1、Designation: D8056 16Standard Guide forElemental Analysis of Crude Oil1This standard is issued under the fixed designation D8056; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses in
2、dicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This guide summarizes the current information aboutthe test methods for elemental and associated analyses used inthe analysis of crude oils. This information c
3、an be helpful intrade between the buyers and sellers of crude oil. Elementalanalyses tests form an important part of quantifying the crudeoil quality.1.2 The values stated in SI units are to be regarded as thestandard. No other units of measurement are included in thisstandard.1.3 This standard does
4、 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 health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Stand
5、ards:2D129 Test Method for Sulfur in Petroleum Products (Gen-eral High Pressure Decomposition Device Method)D482 Test Method for Ash from Petroleum ProductsD1548 Test Method for Vanadium in Heavy Fuel Oil1(Withdrawn 1997)3D1552 Test Method for Sulfur in Petroleum Products byHigh Temperature Combusti
6、on and IR DetectionD2622 Test Method for Sulfur in Petroleum Products byWavelength Dispersive X-ray Fluorescence SpectrometryD3227 Test Method for (Thiol Mercaptan) Sulfur inGasoline, Kerosine, Aviation Turbine, and Distillate Fuels(Potentiometric Method)D3228 Test Method for Total Nitrogen in Lubri
7、cating Oilsand Fuel Oils by Modified Kjeldahl MethodD3230 Test Method for Salts in Crude Oil (ElectrometricMethod)D4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD4294 Test Method for Sulfur in Petroleum and
8、 PetroleumProducts by Energy Dispersive X-ray Fluorescence Spec-trometryD4629 Test Method for Trace Nitrogen in Liquid PetroleumHydrocarbons by Syringe/Inlet Oxidative Combustion andChemiluminescence DetectionD4929 Test Methods for Determination of Organic ChlorideContent in Crude OilD5185 Test Meth
9、od for Multielement Determination ofUsed and Unused Lubricating Oils and Base Oils byInductively Coupled Plasma Atomic Emission Spectrom-etry (ICP-AES)D5291 Test Methods for Instrumental Determination ofCarbon, Hydrogen, and Nitrogen in Petroleum Productsand LubricantsD5708 Test Methods for Determin
10、ation of Nickel,Vanadium, and Iron in Crude Oils and Residual Fuels byInductively Coupled Plasma (ICP) Atomic EmissionSpectrometryD5762 Test Method for Nitrogen in Petroleum and Petro-leum Products by Boat-Inlet ChemiluminescenceD5854 Practice for Mixing and Handling of Liquid Samplesof Petroleum an
11、d Petroleum ProductsD5863 Test Methods for Determination of Nickel,Vanadium, Iron, and Sodium in Crude Oils and ResidualFuels by Flame Atomic Absorption SpectrometryD6259 Practice for Determination of a Pooled Limit ofQuantitation for a Test MethodD6299 Practice for Applying Statistical Quality Assu
12、ranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6470 Test Method for Salt in Crude Oils (PotentiometricMethod)D6792 Practice for Quality System in Petroleum Productsand Lubricants Testing LaboratoriesD7260 Practice for Optimization, Calibration, and Valida-t
13、ion of Inductively Coupled Plasma-Atomic Emission1This guide is under the jurisdiction of ASTM Committee D02 on PetroleumProducts, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom-mittee D02.03 on Elemental Analysis.Current edition approved July 1, 2016. Published July 2016. D
14、OI: 10.1520/D8056-16.2For 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 last approved version of this histo
15、rical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1Spectrometry (ICP-AES) for Elemental Analysis of Petro-leum Products and LubricantsD7343 Practice for Optimization, Sample Handling,Calibratio
16、n, and Validation of X-ray Fluorescence Spec-trometry Methods for Elemental Analysis of PetroleumProducts and LubricantsD7372 Guide for Analysis and Interpretation of ProficiencyTest Program ResultsD7455 Practice for Sample Preparation of Petroleum andLubricant Products for Elemental AnalysisD7482 P
17、ractice for Sampling, Storage, and Handling ofHydrocarbons for Mercury AnalysisD7578 Guide for Calibration Requirements for ElementalAnalysis of Petroleum Products and LubricantsD7621 Test Method for Determination of Hydrogen Sulfidein Fuel Oils by Rapid Liquid Phase ExtractionD7622 Test Method for
18、Total Mercury in Crude Oil UsingCombustion and Direct Cold Vapor Atomic AbsorptionMethod with Zeeman Background CorrectionD7623 Test Method for Total Mercury in Crude Oil UsingCombustion-Gold Amalgamation and Cold Vapor AtomicAbsorption MethodD7691 Test Method for MultielementAnalysis of Crude OilsU
19、sing Inductively Coupled Plasma Atomic EmissionSpectrometry (ICP-AES)D7740 Practice for Optimization, Calibration, and Valida-tion of Atomic Absorption Spectrometry for Metal Analy-sis of Petroleum Products and Lubricants2.2 Other Standards:IP 570 Hydrogen Sulfide in Fuel OilsRapid Liquid PhaseExtra
20、ction Method4ISO 8754 Petroleum Products, Determination of SulfurContent, Energy Dispersive X-ray Fluorescence Spec-trometry5ISO 14596 Petroleum Products, Determination of SulfurContent, Wavelength Dispersive X-ray FluorescenceSpectrometry5UOP 163 Hydrogen Sulfide and Mercaptan Sulfur in LiquidHydro
21、carbons by Potentiometric Titration2UOP 938 Total Mercury and Mercury Species in LiquidHydrocarbons23. Significance and Use3.1 This guide summarizes the test methods used in theelemental analysis of crude oils. Additional information on thesignificance and use of the test methods quoted in this guid
22、ecan be found under discussion of individual test methods inSections 8 through 15.3.2 Crude oils are highly complex hydrocarbons also con-taining some organometallic compounds, inorganic sediment,and water. Nearly 600 individual hydrocarbons, over 200separate sulfur compounds, and about 40 trace ele
23、ments havebeen found in crude oils (1).6Generally, sulfur and nitrogen arethe two most abundant elements found in crude oils except forcarbon and hydrogen. Most other inorganic elements arepresent at trace levels (mg/kg). Sulfur, nitrogen, vanadium,nickel, and iron are the most frequently determined
24、 elements inthe crude oils. Ratios such as vanadium to vanadium + nickel,and iron to vanadium are suggested as being useful for oil typecharacterizations. Since organometallic compounds are con-centrated in the heavy ends of petroleum, transition elementconcentrations and ratios can serve as excelle
25、nt oil-oil corre-lation parameters. Generally, vanadium and nickel contentincreases with asphaltic content of crude oil (API gravity is anindicator). Lighter crude oils contain lesser amounts of metals(2, 3).3.3 Metal complexes called porphyrins are a major compo-nent of metallic compounds in crude
26、oils. The principalporphyrin complexes are Ni+2and VO+2compounds. There arealso other non-porphyrin complexes and other metallic com-pounds present in crude oils (4, 5).3.4 Some typical literature citations in this area are includedin the reference section at the end of this guide.4. Sampling4.1 Col
27、lection of a meaningful and representative sample isoften the most critical step in an analytical procedure. In traceelement analysis, in particular, extreme care must be taken toavoid contamination of the sample during the sampling stepand all subsequent analysis steps. By its very nature, crude oi
28、lis typically non-homogenous, containing some percentages ofsediment and water. It also typically contains volatile lightends, and finally, crude oil will often exhibit high pour pointand high viscosity properties, due to its asphaltenes andparaffin wax content.4.1.1 The water and sediment component
29、 of the crude oilwill tend to naturally separate and stratify in tanks, marinevessel compartments, and in flowing pipelines.4.1.2 There are various types of containers that can be usedfor storage of liquid hydrocarbon products. Not all of them aresuitable for crude oil storage. According to Practice
30、 D5854 fortests of interest in elemental analysis area (salts, sulfur, andtrace metals) in crude oil, the containers employed may bemade of hard borosilicate glass, stainless steel, or epoxy-linedsteel and are considered satisfactory for immediate use, storageup to six months or reuse. Less satisfac
31、tory are tin-platedsoldered steel, polytetrafluoroethylene propylene (PTFE), andhigh-density linear polyethylene containers. See Table 1.4.2 Three principal protocols are available for sampling of arepresentative aliquot from a bulk sample: Practice D4057 formanual sampling, Practice D4177 for autom
32、atic sampling, andPractice D5854 for mixing and handling of liquid samples.4.3 Crude oil to be sampled may be in static storage in atank, a marine vessel, or a pipeline. Stabilized crude oilstypically contain multiple phases, particulates, and volatiles.4Available from Energy Institute, 61 New Caven
33、dish St., London, W1G 7AR,U.K., http:/www.energyinst.org.5Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.6The bold numbers in parentheses refer to the list of references at the end of thisstandard.D8056 162Decisions wheth
34、er to separate the phases and analyze themseparately, or homogenize the whole sample need to be madeprior to analysis.4.4 If the sample does not readily flow at room temperature,heat it to a sufficiently high and safe temperature to ensureadequate fluidity. Great care needs to be taken in heating th
35、eviscous sample prior to analysis. Changes in chemicalcomposition, loss of volatile elements, and so forth are causesfor concern.5. Sample Preparation5.1 Often different test methods for specific determinationof elements require different sample preparation steps. GuideD7455 reviews alternative tech
36、niques for sample preparationfor elemental analysis. The means of sample preparation varyfrom no sample preparation to simple sample dilution toextensive detailed procedures such as sample decompositiondepending on the measurement technique to be used for thefinal determination.5.2 Among the test me
37、thods used for the elemental analysisof crude oil, test methods such as XRF Test Methods D2622or D4294 for sulfur need no special preparation. However, theymay need dilution with a solvent if the sulfur levels are abovethe scope of the test methods. Other non-XRF test methods thatdo not need special
38、 sample treatment include Test MethodD3230 for salt by titration, and Test Methods D5291 forcarbon-hydrogen-nitrogen by combustion.5.3 Some methods require sample dilution such as in atomicabsorption spectrometry (AAS) Test Method D5863 B fornickel, vanadium, iron, and sodium; inductively coupledpla
39、sma-atomic emission spectrometry (ICP-AES) Test MethodD5708 for nickel, vanadium, and iron; and ICP-AES TestMethod D7691 for multi-element analysis of crude oils.5.4 Decomposition agents are employed to bring the desiredparameter in aqueous solution for final measurement. Ex-amples of these are Kjel
40、dahl method for nitrogen: Test MethodD3228, acid decomposition of crude oil for vanadium: TestMethod D1548, and AAS method for nickel, vanadium, iron,and sodium: Test Method D5863 A.5.5 For volatile elements such as nitrogen or sulfur, com-bustion trains using adsorbants have been used in Test Metho
41、dD1552 for sulfur, and Test Methods D4629 and D5762 fornitrogen.5.6 Organic chloride in crude oil is determined by TestMethods D4929 after elaborate pre-treatment of samples toseparate organic chloride fraction from crude oil.5.7 Determination of mercury in crude oil poses specialproblems both in sa
42、mple collection and in measurement. Theseare discussed elsewhere in detail in Practice D7482, TestMethod D7622, and Test Method D7623.6. Calibration6.1 Depending upon the analysis being done, differentcalibration practices may have to be followed. A review ofcalibration practices used in elemental a
43、nalysis is given inGuide D7578.7. Analysis of Crude Oils7.1 A number of elemental analysis techniques have beenused in the analysis of crude oils. These include instrumentaltechniques such as atomic absorption spectrometry (AAS),inductively coupled plasma-atomic emission spectrometry(ICP-AES), induc
44、tively coupled plasma- mass spectrometry(ICP-MS), isotope dilution mass spectrometry (IDMS), neu-tron activation analysis (NAA), energy-dispersive X-ray fluo-rescence (ED-XRF), and wavelength-dispersive X-ray fluores-cence (WD-XRF). The highlights of these techniques and theexamples of their utiliza
45、tion to elemental analysis of petroleumproducts and lubricants, and particularly to crude oils havebeen discussed in detail elsewhere (2, 6, 7).7.2 Parameters that are usually determined for elementalanalysis are listed in Table 2 along with their scope and theapplicability of the test methods to cr
46、ude oil assay. Several ofthe tests methods are not specifically designated for crude oilanalysis but conventionally they are widely used for suchanalyses in the industry.7.2.1 Some of the ASTM tests listed in Table 2 have theirinternational counterparts listed in Table 3 (8).7.3 When performing seve
47、ral tests on a crude oil sample, itis very important to ensure that the sequence of testing isevaluated to minimize altering the properties of the remainingsample to be tested or retained. For crude oil samples, thevapor pressure, H2S, or any other test in which retention oflight ends is critical ne
48、ed to be analyzed first from the originalsample container. For elemental analysis parameters, the se-quence of testing should be mercaptan sulfur, metals by AASor ICP-AES, nitrogen, salts, and sulfur by XRF, in that order.7.4 For several elemental tests, special precautions need tobe taken in handli
49、ng the crude oil samples during analysis.Some of these are listed below in Table 4 excerpted fromPractice D4057.TABLE 1 Recommended Sample Containers for Crude Oil StorageAContainer Material For Immediate Use For Storage for 6 months For ReuseHard Borosilicate Glass Preferred Preferred SuitableStainless Steel Suitable Suitable SuitableEpoxy-lined Steel Suitable Suitable SuitableTin-plated Soldered Steel Not recommended Not recommended Not recommendedPolytetrafluoroethylene Propylene (PTFE) Preferred Not recommended SuitableHigh-density Linear Polyethylene (HDPE) Preferred Not rec
