Characterization Of Petroleum Crude Oils By Fourier .
Petroleum & Petrochemical Engineering JournalCharacterization of Petroleum Crude Oils by FourierTransform Infrared (FT-IR) and Gas Chromatography-MassSpectrometerysAhmad I1*, Sohail SM1, Khan H2, Khan R1 and Ahmad W11Instituteof Chemical Sciences, University of Peshawar, Khyber Pakhtunkhwa,Volume 2 Issue 2Received Date: March 07, 2018Pakistan2DepartmentResearch Articleof Environmental Sciences, University of Peshawar25120, Peshawar,Published Date: March 20, 2018Khyber Pakhtunkhwa, Pakistan*Corresponding author: Imtiaz Ahmad, Institute of Chemical Sciences, University of Peshawar, 25120, Peshawar,Khyber Pakhtunkhwa, Pakistan, Tel: 92-91-9216652; Email: patwar2001@yahoo.co.inAbstractWe attempted to analyze light, medium, and heavy petroleum crude oils by Fourier transform infrared (FT-IR) and gaschromatographic mass spectrometry (GC-MS) so as to identify and quantify the various hydrocarbon group types andheteroatom-containing hydrocarbons. The results inferred that the crude oils studied have quite similar individualhydrocarbons but differ in hydrocarbon group types i.e. paraffinic, olefinic, naphthenic, and aromatic group types andcarbon range products distributions. The RCP-I is dominated by C11–C13, while RCN-II and RCA-III by C5-C10 rangehydrocarbons.Keywords: Petroleum; Characterization; Spectroscopy; Chromatography; GC-MSIntroductionCrude oil is a mixture of hydrocarbons that existed inthe liquid phase in natural underground reservoirs andremains liquid at atmospheric pressure after passingthrough surface separating facilities [1]. Crude oil isnaturally occurring material comprises of varioushydrocarbons including paraffins, olefins, naphthenes,aromatic and heteroatom containing compounds as wellas organometallic compounds of nickel and vanadium(porphyrins) [2]. Its composition/quality varies due to itsorigin and conditions to which it is exposed duringtransportation and storage [3]. It is usually processed at arefinery to obtain useful products like gasoline, diesel,kerosine oil, lubricating oil feed stocks, furnace oil,bitumen/asphalt, etc. [4].Major groups of compounds present in petroleum aresaturated hydrocarbons (straight chained, branched andcyclic hydrocarbons), aromatic hydrocarbons, sulphurbearing compounds, resins and very large aromaticasphaltene compounds [5]. The concentration of differentchemical components depends on the type of the crudeoil. Light and medium crudes yield moreCharacterization of Petroleum Crude Oils by Fourier Transform Infrared (FT-IR) and Gas Chromatography-Mass SpectrometeryPet Petro Chem Eng J
2Petroleum & Petrochemical Engineering Journalaliphatic/naphthenic components compared to heavycrude oil which yields more heavy compounds, such asaromatic structures, and a high concentration ofasphaltenes and resins [6].The phenomenal increase in global energy demand anddepletion of conventional resources, combined withclimate issues has urged careful and environment-friendlyutilization of the proven crude oil reserves. Crude oilsbeing high-cost commodities and valued feed streams forrefiningneed careful characterization. Several attributesincluding cost, environmental impacts, and ability toproduce light premium fuels are considered beforerecommending for refining. Its suitability for downstreamprocessing is judged by detailed characterization [7].However, owing to compositional complexity, itscharacterization and analysis is always considered as achallenging job [8].Extensive studies focused on its characterization aphic, and spectroscopic methods [9-14].Thermal methods can also be effective [15-17]. Elementalanalysis of crude oil shows that it contains mainly carbonand hydrogen in the approximate ratio of six to one byweight [18]. The mixture of hydrocarbons is highlycomplex and the complexity increases with boiling range.The instrumental techniques of chromatography,ultraviolent and infrared spectroscopy together withmass spectrometry facilitate knowledge of the detailedhydrocarbon type composition of the complex crude oil.FTIR and GC-MS are considered as better techniques forpetroleum characterization [19-21]. We illustrate the useof FTIR and GC-MS for detailed analysis of the threeindigenous crude oils i.e. light, medium and heavy crudeoils so as to know about their chemical compositions andheteroatom contents.ExperimentalSamples CollectionCharacterizationandPhysico-Chemical Properties:1. Density; ASTM D 14802. API gravity; ASTM D 40523. Conradson carbon residue; ASTM D 189 – 054. kinematic viscosity; ASTM 4455. pour point; ASTM D 97 – 056. flash point; ASTM D 937. aniline point; ASTM-D 611-048. Whatson characterization constant.Elemental Analysis1. Determination of C, H, N, S and O. The elementalanalysis was carried out by CHNS analyzer.FTIR and GC-MS CharacterizationA double beam FTIR spectrophotometer was used inthis study. In a typical analysis, potassium bromide (KBr)pellets were prepared by using analytical grade KBr. Asmall drop of the test oil was applied to the prepared KBrdisc. The GC-MS analysis was carried with a gaschromatograph coupled with MS analyzer (GC-MSQP2010Shimadzu).Results and DiscussionPhysico-Chemical CharacterizationIt is well documented elsewhere that the physical andchemical characteristics of a crude oil vary considerablywith its composition [2]. The physico-chemicalcharacterization of the crude oils understudy was carriedout. The values for different physicochemical parametersobtained for the oil samples were; densities (0.76,0.85,and 0.94 g/cm3); API gravities (54, 35, 19);viscosities (10, 8, and 14 mm2/s); CCR (0.98, 0.92, and0.98 % wt); pour point (-12, -14, and -16oC ), flash point(96, 93, and 96oC) and Watson characterization constant(K) values( 12, 11 and 10),for LC, MC and HC, respectively.Physico-ChemicalThree indigenous crude oils were used in currentinvestigation and coded as:1. Light crude denoted as LC, Pariwali, oil field2. Medium crude denoted as MC, Naspha oil field3. Heavy crude denoted as HC, Turkawali oil field.The as received oils were characterized by ASTM methods[22]. The properties determined were:The elemental analysis were; C (85.44, 85.91 and 86.10%), H(11.15, 11.30,and 11.55; O(1.85, 1.21, and 0.96), N(0.11, 0.14, and 0.15) and S (1.45, 1.44, and 1.24) for LC,MC and HC, respectively. It can be seen that the nitrogenand sulphur contents are mostly concentrated in thenaphthenic and heavier fractions. The results indicate thatthe LC, MC, and HC oils have different physcio-chemicalproperties agreed to the values of published data and arefound to be light, medium and heavy crudes, respectively[4,23-25].Ahmad I, et al. Characterization of Petroleum Crude Oils by Fourier TransformInfrared (FT-IR) and Gas Chromatography-Mass Spectrometery. Pet PetroChem Eng J 2018, 2(2): 000148.Copyright Ahmad I, et al.
3Petroleum & Petrochemical Engineering JournalFTIR ResultsStructural analysis of petroleum based products isperformed to know about fraction recognition,combustion properties, and efficiency of fuel and qualityinspections. It also influence the quality of the marketableproducts derived from crude products [26].It has been reported elsewhere that crude oils whichhave similar physical properties but possess widelyvarying chemical compositions [27]. The absorptionbands of aliphatic C H bonds, with additional bandsoriginating from groups containing aromatics, oxygen,sulfur, and nitrogen, usually dominate the spectra ofcrude oils [28]. The FTIR of the oils understudy wascarried out. The results are discussed as under:LC: The FTIR analysis of LC was performed. The data isgiven in Table 1. The clear larger size absorption peakswere observed at 2954 and 2822 cm–1 corresponded tothe CH and CH2 stretching vibrations. The other welldeveloped bands centered at 1446 and 1419 cm–1corresponded to the CH, CH3 bending vibrations(deformations) were also observed. A medium intensitypeak appeared at 727 cm–1 showed CH2 bending. Anothermedium intensity band at 1078 cm–1 observed evident theCH bending vibrations [29]. The appearance of thesepeaks reveals the paraffins characterized by CH, CH2 andCH3vibrations.The results exhibited bands appearing at852 and 1647 cm–1 due to CH bending and C C stretching,respectively [30]. A medium peak exhibited at 1725 atcm–1 is indicative of carbonyl compounds i.e. ketone.Similarly, a small band observed at 3550 cm–1 due to O-Hbond stretching vibrations confirmed the alcoholiccontents of the sample under study. It is clear from theresults that the intensities of the bands appeared forparaffins were found to be high which reveals its highconcentration in the sample under test. On the other handband, the peaks observed for aromatics/olefins andoxygenated compounds have poor intensities whichindicate their presence in low concentrations. It may beconcluded from the results that the LC possess long chainparaffins as the major constituents and thearomatics/olefins and oxygenated compounds as theminor components.Position (cm-1)IntensityAssigned configuration727MediumCH2 (bend) aliphatic852WeakC-H (bend) aliphatic1005WeakC-H (bend) aliphatic1273MediumC-O(Stretch) Alcohol1377StrongC-H (bend) aliphatic1446StrongCH3 (bend) aliphatic1647WeakC C (stretch) aromatic1725mediumC O (stretch) ketone2822StrongCH2 (bend) aliphatic2954StrongCH (bend) aliphaticTable 1: FTIR analysis of LC: Major Absorption Peaks Observed.MC: The FTIR analysis of MC was carried out and datahave been presented in Table 2. Some distinct bandsappeared at 2922 and 2852 cm–1 characterizing the CHand CH2 stretching vibrations. Peaks observed at 1456and 1377 cm–1 corresponded to the CH, CH3 bendingvibrations (deformations) were evident. A moderateintensity peak at 727 cm–1 indicated CH2 bending while apeak at 1078 cm–1 showed CH bending vibrations. Theobservation of these bands implies the existence ofparaffins which evidence CH, CH2 and CH3vibrations. Thearomatics/olefins as constituent of the oil under test wasensured by the appearance of some medium intensitypeaks centered at 790 and 1580 cm–1 due to CH bendingand C C stretching, respectively. A small peak exhibited at1715 cm–1 corresponded to ketone as carbonyl compound.For alcoholic contents, a small intensity peak can beobserved at 3525 cm–1 which is due to O-H bondstretching vibrations.Ahmad I, et al. Characterization of Petroleum Crude Oils by Fourier TransformInfrared (FT-IR) and Gas Chromatography-Mass Spectrometery. Pet PetroChem Eng J 2018, 2(2): 000148.Copyright Ahmad I, et al.
4Petroleum & Petrochemical Engineering JournalPosition gStrongAssigned configurationCH2 (bend) aliphaticC-H (bend) aliphaticC-H (bend) aliphaticC-O(Stretch) AlcoholC-H (bend) aliphaticCH3 (bend) aliphaticC C (stretch) aromaticC O (stretch) ketoneCH2 (bend) aliphaticCH (bend) aliphaticTable 2: FTIR analysis of MC: Major Absorption Peaks Observed.HC: The results of FTIR analysis of HC are compiled inTable 3. Some strong intensity bands were observed at2922 and 2852 cm–1which indicate the CH and CH2stretching vibrations. Few peaks noticed at 1456 and1373 cm–1 corresponded to the CH, CH3 bendingvibrations (deformations). A medium intensity band at740 cm–1 revealed CH2 bending and another mediumintensity peak at 1078 cm–1 show CH bending vibrations.The appearance of these peaks indicates the presence ofparaffins which represent CH, CH2 and CH3 vibrations. Thearomatics/olefins contents of the oil under test wasverified by the appearance of some medium intensitypeaks centered at 795 and 1584 cm–1which can bePosition uted to CH bending and C C stretching, respectively.At 1715 cm–1, a small peak evidenced the presence ofketone. A band at 3525 cm–1 due O-H bond stretchingvibrations can be seen which evident the presence ofoxygenates. The results revealed some larger intensitybands characterized the paraffin content in highconcentration of the oils. Conversely, the smaller intensitypeaks for aromatics/olefins and oxygenate contentaccounted for their low concentration. Thus, it may beinferred that the crude understudy contained long chainparaffins as the major components and thearomatics/olefins and oxygenate as the least umStrongStrongWeakmediumStrongStrongAssigned configurationCH2 (bend) aliphaticC-H (bend) aliphaticC-H (bend) aliphaticC-O(Stretch) AlcoholC-H (bend) aliphaticCH3 (bend) aliphaticC C (stretch) aromaticC O (stretch) ketoneCH2 (bend) aliphaticCH (bend) aliphaticTable 3: FTIR analysis of HC: Major Absorption Peaks Observed.GC -MS ResultsThe chemical and physical properties of petroleum aredirectly related to its chemical composition, whichdetermines its market value [31]. The GC-MSdistinguishes and characterizes crude oil sampleaccording to their compound classes [32]. The chemicalcompositions in terms of paraffins, naphtnenes,aromatics, oxygenates and olefins (PNAOO) of the threecrudes were studied by GC-MS. The data was used tocalculate the paraffins, olefins, naphtenes, aromatics,suplur and nitrogen containing hydrocarbon group types.The parffininc hydrocarbons identified in the LC includedmono, di, tri and tetraallylparaffines ranging from hexaneto octacosane, triacontane and tetratriacontane. Amongthe naphthenes, the major compounds identified werefound to be mostly mono, di and tri alkyl cyclohexanes.Ahmad I, et al. Characterization of Petroleum Crude Oils by Fourier TransformInfrared (FT-IR) and Gas Chromatography-Mass Spectrometery. Pet PetroChem Eng J 2018, 2(2): 000148.Copyright Ahmad I, et al.
5Petroleum & Petrochemical Engineering JournalVery few olefins recognized to be present included romatics compounds verified in the crude oil mostlyincluded alkyl derivatives of benzene. Some oxygenatedhydrocarbons were also present which included alcoholand ketonic derivatives of paraffinic and aromatichydrocarbons.were; sec-butyl benzene, 1-methyl, 2-propyl benzene, 1-4diethyl benzene, butane, 2-phenyl, 3-hydroxy, 4-cyano, (1,1-dimethyl propyl benzene), (3, 3-dimethyl butyl)benzene. The oxygenates triasterianone, 3, 3-dimethyl 2hexane-one, 2-butyl octanol. In case of original HC, theconcentrations of paraffins, naphthenes, aromatic,oxygenates and olefins were found.The GC-MS data of MC reveal similar results asobtained for LC. Compared with the main NIST library,most of the paraffins verified were found to be polyalkylderivative of aliphatic hydrocarbons with carbon atomsfrom 6 to as high as 30 per molecule. Abundantlyoccurring paraffins were alkylated, hexane, heptane,octane, nonane and decane. The naphthenic hydrocarbonidentified commonly mono, di or tri alkylcyclohexane.Among the olefins, the specific compounds identifiedwere found to be 2, 3, 4-trimethyl-2-pentene, 11-chloro-1undecene. The aromatics identified were solely the alkylbenzene derivatives. A number of largely occurring ofoxygenates, including hydroxy and ketonic compoundswere also identified.The relative abundance of the hydrocarbons typeswere calculated. The results of LC are provided in Table 4.The proportions of the paraffins, naphthenes, aromatic,oxygenates and olefins were found to be 85.67, 6.13, 6.16,1.43 and 0.73 %, respectively. The carbon rangehydrocarbons were found to be C5-C10, C11-C13, C14-C18andC5-C10 in concentration of 25.26, 58.81, 6.21 and 9.72%, respectively (Table 5). The relative abundance ofhydrocarbons types i.e. paraffins, olefins, naphthenes andaromatics were calculated in case of MC. The results areprovided in Table 4. The proportions of paraffins,naphthenes, aromatic, oxygenates and olefins were foundto be 63.45, 26.20, 7.00, 2.70 and 0.90 %, respectively.The different carbon range hydrocarbons determinedwere C5-C10, C11-C13, C14-C18 and C19-Cn in concentrations of74.40, 16.92, 4.63 and 4.07 %, respectively. Thedistribution of the different hydrocarbons rangecompounds calculated from GC-MS data determined incase of HC is given in Table 4. The concentrations ofparaffins, naphthenes, aromatic, oxygenates and olefinswere found to be 64.52, 14.67, 7.59, 2.70 and 12.08 and1.14 %, respectively. The different carbon rangehydrocarbons were i.e. C5-C10 (61.52 %), C11-C13 (18.69),C14-C18 (8.12 %) and C19-Cn (11.67) as per resultscompiled in the Table 5.From the GC-MS data of HC, the major paraffins verifiedwere found to be alkylated aliphatic hydrocarbonscontaining 7 to as high as 30 carbon atoms per molecules.Mostly these compounds included alkyl derivatives ofhexane, heptane, octane, nonane, decane, ,pentacosane, hexa cosine, octacosane and triacontane.The naphthenes confirmed were found to be di and trialkyl cyclohexane. Among the olefins the specificcompounds identified were found to be 2,3,4-trimethyl-2pentene, 11-chloro-1-undecene. The aromatics 6.2326.0214.67Concentration 2.7112.080.730.91.14Table 4: Hydrocarbon group types distribution determined in LC, MC and HC.C5-C10LCMCHC25.2674.461.52Concentration 4.638.129.724.0711.67Table 5: Carbon Number Distribution determined in LC, MC and HC.Ahmad I, et al. Characterization of Petroleum Crude Oils by Fourier TransformInfrared (FT-IR) and Gas Chromatography-Mass Spectrometery. Pet PetroChem Eng J 2018, 2(2): 000148.Copyright Ahmad I, et al.
6Petroleum & Petrochemical Engineering JournalIt is inferred from the results that all of the three crudeoils studied have quite similar chemical compositions interms of various individual hydrocarbons. However, theydiffer in paraffinic, olefinic, naphthenic, and aromaticgroup types with varying carbon range distributions. Therelative abundance of saturated hydrocarbons suggeststhat the oils are predominantly aliphatic. LC is dominatedby C11–C13, MC by C5-C10 while HC also by C5-C10.7.Datta M (2011) Petroleum Refining in India: Reformand Technical Efficiency in Public SectorEnterprises. Vol 1, Allied Publishers.8.Wang ZD, Fingas MFMF (2003) Development of oilhydrocarbon fingerprinting and identificationtechniques. Mar Pollut Bull 47(9–12): 423-452.9.Silva SL, Silva AM, Ribeiro JC, Martins FG, Da Silva FA,et al. (2011) Chromatographic and spectroscopicanalysis of heavy crude oil mixtures with emphasis innuclear magnetic resonance spectroscopy: Areview. Analytica chimica acta 707(1-2): 18-37.ConclusionsThe study concludes that the three crude oils havealmost similar individual hydrocarbons. However, theydiffer in hydrocarbon group types i.e. paraffinic, olefinic,naphthenic, and aromatic group types. The carbon rangeproducts distributions revealed that LC-I being light crudeis dominated by C11–C13, while MC and HC, being middleand heavy crudes, respectively, are dominated by C 5-C10range hydrocarbons.References1.Selley RC (1998) Elements of Petroleum Geology. 2nd(Edn.), Academic Press, USA.2.Dutt NVK (1990) A simple method of estimating theviscosity of petroleum crude oil and fractions. TheChemical Engineering Journal 45(2): 83-86.3.Falla FS, Larini C, Le Roux GAC, Quina FH, Moro LFL,et al. (2006) Characterization of crude petroleum byNIR. JournalofPetroleumScienceandEngineering 51(1-2): 127-137.4.Odebunmi EO, Ogunsakin EA, andIlukhor PEP (2002)Characterization of CRUDE OILS and petroleumproducts: (i) elution liquid chromatographicseparation and gas chromatographic analysis of crudeoils and petroleum products. Bulletin of the ChemicalSociety of Ethiopia 16(2): 115-132.5.6.Behrenbruch P, Dedigama T (2007) Classification andcharacterisation of crude oils based on distillationproperties. Journal of Petroleum Science andEngineering 57(1-2): 166-180.de Moraes DP, Antes FG, Pereira JS, dos Santos MDFP,Guimarã es RC , et al. (2009) Mi
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