Application of NMR Spectroscopy in the Analysis of Petroleum Derivatives and Products

Složen kemijski sastav i fizikalna svojstva nafte i naftnih goriva čine njihovu karakterizaciju vrlo zahtjevnom. Pojedinačni spojevi, sastojci nafte i proizvoda razlikuju se po molekulskoj strukturi, veličini, polarnosti i funkcionalnosti. Sastav i prisutnost određenih specifičnih ugljikovodičnih skupina u određenom proizvodu ovisi o vrsti goriva i postupku procesa obrade. Kako bi se predvidjeli potencijali goriva ili odredili zahtjevi za poboljšanjem, potrebno je dobro poznavanje sastava goriva. U tu svrhu stalno se razvijaju nove i sve sofisticiranije analitičke tehnike i metode. Spektroskopija NMR ima široku primjenu u istraživanju sastava složenih ugljikovodičnih smjesa nafte i naftnih proizvoda. Pregledom je obuhvaćena njezina primjena u analizi benzinskih i dizelskih goriva. Opisana je važnost razvoja tehnika CP/MAS NMR za snimanje čvrstih uzoraka u analizi naftno-geokemijskih supstrata. Prikazane su mogućnosti spektroskopije NMR u karakterizaciji polimernih aditiva koji se upotrebljavaju u naftnoj industriji.Complex chemical composition and physical properties of oil and fuel make their complete characterization very difficult. Components present in oil and oil products differ in structure, size, polarity and functionality. The presence and structure of specific hydrocarbons in final products depend on the processing procedure and type of the fuel. In order to predict or improve fuel properties it is necessary to determine its composition. Thus, new and more sophisticated analytical methods and procedures are constantly being developed. NMR spectroscopy plays a significant role in analysis and identification of complex hydrocarbon mixtures of petroleum and petroleum products. In this review, we describe the application of NMR spectroscopy for analyzing gasoline and diesel fuels. Hence, by using NMR spectroscopy it is possible to determine gasoline composition and presence of benzene and oxygenates, as well as some important physical characteristics of gasoline such as the research octane number. An application of different NMR techniques made it possible to characterize diesel fuels and middle oil distillates from various refineries. Data so obtained can be used in combination with statistical methods to predict fuel properties and to monitor production processes in the petroleum industry. NMR spectroscopy has proven useful in analysis of FAME which has recently been used as an ecologically acceptable alternative fuel. Furthermore, techniques such as CP/MAS for characterization of solid state oil-geochemical samples are included. Also, possibilities of using NMR spectroscopy in the analysis of polymeric additives are discussed

Polymerization, Thermal Stability and Degradation Mechanism of (Meth)acryl-Dicyclohexylurea and (Meth)acryl-Diisopropylurea Copolymers with Styrene and α-Methylstyrene

U radu je opisan utjecaj dicikloheksiluree (DCU) i diizopropiluree (DiPrU), u bočnom lancu monomera na osnovi (met)akrilata, na kopolimerizaciju sa stirenom (St) i α-metilstirenom (α-MeSt), toplinsku stabilnost i mehanizam razgradnje priređenih kopolimera. Polimerizacija je provedena s dibenzoil-peroksidom (Bz2O2) u butanonu ili dioksanu pri 70 °C, do niske konverzije. Rezultati pokazuju izrazite razlike u početnoj brzini polimerizacije i svojstvima polimera akrilatnih i metakrilatnih monomera u ovisnosti o supstituentu u bočnom lancu. Dok N-akril-N,N--dicikloheksilurea (A-DCU) lako homopolimerizira i kopolimerizira sa St-om i α-MeSt-om, N-metakril-N,N-dicikloheksilurea (MA-DCU) ne homopolimerizira niti kopolimerizira s α-MeSt-om, ali kopolimerizira sa St-om iako sporije nego odgovarajući akrilni monomer. Rezultati istraživanja pokazuju da uvođenje diizopropiluree umjesto dicikloheksiluree u metakrilatnom monomeru također utječe na početnu brzinu polimerizacije. Naime, N-(met)akril-N,N--diizopropilurea (MA-DiPrU) ne homopolimerizira niti kopolimerizira s α-MeSt-om. Polimerizacija sa St-om je sporija u usporedbi s odgovarajućim monomerom koji sadrži DCU. Kopolimerizacija je statistička reakcija u kojoj je, neovisno o sastavu smjese komonomera, uvijek veći udjel St-a u kopolimeru. Toplinsko ponašanje svih polimera u osnovi je slično. Zagrijavanjem pri temperaturama od 100 °C - 450 °C razgrađuju se dvostupnjevitim mehanizmom. U prvom stupnju pri temperaturama od 180 °C - 250 °C dolazi do izdvajanja cikloheksilizocijanata (C6H11NCO), odnosno izopropilizocijanata (C3H7NCO). Čvrsti ostaci identificirani su kao kopolimeri N-(met)akril-cikloheksilamida (A-CHA, MA-CHA), odnosno N-(met)akril-izopropilamida (MA-iPrA) sa St-om ili α-MeSt-om. Stabilni su do 280 °C, a zatim se u jednom stupnju razgrađuju pri temperaturama od 280 °C - 450 °C.This paper describes the polymerization of N-acryl-N,N\u27-dicyclohexylurea (A-DCU), N-methacryl- N,N\u27-dicyclohexylurea (MA-DCU) and N-methacryl-N,N\u27-diisopropylurea (MA-DiPrU) monomers with styrene (St) and α-methylstyrene (α-MeSt), thermal stability and degradation mechanism of prepared copolymers. Free-radical initiated polymerization was performed to low conversion by using dibenzoyl peroxyde (Bz2O2) in butanone at 70 °C under nitrogen stream. It was found that the pendant group in (meth)acrylic monomers have high influence to the polymerization as well as to the copolymer properties. A-DCU readily homopolymerized and copolymerized with St and r1,A-DCU = 0.72 and r2,α-MeSt= 0.07, while MA-DCU does not homopolymerized or copolymerized with α-MeSt under the same conditions, but copolymerized with St to randomly composed copolymers after a long heating of comonomers. Copolymers A-DCU with α-MeSt prepared under different monomer-to monomer-ratios in the feed have random composition with an azeotropic point at ratio of 0.75 (A-DCU) to 0.25 (St). The initial rate of copolymerization indicates that the rate increases almost linearly with the increase of ratio of A-DCU in the comonomer feed. Reactivity ratios determined by the Kelen-Tüdös method are: r1,A-DCU = 0.72 and r2,α-MeSt = 0.07. Molar mass of copolymers increased from 8.5 to 30 (kg mol-1) when mole ratio of A-DCU to α-MeStin the feed increased from 0.1 to 0.9. Poly(A-DCU) and copolymers with α-MeSt decomposed by two-step mechanism. Under TGA (nitrogen,10 °C min-1) conditions in the first step between 180 °C and 250 °C a quantitative yield of cyclohexylisocyanate (C6H11NCO) separated by a decomposition of dicyclohexylurea (DCU). The thermally stable residue represented poly(acryl-cyclohexylamide), poly(A-CHA), and copolymer with α-MeSt, poly(A-CHA-co-α-MeSt). Glass transition temperature (Tg) of poly(A-DCU) was at 184 °C and Tg of residue, poly(A-CHA), was at 161 °C. Tg\u27s of the copolymers are higher for the copolymer with higher A-DCU content. Tg\u27s of residue are increased also when the content of A-CHA in copolymer increased. Copolymers of A-DCU with St have a random composition with an azeotropic point at a ratio of 0.73 (A-DCU) to 0.27 (St). The rate of copolymerization of A-DCU with St increases by the increase of A-DCU in the feed. The reactivity ratio are: r1,A-DCU = 0.80 and r2, St = 0.50. Molar mass of copolymer, prepared at equimolar ratio of monomers in the feed, is Mw = 78.6 kg/mol-1. These copolymers decompose in TGA conditions by two-step mechanism, which correspond to the mechanism explained for the copolymers of A-DCU with α-MeSt. MA-DCU copolymerized with St to randomly composed copolymers. The reactivity ratio determined by the KT method are: r1, MA-DCU= 0.18 and r2, St = 4.84. These values indicate that MA-DCU favors cross-propagation over homopolymerization, while St favors homopolymerization as opposite to cross-propagation. It also shows, that since St is more reactive than MA-DCU, copolymers contain a higher proportion of St units. It was found, that the rate of copolymerization of MA-DCU with St is slower than the rate of copolymerization of A-DCU with St, and that the rate of copolymerization decreases by increasing the amount of MA-DCU in the feed. Molar mass of copolymer prepared at equimolar ratios of comonomers in the feed is Mw=12 kg mol-1. Thermal properties of poly(MA-DCU-co-St) are similar to those previously described in the decomposition of poly[A-DCU-co-St(α-MeSt)]. The results have also shown quite a big influence of DiPrU group in MA-iPrU to the polymerization with St and α -MeSt. Namely, MA-DiPrU does not homopolymerized or copolymerized with α -MeSt, but can polymerize with St only after a long heating of comonomers at 70 °C. The copolymerization of MA-DiPrU with St is a statistical reaction in which regardless of monomer-tomonomer ratios in the feed, an excess of St was in the copolymer. The reactivity ratios (KT method) are: r1, MA-DiPrU = 0.39 and r2, St = 1.03. The obtained data indicate a monomer tendency to alternating structure. The initial rate of copolymerization decreases with increasing the content of MA-DiPrU monomer in the feed. Molar mass of all copolymers are approximately of the same values, Mw = 12 - 8 kg mol-1 and Mn = 8.7 - 6.2 kg mol-1. Thermal behavior of those copolymers correspond to the behavior of acrylic and methacrylic polymers containing DCU as pendant group. Namely, all copolymers decompose under TGA conditions by a two-step mechanism. In the first step between 180 °C and 250 °C isopropylisocyanate (C3H7NCO) separates by degradation of diisopropylurea (DiPrU) in the side chain. The thermally stable residue represents the copolymer of methacryl-isopropylamide with St, which decompose by one-step mechanism between 280 °C and 450 °C

Application of NMR Spectroscopy in the Analysis of Petroleum Derivatives and Products

Složen kemijski sastav i fizikalna svojstva nafte i naftnih goriva čine njihovu karakterizaciju vrlo zahtjevnom. Pojedinačni spojevi, sastojci nafte i proizvoda razlikuju se po molekulskoj strukturi, veličini, polarnosti i funkcionalnosti. Sastav i prisutnost određenih specifičnih ugljikovodičnih skupina u određenom proizvodu ovisi o vrsti goriva i postupku procesa obrade. Kako bi se predvidjeli potencijali goriva ili odredili zahtjevi za poboljšanjem, potrebno je dobro poznavanje sastava goriva. U tu svrhu stalno se razvijaju nove i sve sofisticiranije analitičke tehnike i metode. Spektroskopija NMR ima široku primjenu u istraživanju sastava složenih ugljikovodičnih smjesa nafte i naftnih proizvoda. Pregledom je obuhvaćena njezina primjena u analizi benzinskih i dizelskih goriva. Opisana je važnost razvoja tehnika CP/MAS NMR za snimanje čvrstih uzoraka u analizi naftno-geokemijskih supstrata. Prikazane su mogućnosti spektroskopije NMR u karakterizaciji polimernih aditiva koji se upotrebljavaju u naftnoj industriji.Complex chemical composition and physical properties of oil and fuel make their complete characterization very difficult. Components present in oil and oil products differ in structure, size, polarity and functionality. The presence and structure of specific hydrocarbons in final products depend on the processing procedure and type of the fuel. In order to predict or improve fuel properties it is necessary to determine its composition. Thus, new and more sophisticated analytical methods and procedures are constantly being developed. NMR spectroscopy plays a significant role in analysis and identification of complex hydrocarbon mixtures of petroleum and petroleum products. In this review, we describe the application of NMR spectroscopy for analyzing gasoline and diesel fuels. Hence, by using NMR spectroscopy it is possible to determine gasoline composition and presence of benzene and oxygenates, as well as some important physical characteristics of gasoline such as the research octane number. An application of different NMR techniques made it possible to characterize diesel fuels and middle oil distillates from various refineries. Data so obtained can be used in combination with statistical methods to predict fuel properties and to monitor production processes in the petroleum industry. NMR spectroscopy has proven useful in analysis of FAME which has recently been used as an ecologically acceptable alternative fuel. Furthermore, techniques such as CP/MAS for characterization of solid state oil-geochemical samples are included. Also, possibilities of using NMR spectroscopy in the analysis of polymeric additives are discussed

Polimerizacija, toplinska stabilnost i mehanizam razgradnje kopolimera (met)akril-dicikloheksiluree i (met)akril-diizopropiluree sa stirenom i α-metilstirenom (Polymerization, Thermal Stability and Degradation Mechanism of (Meth)acryl-Dicyclohexylurea and (Meth)acryl-Diisopropylurea Copolymers with Styrene and α-Methylstyrene)

This paper describes the polymerization of N-acryl-N,N'-dicyclohexylurea (A-DCU), N-methacryl- N,N'-dicyclohexylurea (MA-DCU) and N-methacryl-N,N'-diisopropylurea (MA-DiPrU) monomers with styrene (St) and α-methylstyrene (α-MeSt), thermal stability and degradation mechanism of prepared copolymers. Free-radical initiated polymerization was performed to low conversion by using dibenzoyl peroxyde (Bz₂O₂) in butanone at 70 °C under nitrogen stream. It was found that the pendant group in (meth)acrylic monomers have high influence to the polymerization as well as to the copolymer properties. A-DCU readily homopolymerized and copolymerized with St and r_1,A-DCU = 0.72 and r_2,α-MeSt= 0.07, while MA-DCU does not homopolymerized or copolymerized with α-MeSt under the same conditions, but copolymerized with St to randomly composed copolymers after a long heating of comonomers. Copolymers A-DCU with α-MeSt prepared under different monomer-to monomer-ratios in the feed have random composition with an azeotropic point at ratio of 0.75 (A-DCU) to 0.25 (St). The initial rate of copolymerization indicates that the rate increases almost linearly with the increase of ratio of A-DCU in the comonomer feed. Reactivity ratios determined by the Kelen-Tüdös method are: r_1,A-DCU = 0.72 and r_2,α-MeSt = 0.07. Molar mass of copolymers increased from 8.5 to 30 (kg mol^-1) when mole ratio of A-DCU to α-MeStin the feed increased from 0.1 to 0.9. Poly(A-DCU) and copolymers with α-MeSt decomposed by two-step mechanism. Under TGA (nitrogen,10 °C min^-1) conditions in the first step between 180 °C and 250 °C a quantitative yield of cyclohexylisocyanate (C₆H₁₁NCO) separated by a decomposition of dicyclohexylurea (DCU). The thermally stable residue represented poly(acryl-cyclohexylamide), poly(A-CHA), and copolymer with α-MeSt, poly(A-CHA-co-α-MeSt). Glass transition temperature (T_g) of poly(A-DCU) was at 184 °C and T_g of residue, poly(A-CHA), was at 161 °C. T_g's of the copolymers are higher for the copolymer with higher A-DCU content. T_g's of residue are increased also when the content of A-CHA in copolymer increased. Copolymers of A-DCU with St have a random composition with an azeotropic point at a ratio of 0.73 (A-DCU) to 0.27 (St). The rate of copolymerization of A-DCU with St increases by the increase of A-DCU in the feed. The reactivity ratio are: r_1,A-DCU = 0.80 and r_{2, St} = 0.50. Molar mass of copolymer, prepared at equimolar ratio of monomers in the feed, is Mw = 78.6 kg/mol^-1. These copolymers decompose in TGA conditions by two-step mechanism, which correspond to the mechanism explained for the copolymers of A-DCU with α-MeSt. MA-DCU copolymerized with St to randomly composed copolymers. The reactivity ratio determined by the KT method are: r_{1, MA-DCU} = 0.18 and r_{2, St} = 4.84. These values indicate that MA-DCU favors cross-propagation over homopolymerization, while St favors homopolymerization as opposite to cross-propagation. It also shows, that since St is more reactive than MA-DCU, copolymers contain a higher proportion of St units. It was found, that the rate of copolymerization of MA-DCU with St is slower than the rate of copolymerization of A-DCU with St, and that the rate of copolymerization decreases by increasing the amount of MA-DCU in the feed. Molar mass of copolymer prepared at equimolar ratios of comonomers in the feed is Mw=12 kg mol^-1. Thermal properties of poly(MA-DCU-co-St) are similar to those previously described in the decomposition of poly[A-DCU-co-St(α-MeSt)]. The results have also shown quite a big influence of DiPrU group in MA-iPrU to the polymerization with St and α -MeSt. Namely, MA-DiPrU does not homopolymerized or copolymerized with α -MeSt, but can polymerize with St only after a long heating of comonomers at 70 °C. The copolymerization of MA-DiPrU with St is a statistical reaction in which regardless of monomer-tomonomer ratios in the feed, an excess of St was in the copolymer. The reactivity ratios (KT method) are: r_{1, MA-DiPrU} = 0.39 and r_{2, St}= 1.03. The obtained data indicate a monomer tendency to alternating structure. The initial rate of copolymerization decreases with increasing the content of MA-DiPrU monomer in the feed. Molar mass of all copolymers are approximately of the same values, Mw = 12 - 8 kg mol^-1 and Mn = 8.7 - 6.2 kg mol<sup>-1<sup>. Thermal behavior of those copolymers correspond to the behavior of acrylic and methacrylic polymers containing DCU as pendant group. Namely, all copolymers decompose under TGA conditions by a two-step mechanism. In the first step between 180 °C and 250 °C isopropylisocyanate (C₃H₇NCO) separates by degradation of diisopropylurea (DiPrU) in the side chain. The thermally stable residue represents the copolymer of methacryl-isopropylamide with St, which decompose by one-step mechanism between 280 °C and 450 °C