Determination Of Saturates, Aromatics, Resins And .
Journal of Applied Chemical Research, 7, 4, 15-24 (2013)Journal ofAppliedChemicalResearchw w w. j a c r. k i a u . a c . i rDetermination of Saturates, Aromatics, Resins andAsphaltenes (SARA) Fractions in Iran Crude oil Samplewith Chromatography Methods: Study of the GeochemicalParametersElham Keshmirizadeh1,*, Somayeh Shobeirian1, Mahmoud Memariani21Department of Applied Chemistry, Karaj Branch, Islamic Azad University, Karaj, Iran.2Chemistry Research Institute of Petroleum Industry-Geosciences Research Division, Tehran, Iran.Received 22 Jun. 2013; Final version received 14 Aug. 2013AbstractIn this study, Iran crude oil samples (K, L) were separated on the basis of solubility and polarity,resulting in saturates, aromatics, resins, and asphaltenes fractions. The fractions were analyzedby traditional open column chromatography, thin layer chromatography-Flame ionizationdetector in an Itroscan instrument (TLC-FID) and Gas chromatography with flame ionizationdetection for the determination of n-alkane and isoprenoid distribution in oil samples that arechosen as the most suitable structures for the identification and differentiation of crude oilsamples and oil-oil correlations. The precursor organic matters of the analyzed oil samplesof K, L are from a low salinity marine carbonate and reduced depositional environment.The studied oil samples were light and appeared to be mostly of type II, III kerogen mixtureorigin. The Koil sample is moderately mature (OEP and CPI are near 1).Keywords: SARA fractions, TLC-FID, Crude oil, Maturity parameters, Geochemicalparameters.Introductionon the understanding of the physicochemicalOver the last few decades, an increase in properties of the crude oil mixture. Forthe demand for commercial light oil and the petroleum fluids composition and propertiesdecline of the quality of crude oil have been vary continuously from the simplest structuresobserved [1].The recovery of useful productsto macromolecule [2]. The characterizationfrom petroleum has been for several years of the heavy fraction is then based on thean increasingly important task that is basedidentification of a number of families with*Corresponding author: Dr. Elham Keshmirizadeh, Assistant Prof., Department of Applied Chemistry, Karaj Branch, Islamic AzadUniversity, POBOX: 31485-313, Karaj–Iran. Email: ekeshmirizadeh@yahoo.com, Tel: 026-34182305, Fax: 026-34418156.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)16certain properties which can be easily asphaltene flocculation [7, 8].distinguishable from each other [3]. WhileThere is however no single approach thatsimulated distillation by gas chromatographycan rapidly, reliability and simultaneouslyis a routine means for characterization of the characterize crude oil fractions and specificlight end, it is not applicable for heavy-end classesofcompoundsandindividualcharacterization due to inability of GC for compounds in each fraction. Many standardcharacterization of large molecules. Therefore methods(e.g. ASTM D2007, D4124) had beenthe methods employed rely on solubility developed for characterizing the crude oiland other chromatographic techniques [4]. fractions but the gravimetric quantificationThe SARA procedure [5] modified for oftypicalfractionsprovedinadequatecharacterization of the heavy end as already [9,10].Coupling fractionation by TLC anddescribed by Vazquez and Mansoori [6] wasquantification using with flame ionizationused to separate a sample into four classes ofdetection(FID),theTLC-FIDmethodcompounds, namely saturates, aromatic, resins developed in the 1970s showed to offer severaland asphaltenes.advantages: (i) simultaneous fractionationThe saturate fraction consists of a viscous crude oil into saturated, aromatic and polarwhitish translucent liquid mainly composed classes, (ii) applicability for the determinationof paraffin’s and diamond oils. From the four of heavy fractions with high boiling points,fractions separated from the heavy-end only (iii) low cost, simple instrument requirementsthe saturate fraction is easily distinguishable andproceduresaving. Therefore, TLCand separated from the rest of the oil due to method rapidly became extensively appliedthe absence of π-bonds in between saturate for analysis of drugs, crude oils, coal-derivedhydrocarbon molecules. The aromatic fraction liquids [11-13].is a viscous reddish liquid composed ofThe objectives of this paper were: (i) toaromatic hydrocarbons with various degrees compare the extraction efficiency of stitutionsulfur,oxygen,and open column chromatography and the TLC-nitrogen) FID Itroscan separations of crude oils intocontent forming a continuum with respect to classes of compounds such as SARA,(ii)polarity, molecular weight and other properties. to identify specific compounds in the lightThe resin fraction is a dark brown colored, fraction of crude oil using GC, (iii) to explainsthick viscous liquid to semi-solid with a higher how certain non-biomarker parameters, suchdegree of condensation and heteroatom content as ratios involving n-alkanes hydrocarbons,than the aromatics. It plays an important role in are used to assess thermal maturity.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)17Experimentaln-heptane and mixed with activated aluminaSARA Fractionation of Crude Oil(80 200 mesh, Merck, Germany). The slurryA SARA separation system was developed towas dried and loaded on the top of a glasscharacterize crude oils of interest. Crude oil column, packed with neutral alumina sorbent.samples (K, L) for this study were obtained In sequence, n-heptane, toluene, and toluene/from a South west of Iranian source and stored methanol (9:1, v/v) (HPLC grade, Merck,under argon. The asphaltene fraction was Germany) mixtures were used to eluteprecipitated from the corresponding crudesaturates, aromatics, and resins. A total ofoil using n-heptane (HPLC grade, Merck, 350 ml of solvent/g of maltenes was usedGermany). To obtain the asphaltene, a slightly for the chromatographic separation. Thinmodified SARA fractionation procedure was layer chromatography was used to monitorused (Fig 1) [6]. A total of 30 ml of n-heptane/ the complete separation of each fraction.gof crude oil was added. The precipitated Finally, the fractions were rotary-evaporatedportion was filtered and dried under inertto dryness and then weighed. To have a correctgas flow. The sample (with the filter) wasmass balance, the volatile part of the originalextracted with 300 ml of toluene (HPLC grade, sample was also determined using rotavapOver lack, Germany) until no color changes vapor at 26 mbar and 30 C. The obtained masswere observed. The re-dissolved asphaltenebalance and recovery is presented in Table 1.fraction was rotary-evaporated and afterward, The reported SARA-values of the low-yielddried under a continuous stream of nitrogen. samples in this study are corrected to 100 %The extracted solution (maltenes fraction) wasby adjusting the saturate and aromatic values.rotovapped until a stable mass was achieved. Hence, the evaporation loss from the resinThe dried maltenes were then diluted with fraction is considered to be negligible.Table1. SARA fractions of crude oil samples analyzed with TLC-FID Itroscan and traditional open 90.9L*Analyzed by TLC-FID Itroscan, **Analyzed by traditional open column ID procedure of crude oilssubstantiallyshowedRecently, the TLC-FID method has beenthat a sample loading as low as 5–10µg was
18E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)optimal regarding signal-to-noise ratio [14]. and electronics) could meet the followingKarlsen and Larter [15] and Cebolla et al. [16] specifications: Operating temperature: 100 Cinvestigated the effect of scan speed on theto 300 C, sensitivity 0.015 C/g, minimumFID response, and found that the FID responsedetect ability: 5*10 12 g carbon/second,decreased when increasing the scanninglinearity 107.speed. A TLC device (MK-6S, Tokyo, Japan)A Varian cp-3800 gas chromatograph wasequipped with FID detector was used to test used to analyze the oil samples. The gasthe TLC-FID method. The S-III chromarod chromatograph (GC) was equipped with(MKI, Tokyo, Japan) used in this study wasan auto sampler for injections, a flame15.2cm long and 1.0mm in diameter and wasionization detector (FID), and electroniccoated with a layer of silica gel (5µm particle pressure flow controllers to ensure constantsize). During experiments the chromarod wasflow throughout the oven-heating program.spotted with 1µL of extract, and subsequently The GC was operated using the followingwas developed with the following program: analytical materials and conditions: 1 columnn-hexane (30 min), 50% (v/v) hexane–DCM (100 m 250 μm I.D 0.5 μm film thicknesses),(20 min) and 95% (v/v) DCM–methanol (5 injector temperature of 250 C, pressuremin). The chromarod was dried at 40 C for 2283 kPa, split ratio set to 100:1, and FIDmin after each development. For the TLC-FID temperature of 300 C. The GC oven wasmethod, a scan rate of 40 s/scan was used. Airprogrammed from 35 C with a 13 min initialand hydrogen flows were 2000 mL/min and isotherm, then an initial heating rate program160 ml/min, respectively.of 10 C/ min to 45 C with a 15 min hold timeafter which the rate was decreased to 1.9 C/Whole oil GC analysismin to a final temperature of 200 C with 5 minA gas chromatograph capable of oven hold time. Helium carrier gas was used withtemperature programming from 35 C to a minimum purity of 99.999%. The injected200 C in 1 C/min increments was used. A sample volume was 0.5 μl. The crude oil washeated flash vaporizing could provide a linear back flushed 0.3 min after injection to removesample split injection (for example, 200:1).its heavy components. The assignment of theThe associated carrier gas controls couldC7 compounds was based on comparison withprovide reproducible column flows and split chromatogram references provided by theratios. A hydrogen flame ionization detector supplier of a commercial mixture of paraffin’s,designed for optimum response with capillary naphthenesandcolumns (with the required gas controls (ASTM D- 5134).aromatichydrocarbons
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)19Scheme 1. SARA Fractionation According to the Solubility of Each Fraction.Whole oil GC is a common type of analysiscontaining compositions. It is important tofor oil samples. The analysis (Figure 2) willhave good resolution for both the light andgive a complete picture of the hydrocarbons heavy components.present in the oil and also of the sulphur-Figure 2.The GC chromatogram for the analyzed oil samples(K,L). Note:(C9:naphta, C9-C14:Kerosene, C14C20:Diesel, C20 :Residual fuel oil).
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)20Result and discussionother in this study also oil-oil correlation wasAnalysis of crude oil samplesperformed.The crude oil samples were fractionated byFrom an overall comparison the two crude oilsthe traditional and TLC-FID (Itroscan) SARA seem quite similar in composition.technique as described by in the experimental In general, the mass ratios of asphaltenessection.Theexperimentwasrepeated to resins in crude oils around the worldseveraltimes and the average results, reported have been found to be quite small, in theas wt. % are presented in Table 1 and Figure range of 0–0.26. For the crude oils under3. The results obtained from the fractionation study here the average ratio were foundof crude oils K, L were compared with eachto be 0.02 and 0.09 respectively [17-19].Saturate806040Sample K.traditionalSample L.traditionalSample K-TLCSample L.TLC200AsphalteneAromaticResinFigure 3. Star diagram (comparative diagram) for SARA fractions of two samples K, L under traditionalmeasurement and modern measurement.maturity but also affected by other processes,Non-biomarker maturity parametersThis study explains how certain non-biomarker such as source and oxidizing, reducing andparameters, such as ratios involving n-alkanes biodegradation measured using peak heights orhydrocarbons, are used to assess thermal areas from gas chromatography(GC data) andmaturity. Various characteristics of petroleumtype of kerogen, however carbon preferencesamples can be used to assess their relativeindex(CPI) and odd-even preference(OEP)level of thermal maturity.are defined as follows [20]:Alkanes & isopronoids (pristine and phytanes)CPI ଶ [େଶସାେଶ ାେଶ଼ାେଷ ାେଷଶ େଶ ାେଶ଼ାେଷ tios:specificforଵ େଶହାେଶ �ଶ ାେଶଽାେଷଵାେଷଷ(େଶଵା େଶଷାେଶହ)OEP (ସେଶଶାସେଶସ)(2)
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)21CPI and OEP parameters show the strengthwere calculated by the integrated peak areaof the odd carbon in n-alkanes. According tofrom GC (CPI, OEP, Pri/Phy))Table 2 and Figure 4 (geochemical parametersTable 2. The ratios and values of the majority of the used non biomarkers in this study.SampleKCPIEq(1)0.941.10L*Pristane:Pri, 950.530.480.990.950.540.34Broocks noted the presence of the regular As the Pri/Phy ratio for the analyzed oilisoprenoidspristane(Pri)andphytane samples (K, L) are 0.95, 0.95 respectively,(Phy) in crude oils and coal extracts [21]. A therefore a marine influence on the type ofmechanism for the production of relatively the source organic matters can be detected.high concentrations of pristane in oxic The plot of the Pri/nC17 and Phy/nC18 valuestype environments and high concentration for the analyzed sample on the specific plot inof phytane in reducing type environmentsthe Figure 4 indicated a mature marine sourcewas represented [22]. Thus, the Pri/Phy of organic matter (mostly type II, III kerogenratio evolved as an indicator of the oxicitymixture) deposited in a reduced condition withof the initial organic matter’s depositional less effect of biodegradation.environment. The Pri/Phy ratios are veryKerogen is a mixture of organic chemicalhelpful in determining the pale depositional compounds that make up a portion of theenvironment and source of the precursor organic matter in sedimentary rocks. Itorganic matters of the reservoired oil. It isis insoluble in normal organic solventswell known that Pri/Phy ratios 3.0 indicates because of the huge molecular weight of itspredominantly non marine source from component compounds. The soluble portion isterrestrial organic matter,(terrigenous plant known as bitumen. When heated to the rightinput) deposited under oxic to suboxictemperatures in the Earth’s crust, (oil windowconditions [20, 23].An oil accumulation have ca. 60–160 C, gas window ca. 150–200 C,Pri/Phy ratio 0.8 indicates saline to hyperboth depending on how quickly the sourcesaline conditions associated with evaporaterock is heated) some types of kerogen releaseand carbonate deposition, while marine crude oil or natural gas, collectively knownorganic matters usually have Pri/Phy 1.5 [20]. as hydrocarbons (fossil fuels). When such
22E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)kerogens are present in high concentration do not necessarily mean higher maturity; theyin rocks such as shale they form possiblecan also mean a lack of higher n- alkanessource rocks. Shales rich in kerogens that stemming from terrestrial input. The measuredhave not been heated to a warmer temperatureCPI values for the studied oil samples (K,L)to release their hydrocarbons may form oilare respectively equal to 0.94 and 1.1 whichshale deposits [24]. All types of kerogen are means that they are moderately mature oils.introduced in Figure 4.In practice, the OEP can be adjusted to includeany specified range of carbon numbers.Level of thermal maturitySome examples of CPI and OEP variationsThe gas chromatogram of the saturated are shown above (Eq1, Eq2). CPI or OEPhydrocarbon fractions shows a shift in thevalues significantly above (odd preference)normal alkane distribution to lower carbon or below (even preference) 1.0 indicates lownumbers (Figure 2), reflecting relatively thermal maturity. Values of 1.0 suggest, buta moderate level of thermal maturity, The do not prove, that an oil or rock extract isanalyzed oil samples are light samples (Table 1thermally mature. CPI or OEP values belowand Figure 3) this can be interpreted according1.0 are unusual and typify low-maturity oilsto Justwan [25] in terms of increased typeor bitumens from carbonate or hyper salineII, III kerogen mixture contribution. CPI can environments. Organic matter input affectsoffer valuable information on the maturation CPI and OEP. However in this study OEP ofof source rocks and reservoired oil. High CPI K, L oil samples are 0.54 and 0.99 respectively,values (above1.5) always refer to relatively one can conclude that L sample has lowerimmature samples. Low CPI values, however,maturity.
E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)23Figure 4. Pristane/C17 versus Phytane/C18 diagram for the studied oil samples. Note:Type I Kerogen: Sapropelic(containing alginate), Type II Kerogen: Planktonic (marine),Type II Kerogen: Sulfurous (similar to Type II but highin sulfur, Type III Kerogen: Humic(Land plants (coastal)).ConclusionAzad University, Karaj branch) funds herebyThis has resulted in the observation that crude the authors express their gratitude.oil SARA-data can be determined both frommodern method (TLC-FID Itroscan method) Referencesin a fast and simple manner compared to[1] E.J. Swain, Oil Gas J., 93 (2), 37 (1995).the more tedious traditional open column [2] A.M. McKenna, J.M. Purcell, R.P.chromatography-gravimetry method.Rodgers, A.G. Marshall, Energy Fuels, 24,The precursor organic matters of the analyzed 2929 (2010).oil samples of K, L are from a low salinity [3] S.S. Betancourt, G.T. Ventura, A.E.marine carbonate and reduced depositional Pomerantz, O. Viloria, F.X. Dubost, J. Zuo, G.environment. The studied oil samples are lightMonson, D. Bustamante, J.M. Purcell, Energyand appear to be mostly of type II, III kerogenFuels, 23, 1178 (2009).mixture origin. The Koil sample is moderately [4] K.J. Leontaritis, G.A. Mansoori, Int. J.mature (OEP and CPI are near 1).Pet. Sci. Technol., 2, 1 (1989).[5]D.M. Jewell, E.W. Albaugh, B.E. Davis,AcknowledgementR.G. Ruberto, Ind. Eng. Chem. Fundam., 13This research was supported by KIAU (Islamic (3), 278 (1974).
24E. Keshmirizadeh et al., J. Appl. Chem. Res., 7, 4, 15-24 (2013)[6] D.Vazquez, G.A. Mansoori, J. Pet. Sci.[20]Eng., 26, 49(2000).Moldowan, “The Biomarker Guide”, Second[7] A. Gaspar, E. Zellermann, S. Lababidi,Edition, Volume II, Biomarkers and IsotopesJ. Reece, W. Schrader, dx.doi.org/10.1021/in Petroleum Systems and Earth History,ef3001407, Energy Fuels (2012).United Kingdom at the Cambridge University[8] G.A. Mansoori, KU Int. J. Sci. Technol.Press, 684 (2005).Trans., B 1 (2002).[21] J.J. Broock, R.E. Summons, “Sedimentary[9] B.N. Barman, J. Chromatogr. Sci., 34, 219Hydrocarbons,(1996).Life, in Holland, H.D. and Turekian, K.K.[10] B.K. Sharma, S.L.S. Sarowha, S.D. Bhagat,(eds.), Treatise on Geochemistry”, Vol. 8,R.K. Tiwari, S.K. Gupta, P.S. Venkataramani,Biogeochemistry, Elsevier, Amsterdam, 425J. Anal. Chem., 360, 539 (1998).(2004).[11] S. Chopra, F.J. Ahmad, R.K. Khar, S.K.[22] R.P. Philp, “Formation and GeochemistryMotwani, S.M. Zeenat Iqbal, S. Talegaonkar,of Oil and Gas, in Holland, H.D. and Turekian,Anal. Chim. Acta 577, 46 (2006).K.K. (eds.), Treatise on Geochemistry”, Vol.[12] J. Vela, V.L. Cebolla, L. Membrado, J.M.17, Sediments, Diagenesis and SedimentaryAndrés, J. Chromatogr. Sci., 33, 417 (1995).Rocks, Volume Editor, F.T. Mackenzie,[13] N.C. Shanta,
SARA Fractionation of Crude Oil A SARA separation system was developed to characterize crude oils of interest. Crude oil samples (K, L) for this study were obtained from a South west of Iranian source and stored under argon. The asphaltene fraction was precipitated from the corresponding crude o
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