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. MATERIAL SAFETY DATA SHEETS (MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION EQUIPMENT (PPE). COPYRIGHT 1971, 1981, 1986, 2004, 2009, 2010, 20
3、15 UOP LLC. All rights reserved. Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, USA. The UOP Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at serviceastm.org,
4、 610.832.9555 FAX, or 610.832.9585 PHONE. Trace Metals in Organics by ICP-OES UOP Method 389-15 Scope This method is for determining the concentrations of aluminum (Al), calcium (Ca), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), magnesium (Mg), manganese (Mn), molybde
5、num (Mo), nickel (Ni), palladium (Pd), phosphorus (P), platinum (Pt), potassium (K), sodium (Na), strontium, (Sr), tin (Sn), titanium (Ti), vanadium (V), and zinc (Zn) in organic matrices such as crude petroleum, asphalts, vacuum tower bottoms, vacuum gas oils, atmospheric gas oils, diesel and jet f
6、uels and their blending components, pyrolysis oils, and fatty acid derivatives by Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES). The lower limits of quantitation for the above elements, except palladium, are listed in Table 1 (see Note). Table 1 Lower Limits of Quantitation, mg/
7、kg (mass-ppm) Al 0.05 Li 0.03 Pb 0.04 Ca 0.08 Mg 0.04 Pt 0.01 Co 0.02 Mn 0.01 Sn 0.10 Cr 0.04 Mo 0.01 Sr 0.01 Cu 0.01 Na 0.04 Ti 0.03 Fe 0.09 Ni 0.03 V 0.01 K 0.05 P 0.11 Zn 0.03 Determination of additional elements is possible if they are not volatilized during the ashing step and do not form insol
8、uble sulfates. Two different reagents are used in sample preparation, depending upon the sample matrix. Alternatively, some of the elements listed above may be analyzed by Atomic Absorption Spectroscopy (AAS). See UOP Method 391, “Trace Metals in Petroleum Products or Organics by AAS,” for specific
9、metals and their range of quantitation. Metals known to be non-volatile may be analyzed by UOP Method 407, “Trace Metals in Organics by Dry Ashing - ICP-OES.” References ASTM Method D1193, “Specification for Reagent Water,” www.astm.org ASTM Practice D7455, “Sample Preparation of Petroleum and Lubri
10、cant Products for Elemental Analysis,” www.astm.org 2 of 13 389-15 UOP Method 391, “Trace Metals in Petroleum Products or Organics by AAS,” www.astm.org UOP Method 407, “Trace Metals in Organics by Dry Ashing - ICP-OES,” www.astm.org UOP Method 999, “Precision Statements in UOP Methods,” www.astm.or
11、g Outline of Method The sample is treated to reduce the volatility of the metals, then coked and ashed. The residue is treated with aqua regia and, after evaporation, is dissolved in acids. Scandium is added as an internal standard. The concentrations of elements in the resulting solutions are deter
12、mined by ICP-OES. Apparatus References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. Balance, laboratory, readable to 0.01 g Beaker, quartz, low form, 250-mL, Ace Glass, Inc., Cat. No. 5334-14 Bottles, polypropylene, narrow mouth, scr
13、ew cap, 1000-mL, VWR, Cat. No. 16067-124, several required Bottle, wash, VWR, Cat. No. 89094-606, for deionized water Cylinders, graduated, Class B, 5-, 10-, 25-, and 100-mL, VWR, Cat. Nos. 14201-610, -462, -364, and -718, respectively Flasks, volumetric, Class A, 10-, 50-, and 1000-mL, VWR, Cat. No
14、s. 89000-398, -402, and -412, respectively Flasks, volumetric, polypropylene, 25-, 50-, 100-, and 1000-mL, VWR, Cat. Nos. 83008-964, 29615-019, -007, and -062, respectively Furnace, muffle, capable of operation at 600 C, VWR, Cat. No. 30604-158 Hot plate, variable heat, maximum operating temperature
15、 510 C, VWR, Cat. No. 82026-752 Pipet, measuring (Mohr), 5-mL, VWR, Cat. No. 89003-458 Pipets, volumetric, Class A, 1-, 2-, 5-, 10-, 20-, 25-, 50-, and 100-mL, VWR, Cat. Nos. 89003-340, -342, -348, -350, -364, -362, -366-, and -368, respectively Pipet filler, VWR, Cat. No. 53497-053 Regulator, argon
16、, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Model 3122-580 Spectrometer, ICP-OES, computer controlled, having sufficient resolving power and dispersion to separate the analytical lines in the 160 to 800 nm region. The data system shall be capable of pe
17、rforming background corrections, blank corrections, mass/volume corrections and dilution corrections. A commercial grating spectrometer with a band pass of 0.018 nm or less in the first order is satisfactory. PerkinElmer, Optima 7300 DV. Stirring rods, quartz, JSRitter, Cat. No. 21-905 Tongs, beaker
18、, VWR, Cat. No. 82027-374 Watch glasses, quartz, ribbed, 75-mm diameter, Wilmad-LabGlass, Cat. No. C-9990-75, several required 3 of 13 389-15 Reagents and Materials References to catalogue numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. Unless oth
19、erwise specified, references to water mean deionized water. Aqua regia. To prepare, mix 1 mL of concentrated nitric acid with 3 mL of concentrated hydrochloric acid. Prepare a fresh batch each time it is needed. Argon, 99.995% minimum purity Cleaning compound, Alconox detergent, VWR, Cat. No. 21835-
20、032 Gloves, neoprene/natural rubber, VWR, Cat. No. 32917-206 (for size large) Hydrochloric acid, concentrated, trace metals grade, VWR, Cat. No. EM-HX0608-2 Hydrofluoric acid, concentrated, trace metals grade, VWR, Cat. No. EM-HX0628-7, if needed, see Procedure, Sample Preparation, Ashing, Step 8 Ni
21、tric acid, concentrated, trace metals grade, VWR, Cat. No. EM-NX0408-2 Pipet, dropping, VWR, Cat. No. 52950-206 Scandium metal solution, aqueous, 1000-g/mL, SPEX Certiprep, Inc., Cat. No. PLSC-2, for use as internal standard Scandium metal solution, aqueous, 100-g/mL. To prepare 50 mL, pipet 5.0 mL
22、of the 1000- g/mL scandium metal solution into a 50-mL volumetric flask. Fill to the mark with deionized water. Cap and invert several times to mix. The solution should remain stable for one month. Scandium internal standard, 10-g/mL. To prepare 1000 mL, pipet 10.0 mL of 1000-g/mL scandium metal sol
23、ution into a 1000-mL volumetric flask. Fill to the volume mark with water and mix. Store in a 1000-mL polypropylene bottle. The solution should remain stable for one month. Scandium internal standard, 1-g/mL. To prepare 1000 mL, pipet 1.0 mL of 1000-g/mL scandium metal solution into a 1000-mL volume
24、tric flask. Using a graduated cylinder, add 100 mL of concentrated hydrochloric acid. Fill to the volume mark with water and mix. Store in a 1000-mL polypropylene bottle. The solution should remain stable for one month. Standard metal solutions, Al, Ca, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P,
25、Pb, Pd, Pt, Sn, Sr, Ti, V, and Zn solutions of 1000-g/mL concentrations, SPEX Certiprep, Inc., Cat. Nos. PLAL2-2, PLCA2-2, PLCO2-2, PLCR2-2, PLCU2-2, PLFE2-2, PLK2-2, PLLI2-2, PLMG2-2, PLMN2-2, PLMO2-2, PLNA2-2, PLNI2-2, PLP2-2, PLPB2-2, PLPD2-2, PLPT2-2, PLSN2-2, PLSR2-2, PLTI2-2, PLV2-2, and PLZN2
26、-2, respectively Sulfuric acid, concentrated, trace metals grade, VWR, Cat. No. EM-SX1248-6, if needed, see Procedure, Sample Preparation, Ashing, Step 7 Sulfur trioxide pyridine complex, 26412-87-3, Sigma-Aldrich, Cat. No. S7556, or Acros Organics, Cat. No. 13287-1000 Vials, autosampler, 15-mL, Per
27、kinElmer, Cat. No. B0193233 Water, deionized, ASTM D1193 Type III reagent grade water, unless otherwise specified Water, hot, tap The following materials are not required to perform the analyses described herein and are not cited in the Procedure portion of the method. However, they may be useful fo
28、r reference purposes, for 4 of 13 389-15 verification of instrument performance, or as an aid in instrument maintenance. The diluted multi-element standard was used to develop part of the precision statement. Element Blank Oil, 75 viscosity, Conostan Division, SCP Science Wear Metal Multi-Element St
29、andard, 500-g/g (mg/kg) each, AccuStandard, Cat. No. WM-21-50X-8. Dilute by weight in Element Blank Oil to 5 mg/kg. Preparation of Standards The analyst is expected to be familiar with general laboratory practices. Dispose of all materials in an environmentally safe manner according to local regulat
30、ions. CAUTION: All subsequent steps involving additions of reagents and heating of samples must be performed in a properly operating fume hood, and appropriate personal protective equipment must be used. See the MSDS and any local requirements for each material used. Standards are required for each
31、element to be determined. They are prepared to contain a number of elements with compatible chemistries and no overlap of emission lines. Stock standard solutions are prepared first, from which lower level, matrix-matched, calibration standard solutions are then prepared. Calibration standards (incl
32、uding the blank), as well as the final sample preparation, contain the internal standard scandium at a concentration of 1 g/mL Preparation of Stock Standard Solutions Prepare stock standard solutions of 100-g/mL concentration of each element as follows: 1. Pipet 100 mL each of the Al, Ca, Co, Cr, Cu
33、, Fe, Mg, Mn, and Ni 1000-g/mL commercial stock standards into a 1000-mL polypropylene volumetric flask. Dilute to the mark with deionized water. Label as Stock Standard A. 2. Pipet 100 mL each of the Sn, Pd, Pt, V, and Zn 1000-g/mL commercial stock standards into a second 1000-mL polypropylene volu
34、metric flask. Dilute to the mark with deionized water. Label as Stock Standard B. 3. Pipet 100 mL each of the Mo, P, and Ti 1000-g/mL commercial stock standards into a third 1000-mL polypropylene volumetric flask. Dilute to the mark with deionized water. Label as Stock Standard C. 4. Pipet 100 mL ea
35、ch of the K and Na, 40 mL of the Li, and 20 mL of the Sr 1000-g/mL commercial stock standards into a fourth 1000-mL polypropylene volumetric flask. Dilute to the mark with deionized water. Label as Stock Standard D. Use only 40 mL of Li and 20 mL of Sr because the instrument is more sensitive to the
36、se elements. Their concentrations in the stock standard solutions are 40 g/mL and 20 g/mL, respectively. Preparation of Blank and Calibration Standard Solutions Sample preparation differs depending upon the composition of the sample. Lighter materials, kerosene, diesel, atmospheric gas oil, vacuum g
37、as oil, and fatty acid derivatives, are prepared using Preparation A. These materials are typically lower in metals. Heavier materials, vacuum tower bottoms, crude, asphalt, and pyrolysis oil, are prepared using Preparation B. These materials are typically higher in metals. Blank and Calibration Sta
38、ndard Solutions must be matrix-matched to the sample preparation technique. Preparation A is used for metals stabilized with sulfur trioxide pyridine complex. Preparation B is used for metals stabilized with sulfuric acid. Prepare 100 mL of matrix-matched Calibration Standards and a Blank as follows
39、: 5 of 13 389-15 1. For use with samples prepared by Preparation A: Weigh and add 0.5 0.05 g of sulfur trioxide pyridine complex to each of five cleaned (see Procedure, Cleaning of Quartz Beakers) 250-mL quartz beakers. Heat on a hot plate to dryness; the material will melt and then ash. Proceed to
40、Step 3. 2. For use with samples prepared by Preparation B: Using a graduated cylinder, add 8 mL of sulfuric acid to each of five cleaned (see Procedure, Cleaning of Quartz Beakers) 250-mL quartz beakers. Cover each of the beakers with a watch glass. Heat on a hot plate to dryness. Proceed to Step 3.
41、 3. Place the covered beakers in the muffle furnace at 538 C for one hour. Cool to ambient temperature and then uncover. 4. Using a graduated cylinder, add 4 mL of aqua regia to the mineral residue in each beaker and evaporate to near dryness on a hot plate. Cool to ambient temperature. 5. Using a g
42、raduated cylinder, add 10 mL of hydrochloric acid to each beaker and heat to dissolve any residue. When dissolved, cool to ambient temperature. 6. Quantitatively transfer the contents of each beaker with deionized water into separate 100-mL polypropylene volumetric flasks. Label the five flasks 10-m
43、g/kg Calibration Standard A, B, C, D, and Blank. 7. Pipet into each of the five flasks 1.0 mL of the 100-g/mL scandium solution. 8. Pipet 10 mL of Stock Standard A into the flask labeled 10-mg/kg Calibration Standard A. Fill to the mark with deionized water. Follow the same procedure for Standards B
44、, C, and D. The standards contain 10 g/mL of their respective elements, except for 4 g/mL of Li and 2. g/mL of Sr. Fill the flask labeled Blank to the mark with deionized water. The solutions should remain stable for one month. Procedure The analyst is expected to be familiar with general laboratory
45、 practices, the technique of ICP-OES, and the equipment being used. Additional information regarding sample preparation may be found in ASTM Practice D7455, “Sample Preparation of Petroleum and Lubricant Products for Elemental Analysis.” CAUTION: All subsequent steps involving additions of reagents
46、and heating of samples must be performed in a properly operating fume hood, and appropriate personal protective equipment must be used. See the MSDS and any local requirements for each material used. Cleaning of Quartz Beakers Clean the 250-mL quartz beakers before each use as follows: 1. Wash the b
47、eakers with cleaning compound and rinse with deionized water. Rinse the watch glasses with deionized water. 2. Using a graduated cylinder, add 10 mL of concentrated hydrochloric acid to each beaker, bring to boiling on a hot plate and rinse again 4 to 5 times with deionized water. Dry on a warm hot
48、plate, and allow to cool to ambient temperature. 3. Use the same day. 6 of 13 389-15 Sample Preparation, Ashing Sample preparation differs depending upon the composition of the sample. Lighter materials, kerosene, diesel, atmospheric gas oil, vacuum gas oil, and fatty acid derivatives, are prepared
49、using Preparation A. These materials are typically lower in metals. Heavier materials, vacuum tower bottoms, crude, asphalt, and pyrolysis oil, are prepared using Preparation B. These materials are typically higher in metals. Preparation A, Using Sulfur Trioxide Pyridine Complex CAUTION: All handling of reagents is to be performed in a hood. Use proper PPE and lower the hood shield for protection. 1. Weigh into a cleaned, quartz beaker, to the nearest 0.01 g, an amount of sample appropriate to sample type and the expected metals concentration, typica
