Nitrogen Compounds In Petroleum Research Articles

A potential material for removal of nitrogen compounds in petroleum and petrochemical derivates

Activated carbon from coconut shell (Elaeis guineensis), in both crude and chemically modified forms, was evaluated as an adsorbent for removing nitrogen compounds of samples from synthetic and real fuel. The preliminary adsorption tests showed that 97.95 of indoline was removed by sulfuric acid-treated activated carbon (SAAC). The optimum conditions toward adsorption of nitrogen-containing compounds in crude oil (54 °C, 150 rpm and 1.104 g of adsorbent) was evaluated according to the design of experiments (DOE) technique associated with Differential Evolution optimization algorithm and an effective removal of 30.37% of basic nitrogenous compounds present in crude oil was achieved. For comparative effect, the tests were carried out using the previously optimized condition with the vacuum residue, diesel S-500, and diesel S-10, obtaining the removal of 21.56%, 44.44%, and 62.09%, respectively. Complementing the quantitative analysis, the analysis of mass spectrometry confirmed that coconut shell is a potential material for selective adsorption of nitrogenous compounds.

Deep adsorptive desulfurization over ion-exchanged zeolites: Individual and simultaneous effect of aromatic and nitrogen compounds

The presence of aromatics and nitrogen compounds in petroleum fuel has a strong inhibiting impact on deep adsorptive desulfurization (ADS). This work aimed to clarify the individual and simultaneous effect of these compounds on ADS of the most refractory sulfur-containing polyaromatic compounds (dibenzothiophene and 4,6-dimethyldibenzothiophene) over Na–Y, Ni–Y, La–Y, Ce–Y and Ni–Ce–Y zeolites in a fixed bed system at ambient conditions. Polyaromatics (naphthalene) and nitrogen (quinoline and indole) compounds caused a marked decrease in the sulfur adsorption capacity, while the nitrogen compounds decreased the sulfur adsorption capacity more than naphthalene. The negative electrostatic potential of compounds might play an important role in the adsorptive selectivity on the pre-reduced Ni–Y zeolite. The results show that the adsorption sites of aromatics and nitrogen compounds on the adsorbents are the same as for the sulfur compounds. This competitive adsorption was very strong especially for the metal that enhanced π-complexation interaction. The reduced Ni2+ introduced into Na–Y zeolite increased resistance to aromatics and nitrogen compounds on ADS. For the spent adsorbent, the regeneration efficiency, in terms of the desorption amount, depended on the similarity of the polarity of the solvent (hexane and toluene) and adsorbate, where a high temperature and low flow rate of solvent favored the extraction of adsorbates leading to an increased regeneration efficiency. This study provides an insight into the interactions among these three kinds of components and adsorbents, which is useful for further development of the ADS process.

Characterization of basic nitrogen compounds isolated with FeCl3 in vacuum gas oil and its hydrotreated product

The basic nitrogen compounds in petroleum are harmful heteroaromatic compounds, which would substantially affect the refining process and the quality of the resultant products. Obtaining comprehensive molecular information of the basic nitrogen compounds is challenging, particularly for those in heavy oils. In this work, a novel separation method was developed to isolate the basic nitrogen compounds from vacuum gas oil and its hydrotreated product with high recovery and high purity. The basic nitrogen compounds were isolated from the vacuum gas oil and its hydrotreated product by the formation of complexes coordinated with FeCl3. Then, the insoluble complexes were treated by NaOH to destroy the coordinate bonds between the FeCl3 and basic nitrogen compounds. The separated basic nitrogen compounds were characterized by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and comprehensive two-dimensional (2D) gas chromatography coupled with high resolution time of flight mass spectrometry (GC × GC-TOFMS). The separated basic nitrogen compounds facilitated the GC × GC-TOFMS analysis due to the reduced matrix complexity. The basic nitrogen compounds from vacuum gas oil are mainly tricyclic and tetracyclic nitrogen-containing aromatic compounds, such as benzoquinolines and benzacridines. The basic nitrogen compounds from the vacuum gas oil with short alkyl chains can be preferentially removed by hydrotreatment. Moreover, partially saturated products of the basic nitrogen compounds were widely found in the hydrotreated vacuum gas oil, such as tetrahydrobenzoquinolines, octahydrobenzoquinolines, tetrahydroindenoquinolines, and octahydroindenoquinolines. This study contributes to the structural characterization of basic nitrogen compounds in heavy oils and the conversion of these compounds during hydrotreating.

Ultrahigh-Resolution Mass Spectrometry Analysis of Ozonation Products of Petroleum Nitrogen Compounds

Changes that occur at the molecular level in the composition of nitrogen compounds of a petroleum sample from the Yuzno-Yagunskoe field during ozonation have been studied by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry in soft ionization modes. It has been found that N1Ox-containing products accumulate to form new classes of compounds, namely, N1O2, N1O3, N1O4, N1O5, N1O6, and N1O7, while N1 classes undergo degradation. Ozonation of 50% of the feedstock leads to a ~30% decrease in the number of identified empirical formulas of pyridine bases (N1 class).

Carbazoles and benzocarbazoles confirm migration of leaked petroleum through caprocks and overlaying formations of Valhall Well 2/8-8 in the North Sea

A wildcat may not result in a petroleum prospect; however, it may indicate potential need for frontier exploration, since petroleum could leak into economic accumulations. Carbazoles and benzocarbazoles are nitrogen compounds in petroleum and can be employed to explicitly explain migration direction and distance of leaking petroleum. The hypothesis of this study is that the mechanism of the reaction involving the attraction of carbazoles to clay minerals on the matrix of the walls along their migration pathways determines the isomer that is preferentially attached to the mineral matrix. The objectives of this study are (a) to produce a profile for carbazoles and benzocarbazoles ratios in the cap rock overlying the reservoir, (b) to compare carbazole and benzocarbazole ratios to 20S/(20S + 20R) αααC29 Sterane maturity ratios (c) to infer migration direction from the carbazoles and benzocarbazoles ratio. Samples used were side wall cores and drill cuttings of water-based mud drilling. The EOM (extractable organic matter) from various formations overlying the reservoir was obtained using Soxtherm Automatic Equipment. The TPH (total petroleum hydrocarbon) was obtained from the EOM by using a precleaned isolute C18 500 mg / 3 mL column, eluted with hexane, while the polars were eluted with dichloromethane. Fractionation into saturates and aromatics was done using a silver nitrate–silica gel column. The profiles of 1,8/1,3 and 1,8/2,4 dimethyl carbazoles and the benzocarbazoles ratios show a vertical gradient of decreasing ratio with increasing vertical distance from the reservoir. This corroborates the %VRo equivalent of 20S/(20S + 20R) αααC29 Sterane and the carbazole ratios infer vertical migration of leaked petroleum.

Effect of Ni incorporation into goethite in the catalytic activity for the oxidation of nitrogen compounds in petroleum

Samples of Ni-doped goethites were prepared and characterized by Mössbauer spectroscopy, IV, XRD, TPR and BET surface area measurements. Mössbauer data evidenced the incorporation of Ni 2+ in the goethite structure, and this cation-doping caused a significant decrease of the chemical reduction temperature in the TPR process. The catalytic behavior of these Fe 1− x Ni x OOH materials was investigated for the H 2O 2 decomposition to O 2 and the oxidation of quinoline. The successive hydroxylation of quinoline during this oxidation strongly suggests that highly reactive hydroxyl radicals are generated during the reaction involving H 2O 2 on the Ni-goethite grain surface, also confirming that these materials are efficient heterogeneous Fenton catalysts.

The influence of source depositional conditions on the hydrocarbon and nitrogen compounds in petroleum from central Montana, USA

The hydrocarbon and pyrrolic nitrogen compound compositions of 21 crude oils from reservoirs in the Heath–Tyler–Amsden and Swift-Morrison formations of central Montana have been investigated by combined gas chromatography–mass spectrometry. The biomarker and aromatic hydrocarbon data enabled recognition of three composition types within the Heath–Tyler–Amsden oils. The Swift-Morrison oils displayed different hydrocarbon characteristics and are classified as a separate oil group. A number of geochemical parameters, e.g. dibenzothiophene/phenanthrene, C 20-triaromatic steroid hydrocarbon/(C 20 + C 28 triaromatic steroid hydrocarbons) indicate strong variations in petroleum composition from north to south across the region. Oils from the central Montana uplift with high relative C 27-diasteranes/C 29 ααα steranes and Ts/(Ts + Tm) suggests increasing clay contribution to the source, while abundant gammacerane indicates the development of hypersaline conditions with restricted circulation. Oils from the Bull Mountain Basin, represented by the Amsden oils, show relatively low C 27-diasteranes/C 29 ααα steranes and Ts/(Ts + Tm) ratios indicating increasing carbonate contribution to the source, while the decrease of a gammacerane contribution suggests decreasing salinity levels, which may explain the dominance of tricyclic terpane and hence their precursors to the source organic matter. While the changes recorded by the biomarker and aromatic hydrocarbon compositions show strong regional variations, the nitrogen compounds do not respond so strongly. However, weak trends coinciding with source carbonate content were apparent in the following ratios: 1,8-dimethylcarbazole/(1,8-dimethylcarbazole + 1-ethylcarbazole) and carbazole/sum of C 2-carbazoles. The second parameter may be responding to variations in salinity since it co-varies with the behaviour exhibited by the tricyclic terpanes. The source information that can be extracted from biomarkers and aromatic hydrocarbons suggests that primary migration and compositional fractionation during expulsion has exerted little influence on this fraction of petroleum. Meanwhile, primary migration and compositional fractionation during expulsion appear to effect the carbazole and benzocarbazole distributions thereby limiting their application as indicators for source rock facies composition.

Identification of alkyl carbazoles and alkyl benzocarbazoles in Brazilian petroleum derivatives

Carbozoles are important compounds in crude oils, as they may be used as geochemical tracers, being the major type of nitrogen compounds in petroleum. At the same time, they are regarded as undesirable due to the problems they may cause in the refining process, such as catalyst poisoning, corrosion, gum or color formation in final products. As separation and identification of carbazoles are challenging goals, this work presents a chromatographic method, made of a pre-fractionation on neutral alumina followed by the separation and identification of two classes of carbazoles using FeCl 3/Chromossorb W and gas chromatograph with mass spectrometer (GC/MS) (SIM—single ion monitoring mode) analysis. For the first time, a series of alkyl carbazoles and alkyl benzocarbazoles were identified in heavy gas oil (HGO) and atmospheric residue of distillation (ARD) obtained from Brazilian petroleum.

05/00957 Hydropyrolysis of algae, bacteria, archaea and lake sediments; insights into the origin of nitrogen compounds in petroleum

05/00957 Hydropyrolysis of algae, bacteria, archaea and lake sediments; insights into the origin of nitrogen compounds in petroleum

Hydropyrolysis of algae, bacteria, archaea and lake sediments; insights into the origin of nitrogen compounds in petroleum

Nitrogen compounds are ubiquitous in fossil fuels and yet our understanding of their origins in the geosphere is limited. In this study, high hydrogen pressure pyrolysis was performed on sample material representing potential contributors to sedimentary organic matter (algae, bacteria and archaea) and sediments representing early diagenetic accumulations from Lake Pollen (Norway) and Priest Pot (UK). Previous workers demonstrated the structurally conservative nature of high hydrogen pressure pyrolysis in that the technique maximizes the yields of covalently bound hydrocarbon biomarkers from organic matter without adversely affecting their stereochemistry ( Love et al., 1995). Release of covalently bound biomarkers in high yields from kerogen via catalytic hydropyrolysis. In this study, the types and distributions of organic nitrogen compounds in the hydropyrolysates were characterised under similar conditions to such experiments where biomarker hydrocarbons undergo minimal rearrangement. Compounds identified by gas chromatography–mass spectrometry included alkyl-substituted indoles, carbazoles, benzocarbazoles, quinolines and benzoquinolines. Indoles are present in all hydropyrolysates, suggesting a common origin. A potential source of indoles is represented by tryptophan which was shown to degrade through a series of alkylated intermediates to indole. Carbazole, quinoline and benzoquinoline were also found in the hydropyrolysates of algae, bacteria and archaea. The presence of these petroleum-related nitrogen compounds in hydropyrolysates generated from biomass suggests an early origin for petroleum nitrogen compounds. A potential source of naturally occurring nitrogen compounds such as that in the alkaloids has yet to be realised. Benzocarbazoles were absent from hydropyrolysates of algae, bacteria and archeae, but present in those from recent sediments, suggesting their presence may be related to processes occurring during early diagenesis at, or immediately below, the sediment–water interface. In sediments from Lake Pollen, changes in the benzocarbazole ratio [ a]/([ a] + [ c]) ratio coincides with the interval described as a transition from fjord to lake environment, suggesting that benzocarbazoles are sensitive to changes in depositional environment and may have potential to act as a marker for environmental conditions.

Petroleum nitrogen compounds : A sensitive indicator of petroleum migration(Taguchi Prize honored in 1997)

Petroleum nitrogen compounds : A sensitive indicator of petroleum migration(Taguchi Prize honored in 1997)

Adsorptive interaction between nitrogen compounds and organic and/or mineral phases in subsurface rocks. Models for compositional fractionation of pyrrolic nitrogen compounds in petroleum during petroleum migration

AbstractThe results are reported of a range of laboratory chromatographic fractionation experiments with synthetic model compounds and a petroleum pyrrolic nitrogen fraction. Reversed phase separation of pyrrolic nitrogen compounds was governed mainly by the number of carbon atoms in the molecule, with little selectivity toward different positional isomers, whereas normal phase separation of the compounds could be explained in terms of steric effects related to alkylation position. Comparison of experimental results from model compounds with observations made previously using sets of natural samples taken from sedimentary basins clearly suggests adsorptive interactions between organic and mineral phases are involved in the compositional fractionation of pyrrolic nitrogen compounds in petroleum during migration. Detailed studies of the effects of petroleum migration on the molecular distribution of petroleum pyrrolic nitrogen compounds may provide useful, quantifiable, migration‐related geochemical parameters.

Influence of petroleum nitrogen compounds on hydrodesulphurization

A study of the influence of nitrogen compounds in a crude oil on hydrodesulphurization (HDS) of a vacuum distillate and dibenzothiophene in the presence of an industrial hydroraffination catalyst, G-3 ( CoMo Al 2O 3 ) was performed. The nitrogen compounds were separated from the vacuum distillate by ion-exchange and coordination chromatography in the form of acidic, basic and neutral concentrates. It was found that the addition of the concentrate (0.2% N) led to a decrease in degree of hydrodesulphurization of the vacuum distillate and dibenzothiophene. The strongest influence was found for acidic compounds, while the weakest was found for basic ones. The inhibition caused by the nitrogen compounds added is not permanent, and disappears after introduction of a raw material in the absence of nitrogen compounds.

Nitrogen Compounds in Petroleum. IV. Distribution Profiles of Nitrogen Compounds in Petroleum by Solid-Liquid Chromatography

Abstract A simple method for the characterization of nitrogen compounds in petroleum products by the investigation of the distribution profiles of nitrogen compounds using stepwise gradient elution on silica gel has been conducted. Samples were charged onto a 8φ×150 mm glass column containing 3 g of silica gel for column chromatography, followed by 15 ml of hexane to remove the non-polar bulk hydrocarbons from the sample. The eluate collected was removed from the solvent and analyzed for nitrogen, wt % yield and UV absorbance at 220 nm. The same procedure was followed by each 15 ml of 1, 3, 5, 10, 30, 60, 100%(v/v)-THF in hexane eluents. Plots of the nitrogen contents vs. the concentration of eluents gave characteristic patterns for petroleum distillates. The crude and residual oils from different geological sources exhibit similar nitrogen distribution profiles. There are two peak values; the peak at 3%-THF increases and that at 30%-THF decreases as the boiling range of the distillate decreases. Nitrogen compounds are distributed uniformly in a wide range of polar components with regard to adsorptivity on silica gel. The method was further applied to the reaction products of quinoline and indole by irradiation with UV light in isooctane (2,2,4-trimethylpentane) solution.

Nitrogen compounds of petroleum oils (review)

The literature data on the quantitative percentages, group and individual compositions, and structures of nitrogen compounds of all types that have been identified in petroleum oils and directly distilled petroleum fractions are systematized. The general regularities in the structures of the molecules of petroleum nitrogen compounds and their structural relationship with other aromatic components of petroleum oils are noted. The modern concepts regarding the genesis of the most important classes of nitrogen-containing components of petroleum are discussed.

Concentration of Nitrogen Compounds in Petroleum by Silica Gel Adsorption and Sulfuric Acid Extraction Technique

Concentration of Nitrogen Compounds in Petroleum by Silica Gel Adsorption and Sulfuric Acid Extraction Technique

Petroleum nitrogen compounds and oxygen compounds

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPetroleum nitrogen compounds and oxygen compoundsLloyd Robert SnyderCite this: Acc. Chem. Res. 1970, 3, 9, 290–299Publication Date (Print):September 1, 1970Publication History Published online1 May 2002Published inissue 1 September 1970https://doi.org/10.1021/ar50033a002RIGHTS & PERMISSIONSArticle Views419Altmetric-Citations53LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

Nonaqueous differential titration applied to a classification of basic and very weak basic nitrogen compounds in petroleum

Nonaqueous differential titration applied to a classification of basic and very weak basic nitrogen compounds in petroleum

Isolation and Identification of Nitrogen Compounds in Petroleum.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTIsolation and Identification of Nitrogen Compounds in Petroleum.H. V. Drushel and A. L. SommersCite this: Anal. Chem. 1966, 38, 1, 19–28Publication Date (Print):January 1, 1966Publication History Published online1 May 2002Published inissue 1 January 1966https://doi.org/10.1021/ac60233a006RIGHTS & PERMISSIONSArticle Views184Altmetric-Citations58LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (1 MB) Get e-Alerts Get e-Alerts

The nitrogen compounds in petroleum—II. Separation of the nitrogen bases from organic sulphides

DURING investigations of the mtrogen bases m petroleum and petroleum fractions, it has been estabhshed that concentrates of the petroleum bases isolated from the acid extracts are charactemsed by a relatively high content of sulphur Tins is apparently due to the entrainment of organosulphur compounds m the acid layer as the solution becomes enriched with the mtrogen compounds winch, as is well known, are good solvents for sulphur compounds A similar phenomenon has also been observed in the extraction of the mtrogen bases from the products of treating shales and coal [1] As was shown earher [2], 35-100% of the sulphur compounds m concentrates of petroleum bases are orgamc sulpindes I t was decided to carry out the separation of the N-bases and the sulpindes, winch are neutral compounds, from non-aqueous solvents using the catmnexchanger KU-1, winch possesses strong-acid propertms Experiments have shown that separatmn of mixtures of mdlwduaI compounds takes place qmte smoothly and quantitatively even on a single pass of a benzene or aoetm acid solutmn of a mixture through a column or on stirring the solutmn with the catmn-exchanger for 30 minutes The sulphldes remain m the solution and the N-bases are retained by the catmn-exchanger, as was shown in control experiments usmg potentmmetr~c lodate t i tration [3] and potentlometmc tlt ratmn with a solutmn of HC10 a m acetm acid However, at tempts to use tins method for the separatmn of sulphldes from concentrates of petroleum bases were not crowned with success In all eases fractmns were obtained which contained N-bases and sulphides m approximately the same proportmns as m the mltlal materml They could be separated only after oxlchzmg the sulpindes to sulphoxldes, winch was aeeomphshed by the method developed by Karaulova and Gal'pern [4] for sulphur-containing aromatm concentrates The feaslblhty of Oxlchzmg