1、 IT IS THE USERS RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS PROCEDURE IN THE MANNER PRESCRIB
2、ED HEREIN CAN BE HAZARDOUS. SAFETY DATA SHEETS (SDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL THE MATERIALS USED IN THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION EQUIPMENT (PPE). COPYRIGHT 1968, 1980, 2002, 2016, 2018 UOP LLC. All rights re
3、served. Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States. The UOP Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at serviceastm.org, 610.832.9555 F
4、AX, or 610.832.9585 PHONE. Heptane or Toluene Insoluble Matter in Petroleum Oils Using Vacuum Filtration UOP Method 614-18 Scope This method is for the determination of either heptane or toluene insoluble material in petroleum oils. This method covers the range of 0.01 to 25 mass-% insolubles. Solid
5、 particulate materials interfere. More viscous or solid materials such as asphalts may be analyzed using this method but will require using a heated sonicating bath (up to 60C). The data provided by this method may be used as an index to coking tendency of petroleum oils when considering their suita
6、bility as charge stocks to cracking or other processes. Outline of Method A weighed sample is dispersed in ambient temperature solvent, either n-heptane or toluene, refluxed nominally at 80C for 2 hours, and filtered through a weighed glass microfiber filter using vacuum. Samples that cannot be comp
7、letely dispersed should not be analyzed by this method. The glass microfiber filter is dried at 100C and reweighed to obtain the weight of insoluble matter. Definition Asphaltenes are defined as the material present in oil fractions that is not soluble in light paraffinic solvents. They are fine, po
8、wdery, black-brown solids and are polymeric materials spanning a wide range of molecular weights. Their chemical composition is quite complicated. They appear to be closely associated with high molecular weight semi-polar naphthenic materials that require extended digestion time for separation. The
9、terms “heptane-insolubles”, “toluene-insolubles”, and “asphaltenes“ are often used synonymously. Apparatus References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used, unless stated otherwise. Balance, readable to 0.0001 g Clamp, for ring
10、 stand and sample cylinders. minimum opening 38.1-mm, VWR International, Cat. No. C6088-12 Clamp holder, for ring stand and clamp, VWR International, Cat. No. C6088-2 Condenser, glass 300mm with 24/40 fittings, VWR, Cat. No. KT431500-2430 2 of 8 614-18 Cylinder, graduated, 250-mL, Fisher Scientific,
11、 Cat. No. 08-559EC Desiccator, to hold Petri dishes Dishes, Petri, borosilicate glass, 60-mm diameter, Fisher Scientific, Cat. No. 08-746A Electromantle with stirrer, 250ml, VWR, Cat. No. 33749-326 Filter apparatus (300-mL glass filter holder and 1-L filtering flask), VWR, Cat. No. KT953825-0000 Fin
12、denser, Heidolph Radleys, Model RR31100, 400mm long, Cat. No. 015610003 Flask, round bottom 250-mL with 24/40 fitting, VWR, Cat. No. 80068-778 Flask, Erlenmeyer, narrow neck, 250-mL, with penny head, ground-glass, standard taper stopper, Fisher Scientific, Cat No. 10-100E Forceps, stainless steel, w
13、ith flat, polished tips for handling filters, Millipore No. XX62 000 06 Hot plate, stirring, capable of 80C must have round base plate to work with Starfish Work Station, such as Heidolph MR Hei-Tec, Cat. No. 036110582 Oven, capable of operation at 100C Pipet, volumetric transfer, disposable, 2-mL,
14、Fisher Scientific, Cat. No. 13-650-2C Pump, vacuum, Welch Director Direct Drive Pump, Fisher Scientific, Cat. No. 01-115-4 Ring stand, with rectangular base, 140- x 229-mm with 610-mm rod, VWR International Cat. No. 470104-060 StarFish Work Station, Heidolph Radley, works with round-top stirring hot
15、 plates; includes base plate Cat. No. 015890020, monoblock for 250-mL flasks Cat. No. 015890070, rod support Cat. No. 015890410, 5-way clamp for Findenser Cat. No. 015892140 Stir bars, egg shape 1 inch x , VWR, Cat. No. 80062-140 Stir bar retriever, polyethylene, VWR, Cat. No. 80062-180 Tubing, Tygo
16、n, inch ID x inch OD, 1/16-inch wall, VWR International, Cat. No. 89403-882 Ultrasonic bath, heated, 1.5-L capacity, VWR, Cat. No. 89375-494 Wash Bottle, 500-mL, fluorinated HDPE, Fisher Scientific, Cat. No. 03-409-17B Reagents and Materials References to catalog numbers and suppliers are included a
17、s a convenience to the method user. Other suppliers may be used, unless stated otherwise. Desiccant, indicating Drierite, Fisher Scientific, Cat. No. 07-578-3A n-Heptane, 99% minimum purity, Honeywell Burdick there should be no sample left clinging to the bottom. If the sample is not completely disp
18、ersed, place the flask in the ultrasonic bath for 5 minutes. Use a ring stand and clamp to suspend the flask in the bath. Continue this procedure until the sample appears to be completely dispersed. The sample must be completely dispersed in the solvent or the test is invalid. 7. Place a stir bar in
19、 the flask, place flask into the monoblock which has been set on the hot plate, and connect the Findenser. Adjust the stir rate to maintain a moderate vortex, and set heating to achieve 80C, 5C. Apparatus set-up is pictured in Figure 1. An electromantle may also be used for heating/stirring, and wat
20、er-cooled condensers can be used in place of Findenser. See apparatus set-up in Figure 2. As a best practice use of an over-temperature device that will cut power if any of the positions exceed 100C is recommended. 8. Reflux the sample on the stirring hot plate for 2 hours. 9. Place a glass microfib
21、er filter disc (rough side up) in a clean, dry, previously numbered Petri dish and place both the petri dish and filter paper in the oven at 100C for 30 minutes to remove moisture. Remove from petri dish and filter paper from oven and place in a desiccator to cool. 10. Add about 180 mL of diluent so
22、lvent, either n-heptane or toluene, to a 250-mL Erlenmeyer flask, place on hot plate and connect to a Findenser or water condenser. Heat to approximately 80C. Approximately 25-30 mL of warm solvent will be used for the final rinse for each sample in steps 17 to 20. 11. Weigh petri dish and filter pa
23、per to the nearest 0.0001 g. 12. Insert the base of the filter holder in the filtering flask. 13. Place the filter disc on the frit with rough side up in the base of the filter holder. 14. Attach the top (funnel) of the filter holder and clamp in place. 15. Apply a slight vacuum to the filter (see N
24、ote 1). Wet the filter with solvent to ensure good seal. 16. Raise and secure Findenser or water condenser and remove the flask containing the sample from the hot plate. Use a stir bar retriever to remove the stir bar from the sample flask. Rinse off the stir bar and retriever with the diluent solve
25、nt wash bottle. If using water condensers, turn off the water prior to removing flask. Wear heat resistant gloves when handling hot flasks 17. Stopper and shake the flask, then pour the contents on the filter. If the amount of insoluble material is high, pour the contents on the filter in aliquots.
26、18. Rinse stopper into the funnel with diluent solvent to collect any residual sample. 5 of 8 614-18 19. When the level of the solution has receded to the throat of the funnel, rinse the funnel using warm diluent (about 80C) solvent, washing down the sides of the funnel to rinse any sediment onto th
27、e filter (see Note 2). CAUTION: Heptane and toluene have low flash points. 20. Continue with vacuum until the solids on the filter appear to be dry. 21. Unclamp the filter holder and gently remove the funnel. If the sediment is unusually heavy (greater than 40 to 50 mg) some of it may tend to cling
28、to the throat of the funnel at the bottom where it meets the filter. Wash this material onto the filter using diluent solvent. 22. Examine the filter disc. The outer edge should be only lightly discolored if it was properly gripped by the holder. Wash the edge of the filter disc with a fine stream o
29、f diluent solvent to remove any oil that may have seeped under the edge of the holder until the filter appears dry. 23. Turn off the vacuum and carefully transfer filter to the Petri dish in which the disc was originally weighed. 24. Discard the filtrate. 25. Place the dish containing the filter in
30、the oven at 100C for 30 minutes to evaporate any residual solvent. 26. Remove the dish and filter, and cool in a desiccator until it reaches ambient temperature, approximately 30 to 45 minutes. 27. Reweigh to the nearest 0.0001 g. Note and report if any solid particles appear to be present on the fi
31、lter. Calculations Calculate the concentration of heptane or toluene insolubles using the Equation. Insoluble Matter, mass-% = 100(G-T) L- M where: G = gross weight of dish, filter and residue, g T = tare weight of dish and filter, g L = weight of round bottom flask and sample, g M = weight of round
32、 bottom flask, g Note the solvent used when reporting insolubles results. For values from 0.01 mass-% to 10.0 mass-%, report to two decimal places. For values 10.0 mass-% and higher, report to one decimal place. Notes 1. Do not use more vacuum than what is necessary because evaporation of solvent an
33、d consequent chilling of the mixture may occur and cause the wax to precipitate. 2. Rinsing the funnel is best done by using hot solvent. Do not allow the filter cake to become dry when rinsing as cracks may develop, allowing the solvent to flow through the cracks and not through the filter cake. Th
34、is incomplete washing could cause high results. 3. Scope of the method allows for determination of up to 25% insoluble material. Higher levels may be determined; however, precision has not been determined above the method scope. 6 of 8 614-18 Precision Precision statements were determined using UOP
35、Method 999, “Precision Statements in UOP Methods”. Repeatability and Site Precision A nested design was carried out for determining heptane or toluene insolubles in four samples by two analysts. Each analyst carried out tests on two separate days, performing two tests each day for a total of 32 anal
36、yses. Using a stepwise analysis of variance procedure, the within-day and within-lab estimated standard deviations (esd) were calculated for the components at the concentration levels listed in Table 2. Two tests performed by the same analyst on the same day should not differ by more than the repeat
37、ability allowable differences shown in Table 1 with 95% confidence. Two tests performed in one laboratory by different analysts on different days should not differ by more than the site precision allowable differences shown in Table 1 with 95% confidence. Table 2 Repeatability and Site Precision, In
38、solubles, mass-% Repeatability Site Precision Sample Mean Within Day esd Allowable Difference Within Lab esd Allowable Difference “A“ Heptane Insolubles 11.5 0.36 1.4 0.42 2.6 “B“ Heptane Insolubles 0.46 0.019 0.07 0.023 0.09 “C“ Toluene Insolubles 2.69 0.077 0.30 0.102 0.40 “D“ Toluene Insolubles 2
39、2.0 0.12 0.5 0.15 0.6 The data in Table 2 are a short-term estimate of repeatability. When the test is run routinely, a control standard and chart should be used to develop a better estimate of the long-term repeatability. Reproducibility There is insufficient data to calculate the reproducibility o
40、f the test at this time. Time for Analysis The elapsed time for a single analysis is 3.5 hours. The labor requirement is 1 hour. Suggested Suppliers Burdick and Jackson, 1953 S. Harvey Street, Muskegon, Ml 49442, USA, 1-800-322-2766, www.labchemicals- Fisher Scientific, 711 Forbes Ave., Pittsburgh,
41、PA 15219-4785, USA, 1-412-490-8300, Millipore Corp., Prescott Road, Jaffrey, NH 03452 USA, 1-603-532-8711, VWR International, 1310 Goshen Parkway, West Chester, PA 19380, USA, 1-610-431-1700, 7 of 8 614-18 Figure 1 Insolubles Apparatus using Starfish Work Station with Findensers Set up of apparat
42、us for Insolubles determination using Starfish Work Station and Findensers. (1) Heidolph hot plate with monoblock and Findensers, (2) Filtration unit, (3) Solvent heating apparatus. 8 of 8 614-18 Figure 2 Insolubles Apparatus using Electromantle and Water Condensers Set up of apparatus for Insolubles determination. (1) Reflux apparatus and Electromantle, (2) Filtration unit, (3) Solvent heating apparatus. 1 2 3
