distil Taton resid from the original product. ‘94 IF the disilaion residue is too viscous to ow freely at ambiont leriperatur, i is necessary to warm the disilation reside toa sulci temperature that will allow a potion of the material to be wansfered into a previously weighted vial for analysis (see Table 1). After allowing the material inthe vial to coo! to ambient temperature, determine the mass of the ‘est specinien tothe nearest O,| mg and carry out the earbon residue test in accordance with the procedure: described in Section», 10, Cateulation 10.1 Calewate Uke mass % eatbon residue in the original sample, or in the 10 distillation bavioms a follows 10.1.1 Caleulae pervent residue as follows:ly 0 4590-07 140 100 i } i I 020 oo ° 5 0 1s (2 46816.02( 5AMICRO METHOD CARBON AESOLE +3), (© 3.61602 (MICRO METHOD CARBON RESOLE +3) » 8 » 26 FG. 8 Corton Reside (tire) Precision ata 100) sexton rede = 20. a where: A. = carbon reside, g, and W = sample used, g 11. Report 111 Ror value np 4 10-6 cepa she val asin Micto Method carbon residue, percent to the nearest OI (nln) For values above 10, report the value obtained 1 the nearest (.1%% (mim). For Micro Method carbon residue on 10% disillaion residue, percent 1 the nearest 0.1 % (mim), 12, Precision and Bias © 12.1 The precision of this (es method as determined by (see Note 3) statistical examination of interlaboratory results is as follows ‘Nove $—Prcson daa wore gear by a sk ore ln 2004. TRe roond robie involved nie labora pevoeer ate in Alps alu. The ang ovals samples wa fom 0. 81025 BE (ond), No precision daa or eulaton das ei for maul otsised see lt ASTM natin Hee a my sng ses pat RR B19, sing 19 & boom or Sem. va, o hh, See X11 and Fp NTE raping a separate 13 comeaion ata tl wa peo Bewe “Test Methods D 49 and D530, 122 Repeotabiliy—The difference between two test re- sul, obtained by the same operator with the same appari ‘under constant operating contions on identical lest rater ‘would in the Tong eu, io the nal and enereet operation of the test method, exceed the vals shown in Fig. 3 in only one cise in twenty. 123 Repraducibilin—The difference between wo single and independent resuls, obtained by different aperators Work ing i different iboratores on identical est material, woud, in the long run, in the normal and eoreet operation of the test, rethod, exceed the values shown in Fig 3 in only one casein twenty 12.8 Bigs —The proceduce in Test Method D 4530 for mes suring cacbon residue of petroleum by the carbon residue method has no bias because the mass % of carbon residue ea be defined only in ceras of the test metho 13. Keywords 13.1 carbon residue: carbon residue (mero method: diesel Fuel lubricating dil; pouoieure products te tay enn seme Rp RR D102.: Qy 0.4590 -07 APPENDIXES: (Nonmandatory Information) XII A correlation (See Fig. X11) has been derived between the carbon residue test by the micro method and the ‘Conradion carbon residue test (see Test Methed D 188) in @ cooperative program involving 18 laborstories and six petvor Teatn materials. X12 Statistical analysis using modified Students ¢ tests ‘and nonparametic analysis show that, considering the preci- sions of both tests, thee is no difference between the two ‘methods, The date generated by the earbon residue tes by the Iiero method are statistically equivalent «9 the Conrson cachon residue 1st, except for better precision in the miro method residue tes. XI, CORRELATION TO OTHER METHODS IG, x1.1 Corttation of Gonradson and Carbon Resi (Micro) Tests 1X2, HELPFUL, HINTS FOR THE ANALYST X2.1_An exhaust system should be provided that will remove the small amount of smoke produeed during carbon residue testing. Any suction line sed lo draw the smoke aw should not be connected diectly to the MCRT chimney, Allow 1 small space between the chimney and the suetion Tie, This prevents a negative pressure from being created within the ‘paras, X22 The stmple vals should be handled only with loved nan oF forceps. X23 ‘The larger 4-dram vials should be used only for light oils and the samples that aro expected to yield residues fess ‘han 0.10 mim %. ‘X2A_ The final vesidve should be less than about 50 mg and preferably around 25 mg. If t6o much sample is taken, the material may boil over during heating, especially with hight residue oil. Use the equation andthe (able given inthis test method as a guide Tor recommended sample masses to be ‘akea, X25_IFthere is sparing o Foaming of samples during the initial heating stage, this may be due tothe presence of water inthe sample. A smaller sample size can be used or the water can be removed hy geatle heating in vacoum, fllowed by sitvogen sweep.lp 0 4500-07 SUMMARY OF CHANGES Subcommites D02.06 has identified the location of selected changes to this standard since the last ise (© 4530-06") that may impact the use of tis standard, (Approved Nov. 1, 2007.) (1) Updaved 9.3 and 95. Suibconntitise 02.06 has identified the location of selesiod changes to this standard since the fast issue (© 4530-03) that may impact the use of this standard, (Approved Jan, 1, 2006.) (2) Revised 11.1 G) Added Footnote 6. (@) Updated Fig. and Noe 5. ASTM minal oes poston apectg a ay a att ts azo in comcken wh my Yom rane ‘nih sandr, Ural edt ae express sd a neath ay ey sch a ane a nga sun rg ey a ot pa i staat stern yi yt ponte tc canmto ard rei oe yas ad “oaironand er raped win er conan anos ata vs saat alae sachet ul prone eevee cts cnon aren he ‘Me your row ta AST Cosa on Sanat oo sais oon poe ‘rs sont copyighed by ASTHt ato, 20 Bor Harr Drv, FO Box CQ, Wet Cnshochn PA 828 2050, ned Sis, na repr gi mate capes 2 er rar ay be ceed Oy concen AGT soe ios a Tesi Ses re), 10H a8 fv oF sens Tomal Height AGT wens