Anal. Chem. 1009, 65, 171R-198R
Petroleum and Coal Jane B. Hooper, Coordinator Marathon Oil Company, Petroleum Technology Center, P.O. Box 269, Littleton, Colorado 80160-0269
Coal and Coke Jane V. Thomas Wyoming Analytical Laboratories, 605 South Adams, Laramie, Wyoming 82070
Crude Oil and Shale Oil Dennis L. Button Marathon Oil Company, Indianapolis, Indiana 46268-0007
Heavy Oils (Natural and Refined) Kurt A. Lintelmann Marathon Oil Company, Petroleum Technology Center, P.O. Box 269, Littleton, Colorado 80160-0269
Lubricants Richard J. Trocino Research & Development Department, Texaco, Inc., P.O. Box 509, Beacon, New York 12508
Natural Gas and Refined Products Jane B. Hooper Marathon Oil Company, Petroleum Technology Center, P.O. Box 269, Littleton, Colorado 80160-0269
Source Rocks R. Paul Philp School of Geology and Geophysics, University of Okalahoma, Norman, Oklahoma 73019
INTRODUCTION The articles chosen for this review came from Chemical Abstracts (October 1990to October 1992). I have limited the selected abstracta to those originally written in English or to those translated into English. For this edition I have changed the group headings and content to distribute the reference material more evenly. This change required the addition of another author. See the following for an outline of the review contents.
Review Contents Coal and Coke Proximate and Ultimate Analysis and Sulfur Forms Inorganic Constituents Calorific Analysis Oxidation and Weathering Physical Methods On-Line Analyzers Spectroscopic Methods Solvent Swelling Miscellaneous
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0003-2700/93/0365-0171R$12.00/0
Crude Oil and Shale Oil Crude Oil Shale Oil Heavy Oils (Natural and Refined) Chromatographic Methods Spectroscopic Methods Pyrolytic Methods Miscellaneous Methods Lubricants Lubricating Oils Lubricant Additives Greases Solid Lubricanta Synthetic Lubricanta Natural Gas and Refined Producta Natural Gas and Natural Gas Liquids Gasoline Kerosine and Diesel Jet Fuel Fuel Oil Source Rocks Introduction Source Rock Extracts Kerogens Q 1983 American Chemical Society
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Coal and Coke Jane V. Thomas Wyoming Analytical Laboratories, 605 South A d a m , Laramie, Wyoming 82070 The volume of research on coal and products from coal is evident in not only the number of review articles but also the limited, specific nature of the review articles, many of which have been included here to conserve space and still assist in literature searches. Many researchers are using the Argonne premium coal samples for their investigations, so the data on these samples are now being published and made available for multiple comparisons for all researchers.
PROXIMATE AND ULTIMATE ANALYSIS AND SULFUR FORMS Proximate Analysis. W a n e ( A I ) discussed proximate analysis of coal, oil shale, low-quality fossil fuels, and related materials by thermogravimetry in a review with 17references. Moisture. Wroblewski and Verkade (A2) used phosphorus-31 NMR to investigate the possibility of differentiating types of moisture in coals, studying the moisture release from four Argonne premium coal samples into selected solvents; Wroblewski with co-workers (A3) developed a method for the determination of moisture in coals by derivatizing pyridine-extracted moisture with a 31P NMR tagging agent. Nitrogen. To determine the evolution of nitrogencontaining compounds during coal pyrolysis as a precursor reaction in combustion, Bartle, Taylor, and Williams (A4) used high-temperature pyroprobe gas chromatography of coal with flame ionization detection for hydrocarbons and thermionic detection for selectivedetection of nitrogen-containing compounds; rapid yrolysis at 1670 K was combined with temper atur e-stage GC. Forms of Sulfur. Markuszewski and associates (A5)used selectivedegradation with perchloricacid mixtures to improve the differentiation of sulfur forms in coals. Straszheim and others (A6)worked with samples from two seams of higher sulfur lignites from North Dakota and characterized them for sulfur-reduction potential (cleanability). Huggins and co-workers (A7) developed a method for the quantitative determination of the two principle inorganic sulfur forms (pyritic,sulfate) and the four major organic functional groups (sulfide,thiophene, sulfoxide,sulfone)likelyto be encountered in coals of different ranks and de ees of oxidation;the method and its applicationsare discusser The direct characterization and uantification of sulfur-containing functional groups in coal 3uring in-situ high-temperature oxidation and pyrolysis was carried out by Taghiei et al. ( A @ ,using sulfur K-edge X-ray absorption near-edgestructure (XANES) spectroscopy for the fine structure investigation. Hackley and co-workers (A9) discussed tracking forms of sulfur in coal research using natural sulfur-34/sulfur-32ratios in a review article with 42 references; the method is based on ratios of pyritic and organic differences between the 34S/32S sulfur. Organic Sulfur. Calkins et al. (AIO) described and compared three methods of speciating and quantifying the forms of organically bound sulfur in coal; all three methods (one based on chemical reactivity and the other two based on direct measurement by X-ray absorption spectroscopies) indicated that low-rank coals containing sulfur tend to be high in sulfidic sulfur while higher rank coals tend to have mostly thiophenic sulfur forms. Ge and Wert ( A l l ) used transmission electron microscopy to investigate the spatial variation of organic sulfur in coal, determining the concentration of organic sulfur in close proximity to sulfides. The characterization of organic sulfur compounds in coals and coal macerals was accomplished by Palmer and co-workers (A12),using peroxyacetic acid oxidation to investigate the type and distribution of organic sulfur species in vitrinite, sporinite, and inertinite from two midwestern coals.
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INORGANIC CONSTITUENTS Hamilton and Salehi (AI3) used the scanning electron microscopeto study the effect of inherent mineral matter on the response of inertinite to backscattered electrons. 172R
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Jane V. Thomas, analytical chemist and President of Wyoming Analytical Laboratories, Inc., has been working wfth coal analysis since her first job in the coal laboratory at the Illinois State Geological Survey In 1963. She has a B.S. in chemistry and in biology from Murray State University (1962, Murray, Kentucky)and a master’s degree in chemistry from the University of Wyoming (1971, Laramie, Wyoming). She has been an active participant with ASTM Committee D-5 on Coal and Coke since 1974, serving as secretary for subcommtttees dealing with trace element analysis and chairing task groups working toward accreditation standards.
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Huggins and Huffman (AI4) used X-ray absorption fine edge spectroscopy (XAFS) to investigate the forms of occurrence of chlorine in selected U.S. coals. Cox (A15) presented a review with 22 references on chemical,extraction-based,and ion chromatographicmethods for the determination of chlorine in coal. McCormick and FitzPatrick (A16)discussed the removal of chloride from coal by water leaching in a review with 18 references; topics discussed include an economic analysis, feasibility and siting implications, environmental constraints (especially water pollution), the role of filter cake washing to chloride removal, development of a mathematical model, ion-exchange considerations, waste and water management, mass balances, and associated equipment requirements. Trace Elements. The principles of neutron activation analysis and irradiation and postirradiation procedures are some of the topics discussed by Orvini (A17) in a review with 17 references on the determination of trace elements in coal by nuclear analytical methods.
CALORIFIC ANALYSIS The applicability of differential thermal analysis (DTA) for determining the calorific values of eight coals of different origin and rank and their respective chars was tested by Munoz-Guillena et al. (A18)after analyzing its suitability to establish the enthalpy of the C-02 reaction; comparison of the calorific values obtained by DTA to those obtained from the ASTM method and to those calculated from a semiempirical equation indicated that DTA could be applicable for determining the calorific values of coals when a bomb calorimeter is not available or when the amount of representative sample is too small for direct determination. Christie and Mainwaring (A19)examined the low-temperature heating of low-rank coals by both differential thermal/ thermogravimetric analysis (DTA/TGA) and immersion calorimetry in a study of oxidative and immersional heating on low-rank coal surfaces. Ma (A20) and others used a coal standard and differential scanning calorimetry to directly determine the specific energy of several types of Australian coal.
OXIDATION AND WEATHERING Using fluorescencemicroscopy in the detection of low-level oxidation in bituminous coals, McHugh and co-workers ( M I ) measured the fluorescence intensities at 650 nm in both Australian and German carboniferous coals and found that the intensities decreased with the duration of oxidation; the response of fluorescence intensity levels to oxidation for a particular coal depends on its rank, depositional history, and the conditions of storage prior to testing. Mitchell and coworkers ( A B )also used vitrinite fluorescence as a measure of changes in coal thermoplasticity and weathering. The eight Argonne premium coal samples were analyzed by Weitzsacker and Gardella (A23),using electron spectroscopy for chemical analysis (ESCA or XPS) and to determine the surface elemental composition; analyses were performed upon opening the vials, again a t 3-24 h after opening to
PETROLEUM AND COAL
evaluate oxidation due to air exposure, and again after 10 months and after severe oxidation by radiofrequency glow discharge. Bensley and Crelling (A241 provided a review with 21 references on UV fluorescence microspectrophotometry of coal macerals for rank analysis and detection of weathering of coals.
PHYSICAL METHODS In a study of the settling and rheolo of suspensions of narrow-sized coal articles, Turian et f ( A 2 5 ) determined settlin rates, yierd stresses, and shear stress-shear rate depenfencies as functions of solidsconcentrations for aqueous suspensions of coal articles of narrow-sized fractions; relations developed incgde viscosity- and yield-stress concentration correlations incorporating the maximum packing volume fraction of solids. Straszheim and Markuszewski (A26, A27) used scanning electron microscope-based automated image analysis (SEM-AIA) to characterize the association of mineral matter with organic coal components in order to predict cleanability for selected chemical processes and to quantitatively assess the association of mineral matter with coal. Cody and Davis ( A B )used SEM for direct imaging of coal pore space accessible to liquid metal.
ON-LINE ANALYZERS Oliveira (A29, A30) and Salgado (A31) used prompt neutron activation analysis to determine the elemental composition of bulk samples and carried out a simulation using the Monte Carlo neutron hoton code to study neutron flux distributions generategby a 241Am-Besource in a ran e of bituminous coals contained in a parallel-faced slab. desolinski and De Jesus (A32) discussed a portable coal face ash monitor based on simultaneous measurement of backscattered y radiation at two different energies. Cooper (A33) discussed advances in on-line particulate composition analysis especially for the use of on-line automated procedures for establishingcom osition data in a review with 32 references; topics and procegres discussed include X-ray diffraction, X-ray fluorescence, prompt neutron activation on-stream analysis, magnetic resonance procedures (e.g., EPR) and on-line characterization of particulate composition by chemical extraction and colorimetric (flow injection) analysis. Rose (A34)discussed methods for assessing the accuracy of on-line coal analyzers. Vourvopoulos (A35) discussed industrial on-line bulk analysis using nuclear techniques in a review with 15 references.
SPECTROSCOPIC METHODS Applications of spectroscopy in coal characterization were reviewed by Thomas and Herod (A36)with 20 references on the use of mass spectroscopy, NMR, and FTIR spectroscopy in characterizing coal. Seven Argonne premium coal samples ran ing from lignite to low-volatilebituminous in rank were ana!yzed by Yun and co-workers ( A 3 3 by pyrolysis-field ionization mass spectrometry in order to determine the existence and structural nature of a thermally extractable “mobile phase”; Curie point pyrolysis-low voltage mass spectrometry was employed to demonstrate the importance of mild oxidation for the thermally extractable mobile-phase components. Infrared and FTIR. Since emission FTIR spectroscopy produces high-quality spectra of coal in the temperature range 200-700 OC, and since the emission spectra are qualitatively similar to transmission spectra and are therefore easier to interpret, Cole-Clarke and Vassallo (A38) employed this technique and an Australian black coal to show that emission spectrosco y can be used to trace changes in aliphatic CH groups antalso changes in the inherent mineral matter; the technique has possibilitiesin the studies of coal carbonization, including development of fluidity, and coal oxidation. Yu and co-workers (A39) carried out diffuse and specular reflectance FTIR analysis of both fossil resin (resinite) and coal to study surface oxidation reactions which occur during the selective flotation of fossil resin from coal by ozone conditioning. Robbins (A40) applied FTIR spectroscopy of
low-temperature ashesto the determination of coal mineralogy and the prediction of ash properties during coal combustion. NMR. Argonne premium coal samples were characterized by Dela Rosa and co-workers (A411 by using FTIR spectroscopy and a variety of transient techniques in solid-state H and 13C NMR s ectroscopy. Carbon-13 NMR techniques for structural stuges of coals and coal chars were discussed by Orendt et al. (A42)in a review with 57 references. Gerstein et al. (A43)presented a review with 38 references on proton NMR spectroscopy of coals, cokes, and coal-derived liquids.
SOLVENT SWELLING Correlations between swelling and coal properties are discussed in a paper by Jones and co-workers ( A M ) on the swelling of low-rank coals;they measured the swellingof coals from different sources by pouring the solvent on coal samples in glass tubes and measuring coal height before and after contact with solvent. Spears and co-workers (A#) studied the H-bondin ability of functional groups in ores of Argonne premium coa! samples exposed using an EPR technique. Changes in the macromolecular structure of various coals induced by pyrolysis in H or He were studied by Suuberg and co-workers (A46) by solvent swelling of the quenched chars. Differential scanning calorimetry and solvent-swelling techniques (with THF and pyridine) were applied by Yun and co-workers (A47)to evaluate low-temperature coal structural changes prior to any major pyrolytic bond cleavage.
MISCELLANEOUS Mikula and Parsons (A48)discussed characterization and control of dustiness with alternatives to the ASTM D547 dust test. MiscellaneousReviews. Quick coal test procedures were discussed by Neavel (A49) in a review on analytical control procedures: air drying, rapid moisture and ash analyses and sulfur determinations, and calorific value determinations in coals. Mahajan (A50)presented a review with 25 references on the measurement of coal surface area b carbon dioxide absorption, also discussing the COz-inducecrswelling in coals and its effect on surface area and porosity measurement. Fullerton and others (A51) discussed rocess engineering studies of the perchloroethylene coal ckaning process in a review with eight references on coal desulfurization with perchloroethylene, including limitations, development, commercial status, and relevant engineering issues. Mass spectrometric studies of coals and coal macerals were discussed by Winans (A52) in a review with 22 references, which also includes a discussion of the examination of process-derived liquids by pyrolysis-high-resolution mass spectroscopy. (Al) Warne, S. St. J. Trends Anal. Chem. Wgl, 70(6), 195-9. (A2) Wroblewskl, A. E.; Verkade, J. G. Energy Fuels 1892, 6(4), 331-5. (A3) Wroblewski, A. E.; Relnartz, K.; Verkade, J. 0. Energy Fuels 1891, g6), 786-91. (A4) Bartle, K. D.; Taylor, J. M.; Williams, A. Fuel 1082, 71(6), 714-5. (A5) Markuszewski, R.; Zhou, X.; Chrlswell, C. D. Prepr.-Am. Chem. Soc., Div. Fuel Chem. 1892, 37(1), 417-23. (A6) Straszhelm, W. E.; Markuszewski, R.; Pollard, J. L.; Norton, 0. A. Coal Sci. Technol. 1881, 78, 55-70 (Process Util. High-Sulfur Coals 4). (A7) Huggins, F. E.; Mltra, S.; Vaidya, S.; Taghiel, M. M.; Lu, F.; Shah, N.; Huffman, G. P. Coal Sci. Technol. 1891, 78, 13-42 (Process. Utll. HiahSulfur Coals 4). (A8) Taghiel, M. M.; Huggins, F. E.; Shah, N.; Huffman,0.P. EnergyFuels1882, 83). .~.,,293-300. (A9) Hackley, K.C.; Liu, C. L.; Coleman, D. D.; Kruse, C. W. In Advances in cOa/SpctroscOp~Meuzelaar,H. L. C., Ed.; Plenum: New York, 1992 pp 69-89. (A10) Calkins, W. H.; Torres-Ordonez,R. J.; Jung, 6.; Gorbaty, M. L.; George, G. N.; Kelemen, S. R. Energy Fuels 1992, 6(4), 411-3. ( A l l ) Ge, E.; Wert, C. ACS Symp. Ser. 1890, No. 429, 316-25 (Geochem. Sulfur Fossil Fuels). (A12) Palmer, S. R.; Hippo, E. J.; Kruge, M. A.; Crelilng, J. C. ACS Symp. Ser. 1880, No. 429, 296-315 (Geochem. Sulfur Fossil Fuels). (A13) Hamilton, L. H.; Salehl, M. R. Pub/. Australes. Inst. Mln. Metall. 1981, 976)1-2 (Queensl. Coal Symp., 1991). (A14) Huggins,F. E.;Huffman,0.P. CoalSci. Technol. 1881, 77,42-61 (Chlorine Coal). (A15) Cox, J. A. Coal Sci. Techno/. 1881, 77, 31-42 (Chlorine Coal). (A16) McCormick,J. M.; FitzPatrlck,J. A. CoalSci. Technol. 1881, 17,449-67 (Chlorine Coal). (A17) Orvlni, E. J. Coal Qual. 1889, 43-4). 88-95. (A18) MunozGuIllena, M. J.; Linares-Solano, A.; Salinas-Martinez de Lecea, C. F0el1982, 77(5), 579-83. (A19) Christie, G. 6.; Malnwaring. D. E. Fuel 1982, 77(4), 443-7.
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PETROLEUM AND COAL (A20) Ma. S.; Hill, J. 0.; Heng, S. Themochlm. Acta 1991, 790(2), 291-7. (A21) McHugh, E. A.; Diessel, C. F. K.; Kutzner, R. Fuel1991, 70(5),647-53. (A22) Mltchell, G. D.; Davis, A.; Rathbone. R. F. Ironmaking Conf. Proc. 1991, 50, 199-206. (A23) Weltzsacker, C. L.; Gardella, J. A., Jr. Anal. Chem. 1992, 64(9), 106875. (A24) Bensley, D. F.; Crelllng, J. C. I n Advances in Coal Spectroscopy; Meuzelaar, H. L. C., Ed.; Plenum: New York, 1992; pp 119-39. (A25) Turlan, R. M.; Hsu, F. L.; AvramMls, K. S.; Sung, D. J.; Allendorfer, R. K. AIChE J. 1992, 38(7), 969-87. (A26) Strasrhelm, W. E.; Markuszewskl, R. Coal Prep. (Gordon & Beach) 1992, 70(1-4), 59-75. (A27) Straszhelm, W. E.; Markuszewskl, R. ACSSymp. Ser. No. 461, 31-43 (Coal SCI. 2). (A28) Cody, G. D.; Davis, A. Energy Fuels 1991, 5(6), 776-61. (A29) Olivelra, C.; Salgado, J. Nffii. Geophys. 1991, 5(3), 315-28. (A30) Oiivelra, C.; Salgado, J. Nucl. w h y s . 1991, y3), 329-37. (A31) Saigado, J.; Olivelra, C. Nucl. Instrum. Methods phys. Res., Sects 1992, 8644). 465-9. (A32) Wesoilnski, E. S.; De Jesus, A. S. M. Nucleer Techniques Exploretion and ExpkiteHon of Enefgy and Mlnwal Resources, Proceedings of an Internatlone1Symposlum, Vienna, June 5-8, 1990; 1991; pp 33-46. (A33) Cooper, H. R. Powder Technd. 1992, 69(1), 93-9. (A34) Rose, C. D. J. CoalQual. 1991, 70(1). 19-28. (A351 Vourvopoulos, 0.Nucl. Instrum. Methods phys. Res., Sect. E 1991, E567(Part 2), 917-20. (A36) Thomas, L. D.; Herod, A. A. Analyticel Applications of Spectroscopy, [Rocesdngs of an Intemtbnal Conference on Spectroscopy across the Spectrum), 2nd, 7990; Davies, A. M. C.. Creaser, C. S., Eds.; Royal Society of Chemistry: CambMge, U.K., 1997; pp 739-45.
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(A37) Yun, Y.; Meurelaar, H. L. C.; Slmmielt, N.; Schulten, H. R. ACS Symp. Ser. 1991, No. 467, 89-110 (Coal Scl. 2). (A38) Cole-Clark, P. A.; Vassallo, A. M. Fuel 1992, 77(4), 469-70. (A39) Yu. Q.; Bukka, K.; Ye, Y.; Miller, J. D. Coal Rep. (Gordon & Beach) 1992, lql-4), 77-92. (A40) Robblns, G. A. ACS Symp. Ser. 1991, No. 461, 44-60 1-( Scl. 2). (A41) Dela Rosa, L.; Ruskl, M.; Lang, D.; Qersteln, B. Solomon, P. Energy Fuek 1992, 6(4), 460-8. (A42) Orendt, A. M.; Solum, M. S.; Sethl, N. K.; Pugmire, R. J.; Grant, D. M. I n Advances In CoalSpectroscopy; Meuzelaar, H. L. C., Ed.; Plenum: New York, 1992; pp 215-54. (A43) Gersteln, E. C.; Pruski, M.; Michel, D. I n Advances In CoalSpectroscopy; Meuzelaar, H. L. C., Ed.; Plenum: New York, 1992; pp 193-213. (A44) Jones, J. C.; Boother, M.; Brown, M. J. Chem. Techno/. Ebtechnd. 1991. 52(2), 257-64. (A49 Spears, D. R.; Sady. W.; Klspert, L. D. Repr. Pap.-Am. Chem. Soc., Dlv. Fuel Chem., 1991, 36(3), 1277-82. (A46) Suuberg, E. M.; Otake, Y.; Deevl, S. C. Prepr. Pap.- Am. Chem. Soc., Dlv. Fuel Chem. 1991, 36(1), 258-66. (A47) Yun. Y.; Otake, Y.; Suuberg. E. M. Prepr. Pap.-Am. Chem. Soc., Dlv. Fuel Chem. 1991, 36(3), 1314-24. (A48) Mlkula, R. J.; Parsons, I.S. CoaiRep. (GwdonB &each) 1991, 9(3-4), 199-212. (A49) Neavel, R. C. Roc. C0nf.-Int. Coal Test. Conf. 1990, 8,29-32. (A50) Mahajan, 0. P. Carbon 1991, 29(6),735-42. (A51) Fullerton, K. L.; Lee, S.;Kullk, C. J. FOelSci. Technol. Int. 1991, 9(7), 873-88. (A52) Winans, R. E. Advances in Coaispectroscopl: Meurelaar, H. L. C., Eds.; Plenum: New York, 1992; pp 255-74.
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Crude Oil and Shale Oil Dennis L. Sutton Marathon Oil Company, Indianapolis, Indiana 46268-0007 This year's review on crude oil and shale oil references slightlyfewer articles than in the 1991publication. This may in part reflect the economic belt tightening which has been experienced within the oil industry. Also, the number of articles pertaining to coal liquids is down tremendously. Because of the new section on Source Rocks, some of the articles which may previously have appeared under this heading (in the biomarker subsection) can now be found in section F.
CRUDE OIL Bulk Characterization. Articles reviewed in this section emphasize the properties of the crude as a whole. Chromatographic. While gas chromatographic (GC) simulated distillation (SIMDIS) has been widely used for many years, current research strivesto extend the temperature range of applicability and to provide more reliable analyses. Improved packed and capillary columns have been developed which are applicable to the two ASTM GC SIMDIS methods-D2887 and D3710 (SI).Martin detailed techniques used to perform onstream SIMDIS of the higher boiling point samples encountered in refinery processes (B2).A review with seven references addresses the application of GC SIMDIS to process GC and highlights performance testing and case examples (B3),while a review by scientists at Supelco discusses the evolution of SIMDIS from the early use of largediameter packed columns to current trends using hightemperature fused-silica capillary columns (B4). The use of high-temperature GC with atomic emission detection (AED) to provide details of not only C, H, and S but also V and Ni was documented. The nickel sensitivity provides a means of analyzingvolatile Ni compounds without much need of preconcentration (B5). Kosman characterized refinery streams and heavy oils by GC-AED (B6) and also published a review with four references on the use of GCAED for multielement detection and quantitation in petroleum and products (B7). The effect of the degree of aromaticity and alkyl substitution of polyaromatic hydrocarbons on GC-FID response factors was evaluated. The conclusions, based on these response factors, were that the analysis of crudes using D2887 would give conservative estimates of distillate yields with uncorrected procedures (B8). Lubkowitz and Bellows described a technique whereby only the more volatile components of a complex mixture (such as crude) are introduced to an analytical column while the heavier constituents are back-flushed to vent (B9). A rapid PONA (paraffins, olefins, naphthenes, aromatics) determination of process streams has provided timely information for monitoring and control of refinery operations (BIO). Headspace GC was utilized as the basis for measuring vapor pressures of petroleum mixtures. An important goal of this work was to develop a method for heavy crudes which would complement the Reid vapor pressure technique (BII). GC retention behavior of dibenzothiophenederivatives on a smectic liquid phase was studied and the information applied to the analysis of crudes (BIZ). Complex hydrocarbon mixtures, such as those obtained from de raded oils, refined petroleum fractions, and oil-containing sefiments, were oxidized to yield chromatographically resolvable mixtures which could then be analyzed by GC/MS. The oxidation profiles could then be used to fingerprint the oils by calculatingthe intersample Euclidean distances, which are then input into a multidimensional scaling program that allowed similar samples to be clustered (B13). Diamondoids of the trimantane series, previously unreported petroleum constituents, were tentatively identified in crudes from the Smackover formation (Alabama) using GCMS (B14).GC/isotope ratio mass spectrometry makes it possible to measure the 13C/12Catomic ratios of particular componentsin crude oil, natural gas, or source rocks. Various saturate classes from a North Sea crude were studied (B15). Nali et al. compared anew GC/MS/MS approach to the more conventional GC/MS analysis for monoaromatic steroids (B16).Other applicationsof GC/MS to crude characterization
Dennls L. Sutton is currenttythe laboratory supervisor at Marathon Oil Company's Indianapolis refinery. Previously at the Technology Center in Littleton, CO, Dennis was responsible for Marathon's crude oil evaluation project and worked on the developmentof methodologiesforthe fiscal analyses of North Sea crudes. He is a member of ACS and is active in ASTM D-2. He received his bachelor's degree from the University of Colorado in 1979.
have included hydrocarbon type analyses using magnetic and quadrupole instrumentation (BI 7) and comparison of GC/ MS with direct samplin ion trap MS (B18). Welch and Hoffman cfemonstrated the use of a sophisticated LC/GC/MS system for the analysis of fossil fuels including solvent-refined coal, kerosine, and crude oil (B19). A polar aminocyano-bonded silica high-temperature liquid chromatographic (LC) column was used for the class separation of nitrogen compounds in crude petroleums. The results can be used to compare oils and associated source rocks (B20). A reversed-phase high-performance LC method was evaluated for the separation of terpane, sterane, and alkane biomarkers (B21).A reviewwith 71references features the uses of complexation chromatography to the analysis of and a broad review coal liquids and petroleum products (B22) with 311 references covers applications of chromatography to petroleum, coal, oil shale, and synthetic fossil fuels (B23). Rheological. A graphical method was suggested for the determination of wax separation temperature of crude oils from viscosity shear stress measurements. The method has the advantage over the ASTM pour point method as it gives consistent results for crudes treated with flow improver additives (2324). Wax precipitation from North Sea crudes was examined by both low-resolutionpulsed NMR (B25)and differential scanning calorimetry (DSC) (B26). The NMR estimated solid-phase content at -40 "C correlated well with the amount of wax determined by dimethyl ketone precipitation at -25 "C. Other wax-related articles described waxy crude handling in Nigeria (B27),characteristics of high-pourpoint crudes that respond to flow modifiers (B28),and an analytical protocol for characterizing waxy crude oils (B29). Bombay High (India), having a pour point of 30 "C, was the focus of severalwax-related studies. Agrawal et al. utilized a centrifugation technique to investigate its sedimentation tendency (B30). Photomicroscopy proved to be a valuable tool for the direct observation of the physical phenomenon occurring during the cooling of Bombay High (B31). The crystallization of n-paraffins in the waxes from the middle distillate fractions was studied using X-ray diffractometry and photomicroscopy. In isolated petroleum waxes, the n-paraffins were found to crystallize with a predominantly orthorhombic structure, while in solvents forming gels, the lattice changes to a hexagonal structure (B32). Mehrotra responded to an earlier article by Agrawal et al. regarding the wax deposition of Bombay High under flowing conditions (B33). A general correlation for estimating the viscosity of undersaturated crude oils was developed based on 253 experimentally obtained oil viscosities on 41 different oils. The authors concluded that the new correlation clearly outperformed the existing correlations (B34). Closmann and Seba obtained data for molecular weight as a function of oil viscosity (B35). A method for estimating the viscosity of petroleum and its fractions is based on the similarity of the behavior of vapor pressure and kinematic viscosity variation with temperature. The method was tested on 15world crudes with an overall deviation of 6 % (B36). Singh et al. developed a simple and general equation which predicts the viscosity of crude oil or its fractions by identifying viscosity sensitivity to temperature changes. Viscosity is predicted over a wide ANALYTICAL CHEMISTRY, VOL. 65, NO. 12, JUNE 15, 1993
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temperature range based on a single viscosity measurement, and the overall average absolute deviation is 0.82% (B37). Allan and Teja described a new method em loying the effective carbon number for the correlation a n f rediction of viscosity of liquid hydrocarbonsand mixtures. T i e method was also applied to eight crude oil fractions (B38). An empirical correlation for oil viscosity at the bubble point was developed based on Canadian and Middle Eastern oil data. The correlation postulates a simple relationshi between oil viscosity and density at the bubble oint (B39). fn two related works, the rheological behavior of 8audi crudes (ArabHeavy, Arab Light, and Arab Berri) was studied (B40, B41). Experimental techni ues for waxy crude oils are described that enable reproducib e, steady-state, flow property data to be obtained from rotational viscometers. These data are applicable to ipeline design (B42). The wax precipitation tendency oftighly opaque wax crude petroleums has been determined by a method basedron near-infrared (IR) s ectroscopy coupled to a fiber optic system. The near-IR Iata were supported by viscosity-temperature correlations and by differential scanning calorimetry (B43). Spectroscopic. Distillate fractions from the Alwyn (North Sea) crude were characterized by one- and two-dimensional nuclear magnetic resonance (NMR) spectroscopy. Average molecular weights and structural parameters were calculated. Also, the limitations of NMR in res ect to high-boilin aliphatic fractions were noted (B44). Ereen et al. reporte! some preliminary results for the identification of sulfur forms in petroleum b 13C NMR. In principle, dialkyl sulfides, alkylaryl sulfidies, di 1 sulfides, benzothiophenes, and dibenzothiophenes canye distinguished (B45). Six North Sea crudes and their corres onding silica-adsorbed fractions were analyzed by I3C!M N € and subsequent rinci al comonent analysis (B46). Focusin on Bomlay d q h and katnagari (India), crudes were c assified b stepmse discriminant analysis of their proton a n d W NM.6 s ctra (B47). First-derivative spectroscopywas combined wit total scanning fluorescence to differentiate between similar or overlapping spectrums of crude oils and fractions. Applications for the technique included comparison of weathered crude with the original sample (B48). Review articles hi hlighted the charact6rization of petroleum by atomic a sorption s ectrometry (B49), inductively coupled plasma methods inductively coupled plasma atomic emission spectrosand Raman spectroscopy (B52). copy (ICP-AES) (B51), Polarity. The classification of crude oils according to their polarity was found to be advantageous for comparison and evaluation of petroleums (B53,B54). For production, polarity can predict the emulsion tendency of the crude. For downstream operations, the polarity relates to the ease of refining the crude into usable products. Other. Two extensive reports were published on the analysis of heavy oils. Compositional data on the Cerro Negro Orinoco belt crude oil (Venezuela)and new analytical methods were presented. Most of the chapters focus on the methods rather than the analytical data. In addition, published work on the analysis of heavy oils, tar sand bitumens, and like materials is reviewed, and the overall state of the art in analytical methodology for heavy fossil fuels is assessed (B55, B56). Of 5274 water determinations utilizing the distillation method (D4006) and the Karl Fischer titrimetric method (D4928),the latter was found to be accurate and efficient and is thus recommended. The distillation requires about 2 h while the Karl Fischer titration takes only 5 min (B57,B58). Two review articles address the subject of testing and monitoring sediment and water in crude oil (B59, B60). The densities of two crude oils (with bubble pressures of >0.6 MPa) at 288-343 K and
