1、Designation: D8056 18Standard 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. Scope*1.1 This guide summarizes the current information aboutthe test methods for elemental and associated analyses used inthe analysis of crude oils. This information
3、can 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 doe
4、s 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, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.4 This internation
5、al standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committ
6、ee.2. Referenced Documents2.1 ASTM Standards: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Device Method)D482 Test Method for Ash from Petroleum ProductsD1548 Test Method for Vanadium in Heavy Fuel Oil1(Withdrawn 1997)3D1552 Test Method for Sulfur in Petrol
7、eum Products byHigh Temperature Combustion and Infrared (IR) Detec-tion or Thermal Conductivity Detection (TCD)D2622 Test Method for Sulfur in Petroleum Products byWavelength Dispersive X-ray Fluorescence SpectrometryD3227 Test Method for (Thiol Mercaptan) Sulfur inGasoline, Kerosine, Aviation Turbi
8、ne, and Distillate Fuels(Potentiometric Method)D3228 Test Method for Total Nitrogen in Lubricating 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 Automa
9、tic Sampling of Petroleum andPetroleum ProductsD4294 Test Method for Sulfur in Petroleum and PetroleumProducts by Energy Dispersive X-ray Fluorescence Spec-trometryD4629 Test Method for Trace Nitrogen in Liquid Hydrocar-bons by Syringe/Inlet Oxidative Combustion and Chemi-luminescence DetectionD4929
10、 Test Method for Determination of Organic ChlorideContent in Crude OilD5185 Test Method 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, Hydr
11、ogen, and Nitrogen in Petroleum Productsand LubricantsD5708 Test Methods for Determination of Nickel,Vanadium, and Iron in Crude Oils and Residual Fuels byInductively Coupled Plasma (ICP) Atomic EmissionSpectrometryD5762 Test Method for Nitrogen in Liquid Hydrocarbons,Petroleum and Petroleum Product
12、s by Boat-Inlet Chemi-luminescenceD5854 Practice for Mixing and Handling of Liquid Samplesof Petroleum and Petroleum ProductsD5863 Test Methods for Determination of Nickel,Vanadium, Iron, and Sodium in Crude Oils and ResidualFuels by Flame Atomic Absorption SpectrometryD6259 Practice for Determinati
13、on of a Pooled Limit ofQuantitation for a Test Method1This 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 June 1, 2018. Published June 201
14、8. Originallyapproved in 2016. Last previous edition approved in 2016 as D8056 16. DOI:10.1520/D8056-18.2For 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 standard
15、s Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United S
16、tatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to
17、Trade (TBT) Committee.1D6299 Practice for Applying Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6470 Test Method for Salt in Crude Oils (PotentiometricMethod)D6792 Practice for Quality Management Systems in Petro-leum Products, Liq
18、uid Fuels, and Lubricants TestingLaboratoriesD7260 Practice for Optimization, Calibration, and Valida-tion of Inductively Coupled Plasma-Atomic EmissionSpectrometry (ICP-AES) for Elemental Analysis of Petro-leum Products and LubricantsD7343 Practice for Optimization, Sample Handling,Calibration, and
19、 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 Practic
20、e 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 Total
21、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 OilsUsing I
22、nductively 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 LubricantsD8150 Test Method for Determination of Organic ChlorideContent in Crude Oil by Distil
23、lation Followed by Detec-tion Using Combustion Ion Chromatography2.2 Other Standards:IP 570 Hydrogen sulfide in fuel oilsRapid liquid phaseextraction method4ISO 8754 Petroleum productsDetermination of sulfurcontentEnergy dispersive X-ray fluorescence spectrom-etry5ISO 14596 Petroleum productsDetermi
24、nation of sulfurcontentWavelength dispersive X-ray fluorescence spec-trometry5UOP 163 Hydrogen sulfide and mercaptan sulfur in liquidhydrocarbons by potentiometric titration2UOP 938 Total mercury and mercury species in liquidhydrocarbons23. Significance and Use3.1 This guide summarizes the test meth
25、ods used in theelemental analysis of crude oils. Additional information on thesignificance and use of the test methods quoted in this guidecan be found under discussion of individual test methods inSections 8 through 15.3.2 Crude oils are highly complex hydrocarbons also con-taining some organometal
26、lic compounds, inorganic sediment,and water. Nearly 600 individual hydrocarbons, over 200separate sulfur compounds, and about 40 trace elements havebeen found in crude oils (1).6Generally, sulfur and nitrogen arethe two most abundant elements found in crude oils except forcarbon and hydrogen. Most o
27、ther inorganic elements arepresent at trace levels (mg/kg). Sulfur, nitrogen, vanadium,nickel, and iron are the most frequently determined elements inthe crude oils. Ratios such as vanadium to vanadium + nickel,and iron to vanadium are suggested as being useful for oil typecharacterizations. Since o
28、rganometallic compounds are con-centrated in the heavy ends of petroleum, transition elementconcentrations and ratios can serve as excellent oil-oil corre-lation parameters. Generally, vanadium and nickel contentincreases with asphaltic content of crude oil (API gravity is anindicator). Lighter crud
29、e oils contain lesser amounts of metals(2, 3).3.3 Metal complexes called porphyrins are a major compo-nent of metallic compounds in crude oils. The principalporphyrin complexes are Ni+2and VO+2compounds. There arealso other non-porphyrin complexes and other metallic com-pounds present in crude oils
30、(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 Collection of a meaningful and representative sample isoften the most critical step in an analytical procedure. In traceelement analysis, in particular, extreme care
31、 must be taken toavoid contamination of the sample during the sampling stepand all subsequent analysis steps. By its very nature, crude oilis typically non-homogenous, containing some percentages ofsediment and water. It also typically contains volatile lightends, and finally, crude oil will often e
32、xhibit high pour pointand high viscosity properties, due to its asphaltenes andparaffin wax content.4.1.1 The water and sediment component 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 conta
33、iners that can be usedfor storage of liquid hydrocarbon products. Not all of them aresuitable for crude oil storage. According to Practice D5854 fortests of interest in elemental analysis area (salts, sulfur, andtrace metals) in crude oil, the containers employed may bemade of hard borosilicate glas
34、s, stainless steel, or epoxy-linedsteel and are considered satisfactory for immediate use, storageup to six months or reuse. Less satisfactory are tin-plated4Available from Energy Institute, 61 New Cavendish St., London, W1G 7AR,U.K., http:/www.energyinst.org.5Available from American National Standa
35、rds 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 182soldered steel, polytetrafluoroethylene propylene (PTFE), andhigh-density linear polyethylene containers. See Ta
36、ble 1.4.2 Three principal protocols are available for sampling of arepresentative aliquot from a bulk sample: Practice D4057 formanual sampling, Practice D4177 for automatic sampling, andPractice D5854 for mixing and handling of liquid samples.4.3 Crude oil to be sampled may be in static storage in
37、atank, a marine vessel, or a pipeline. Stabilized crude oilstypically contain multiple phases, particulates, and volatiles.Decisions whether 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 r
38、oom temperature,heat it to a sufficiently high and safe temperature to ensureadequate fluidity. Great care needs to be taken in heating theviscous sample prior to analysis. Changes in chemicalcomposition, loss of volatile elements, and so forth are causesfor concern.5. Sample Preparation5.1 Often di
39、fferent test methods for specific determinationof elements require different sample preparation steps. GuideD7455 reviews alternative techniques for sample preparationfor elemental analysis. The means of sample preparation varyfrom no sample preparation to simple sample dilution toextensive detailed
40、 procedures such as sample decompositiondepending on the measurement technique to be used for thefinal determination.5.2 Among the test methods used for the elemental analysisof crude oil, test methods such as XRF Test Methods D2622or D4294 for sulfur need no special preparation. However, theymay ne
41、ed dilution with a solvent if the sulfur levels are abovethe scope of the test methods. Other non-XRF test methods thatdo not need special sample treatment include Test MethodD3230 for salt by titration, and Test Methods D5291 forcarbon-hydrogen-nitrogen by combustion.5.3 Some methods require sample
42、 dilution such as in atomicabsorption spectrometry (AAS) Test Method D5863 B fornickel, vanadium, iron, and sodium; inductively coupledplasma-atomic emission spectrometry (ICP-AES) Test MethodD5708 for nickel, vanadium, and iron; and ICP-AES TestMethod D7691 for multi-element analysis of crude oils.
43、5.4 Decomposition agents are employed to bring the desiredparameter in aqueous solution for final measurement. Ex-amples of these are Kjeldahl method for nitrogen: Test MethodD3228, acid decomposition of crude oil for vanadium: TestMethod D1548, and AAS method for nickel, vanadium, iron,and sodium:
44、Test Method D5863 A.5.5 For volatile elements such as nitrogen or sulfur, com-bustion trains using adsorbants have been used in Test MethodD1552 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
45、 of samples toseparate organic chloride fraction from crude oil.5.7 Determination of mercury in crude oil poses specialproblems both in sample collection and in measurement. Theseare discussed elsewhere in detail in Practice D7482, TestMethod D7622, and Test Method D7623.6. Calibration6.1 Depending
46、upon the analysis being done, differentcalibration practices may have to be followed. A review ofcalibration practices used in elemental analysis 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 i
47、nstrumentaltechniques such as atomic absorption spectrometry (AAS),inductively coupled plasma-atomic emission spectrometry(ICP-AES), inductively coupled plasma- mass spectrometry(ICP-MS), isotope dilution mass spectrometry (IDMS), neu-tron activation analysis (NAA), energy-dispersive X-ray fluo-resc
48、ence (ED-XRF), and wavelength-dispersive X-ray fluores-cence (WD-XRF). The highlights of these techniques and theexamples of their utilization to elemental analysis of petroleumproducts and lubricants, and particularly to crude oils havebeen discussed in detail elsewhere (2, 6, 7).7.2 Parameters tha
49、t are usually determined for elementalanalysis are listed in Table 2 along with their scope and theapplicability of the test methods to crude 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 several tests on a crude oil sample, itis very important to ensure that the sequence of testing isevaluated to minimize altering the properties of
