Nitrogen compound distributions in hydrotreated shale oil products from commercial-scale refining

The distributions of nitrogen compounds in crude and hydrotreated shale oil products have been determined. About 11600 m³ (73000 bbl) of Paraho retorted shale oil were hydrotreated by The Standard Oil Company of Ohio at their Toledo refinery. A hydrotreated whole product, a jet fuel, a diesel fuel, and a residuum were produced and individually separated into compound-type fractions by adsorption chromatography. The nitrogen compound types in these fractions were characterized by i.r. spectroscopy, differential potentiometric titration, and high-resolution m.s. The distributions of nitrogen compound types and nitrogen base types in the hydrotreated products are compared with those in the Paraho retorted shale oil feedstock used in the hydroprocessing. The nitrogen compound types that were readily hydrodenitrogenated during commercial-scale refining are similar to nitrogen compound types removed during one-pass, bench-scale hydroprocessing.     

Upgrading coal-derived liquids to diesel fuel

Distilled fractions of a coal-derived liquid from the H-Coal process were upgraded to diesel fuel by catalytic hydrotreatment. The total hydrotreated products were distilled into naphtha (<180°C) and diesel fuel fractions (>180°C) and the diesel fractions were analysed for hydrocarbon-type composition, hydrogen content and some diesel fuel properties. GC—MS-analyses were carried out on the hydrocarbon-type fractions to identify individual chemical compounds. To investigate the effect of different distillation cut points on diesel fuel yield and properties, cut points for one hydrotreated product were varied. The diesel fuel cetane numbers were correlated with percentage hydrogen, total aromatics and saturates. Cetane numbers above 40 were obtained for diesel fuels containing (i) more than 75% saturates, (ii) less than 15% total aromatics and (iii) a hydrogen content above 12.8%. Compounds identified by GC—MS-analyses (in the diesel fractions) were typical aromatic and cycloparaffin compounds. Normal-and iso-paraffin compounds were not detected. By varying the distillation cut point from 135 to 180°C, the cetane number of the residual diesel fraction improved from 37 to 44. This increase is ascribed to the removal of aromatic compounds in the 135–180°C boiling point range.     

Aufklärung der Molekülstruktur von Rohölinhaltsstoffen durch NMR-Spektroskopie. IV. Strukturtypen- und Strukturgruppenanalyse von Erdölfraktionen durch 1H-NMR-Spektroskopie

Elucidation of the Molecular Structure of Petroleum Constituents by N.M.R. Spectroscopy. IV. Analysis of Petroleum Fractions with Respect to Types of Structure and Structural Groups by ¹H N.M.R. Spectroscopy An improved method is presented which permits a quantitative analysis of crude oil products with a final boiling point below 400°C by means of the data of the ¹H n.m.r. spectrum and the average boiling point of the petroleum fractions. The types of aromatic structures are distinguished with respect to mono-, bi-, and tricyclic aromatics, and additionally, further structural group information is obtained.     

Characterization and utilization of hydrotreated products from the Whiterocks (Utah) tar sand bitumen-derived liquid

The bitumen-derived liquid produced in a fluidized-bed reactor from the Whiterocks tar sand was hydrotreated over a sulphided Ni-Mo/Al₂O₃ hydrodenitrogenation catalyst in a fixed-bed reactor. The process variables studied were temperature (617–680 K), pressure (11.0–17.1 MPa) and liquid hourly space velocity (0.18–0.77 h⁻¹). The feed and the hydrotreated liquid products were analysed by gas chromatography-mass spectrometry analyses. The compounds identified in the bitumen included isoprenoids; bicyclic, tricyclic, and tetracyclic terpenoids; steranes; hopanes; and perhydro-β-carotenes. Normal and branched alkanes and alkenes and partially dehydrogenated hydroaromatics were identified in the bitumen-derived liquid. Comparison of the compounds identified in the bitumen and the bitumen-derived liquid indicated that the dealkylation of long alkyl side chains 0to form - and isoolefins and the cleavage of alkyl chains linking aromatic and hydroaromatic clusters were the dominant pyrolysis reactions. Monoaromatic hydrocarbons were the predominant aromatic species in the hydrotreated product. The properties of the jet fuel fractions from the hydrotreated products met most of the jet fuel specifications. The cetane indices indicated that these fractions would be suitable for use as diesel fuels.     

Manufacture of aromatic hydrocarbons from coal hydrogenation products

The manufacture of aromatic hydrocarbons from coal distillates was experimentally studied. A flow chart for the production of benzene, ethylbenzene, toluene, and xylenes was designed, which comprised the hydrogen treatment of the total wide-cut (or preliminarily depehenolized) fraction with FBP 425°C; fractional distillation of the hydrotreated products into IBP-60, 60–180, 180–300, and 300–425°C fractions; the hydro-racking of middle fractions for increasing the yield of gasoline fractions whenever necessary; the catalytic reform of the fractions with bp up to 180°C; and the extraction of aromatic hydrocarbons.     

Structural characterization of fractions of petroleum pitch and ethylene pyrolysis tar by 1H and 13C n.m.r. spectroscopy

A petroleum pitch and > 288 °C fraction of an ethylene pyrolysis tar are separated by sequential solvent extraction into fractions differing in average molecular weight. Average molecular parameters for each fraction are obtained using their H and ¹³C n.m.r. spectra. Average molecular structures which correlate with the observed data are drawn. The data presented here suggest that the average molecule of the fractions of both petroleum pitch and pyrolysis tar can be represented by an oligomeric structure in which small aromatic clusters are joined by aliphatic bridges and/or biaryl linkages. This contradicts the accepted assumption that the aromatic ring system in petroleum-derived products is fully condensed. Although the average molecular structure of the fractions of pitch and ethylene pyrolysis tar are basically similar, they differ in the number and types of ring-saturated carbons.     

Characterization of coal liquids by 13C n.m.r. and FT-i.r. spectroscopy — fractions of oils of SRC-I and asphaltenes and preasphaltenes of SRC-I and SRC-II

Coal-derived products of SRC-I liquefaction of Blacksville coal and vacuum tower bottoms (VTB) of SRC-II liquefaction of Powhatan mine coal (both bituminous and from the Pittsburgh Seam) were separated into fractions by solvent extraction. The SRC-I was first extracted with ethylacetate, and solubles were subsequently separated into oils and a mixture of asphaltenes and preasphaltenes (APA). The VTB was Soxhlet extracted with pentane to remove any residual oils, followed by tetrahydrofuran to recover APA. The APA portions were then separated by sequential elution solvent chromatography (SESC) into fractions differing in chemical functionality, and then examined by ¹³C n.m.r. and FT-i.r. spectroscopic techniques. APA are intermediates and end products of coal liquefaction. SRC-II APA are of higher molecular weight than the APA of SRC-I. The lower numbered fractions of APA of SRC-I in SESC separation have the same functional groups as the corresponding fractions of middle and heavy distillates. However, the higher numbered fractions are rich in oxygen, which is mainly in carbonyl groups. Part of the carbonyl groups are in esters which cross-link aromatic clusters. Therefore, APA and the coal itself are ‘oligomeric’ in structure, with aromatic clusters linked by carbon bridges with different functional groups. The nature of carbonyl groups in APA has been analysed in detail.     

Systematic characterization of petroleum residua based on SFEF

Supercritical fluid extraction and fractionation (SFEF) has been used to separate a variety of petroleum residua and other heavy oils into narrow-cut fractions with total yields up to 75-90%. Any insoluble material, or end-cut, corresponds to the asphaltene fraction in the parent oil. The narrow-cut fractions were analyzed comprehensively and separated into the solubility classes of saturate, aromatic, resin, and asphaltene fractions. The boiling points were measured up to 700 °C and correlations were established with the key factors such as density and molecular weight. This allows extrapolation of boiling points of residue fractions up to 1000 °C. Unlike bulk property measurements, the narrow-cut characterization data show increasing concentrations of key contaminants as the fractions become heavier. The solubility parameter for each narrow-cut fraction was measured using high-pressure fluid phase equilibrium with propane. The corresponding values for the end-cuts were obtained by the conventional precipitation method. The distribution and reactivity of sulfur species were determined by XPS in the bitumen pitch fractions and the corresponding residua produced during thermocracking and hydrocracking. The average structures for the narrow-cuts were constructed from molecular weight and elemental analyses together with FTIR, ¹H-NMR and ¹³C-NMR data. The results were used to develop a generalized feedstock characteristic index, K_R. This index shows good correlation with feedstock hydrocarbon constituents and can be used to assess feedstock reactivity and processability. Downstream refiners can use the narrow-cut data and K_R values for process optimization by either cutting deeper into residua bottoms to increase yield or by selecting the most appropriate process units for the various residue fractions. This information can also be used by upstream operators to determine the economic feasibility of utilizing the end-cut onsite.     

Aromatic products of 340 °C supercritical-toluene extraction of two Turkish lignites: an n.m.r. study

Fractions of Elbistan and Seyitomer (Turkish) lignites, extracted with supercritical toluene at 340 °C and 8 MPa, have been separated by solvent extraction and silica-gel chromatography. Analyses by n.m.r. and i.r. spectroscopies and other methods have been combined in structural-analysis schemes to yield information about the average molecule in aromatic extracts. Carbon aromaticities, f_a, derived from 22.63 MHz ¹H-decoupled pulse Fourier-transform (PFT) ¹³C-n.m.r. are more widely spread for Elbistan (0.34–0.56) than for Seyitomer (0.40–0.43), and are lower than for supercritical-gas (SCG) products from bituminous coals. ¹³C-n.m.r. also reveals the presence of aromatic ether-O in polar fractions. Narrow aromatic signals in 100 MHz ¹H-n.m.r. spectra suggest the presence of single-aromatic-ring average structures. In the hexane-soluble aromatics, 27% (Elbistan) and 29% (Seyitomer) of the available sites are substituted by alkyI groups, some of which are at least eight carbon atoms long; the hexane-soluble polar and asphaltene/asphaltol fractions contain fewer such groups.     

Analysis of coal-derived liquid obtained by mild hydrogenation: 2. Neutral oil distilling at 343–464 °C

Coal-derived liquid, from Japanese Taiheiyo coal, obtained under mild hydrogenation was analysed to elucidate the chemical structure of parent coal. The n-hexane soluble neutral part was fractionated into 7 parts by vacuum distillation. The analysis of the lower three fractions has already been reported. The higher boiling three fractions, DS04 (5.1 wt% of neutral oil), DS05 (27.3 wt%) and DS06 (27.7 wt%) were separated by liquid chromatography according to hydrocarbon types and each sub-fraction was analysed by g.c. and g.c.-m.s. Saturates were most abundant and in the distribution of n-alkanes, even carbon number saturates were greater than those of odd carbon. Some sub-fractions contained tricyclic diterpanes, steranes and hopane type triterpanes. Mono-, di- and tri-aromatic diterpanes were also found. Two aromatic ring hydrocarbons with some naphthene rings were the most abundant type.     

Analysis of coal-derived liquid obtained by mild hydrogenation: 1. Neutral oil distilling at 186–343 °C

Taiheiyo coal (77% C) was hydrogenated under mild conditions to preserve the unit structure of the parent coal as far as possible. The n-hexane-solubles (yield, 49.8 wt% daf coal) were washed with acid and base and the neutral material separated into 7 fractions by vacuum distillation. The three lower boiling fractions, DS01 (7.3 wt% neutral oil), DS02 (3.6 wt%) and DS03 (4.8 wt%), were further separated by liquid chromatography into hydrocarbon subfractions which were analysed by g.c. and g.c.-m.s. Saturates are most abundant, especially the n-alkanes which comprise ≈9–13 wt% of each fraction. The saturates also contain isoprenoids (C₁₅, C₁₆, C₁₈, C₁₉ and C₂₀), branched alkanes, n-alkyl cyclohexanes, terpanes and others. With increasing boiling point, smaller amounts of monoaromatic ring hydrocarbons and more di- or triaromatic ring hydrocarbons are found. The alkyl side-chains of aromatic nuclei have a large carbon number, especially in the smaller rings. The existence of phenyltetralin or phenylnaphthalene shows a feature of bonding between aromatic nuclei.     

Structural characterization of Saudi Arabian heavy crude oil by n.m.r. spectroscopy

Saudi Arabian heavy crude oil was separated into six fractions, including five distillate fractions (<93, 93–204, 204–260, 260–343 and 343–454 °C) and a >454 °C distillation residue. Each fraction was analysed by ¹H and ¹³C n.m.r. spectroscopy, and combined gained information from these analyses provided reliable average structural parameters. These included estimation of aliphatic and aromatic content, average paraffinic chain length, and estimation of hydrogen, methyl and alkyl bearing aromatic carbons for each of the six fractions. The extent of branching in paraffinic chains and amount of aromatic bridgehead carbons were also calculated.     

The distribution of sulfur compounds in hydrotreated jet fuels: Implications for obtaining low-sulfur petroleum fractions

The mechanism by which jet fuels are hydrotreated to reduce sulfur levels has some important implications in terms of the species and distribution of sulfur compounds remaining in the fuel. The species of sulfur that are most difficult to remove by hydrotreating, such as benzothiophenes and methyl- and dimethyl-benzothiophenes, are concentrated in the higher-boiling fraction of the fuel. Consequently, the lower-boiling fractions of the fuel contain much less sulfur. It may be possible, therefore, to obtain petroleum fractions that contain low levels of sulfur simply by distillation of the jet fuel into low-boiling and high-boiling fractions. A multi-element simulated distillation procedure according to ASTM D-2887, standard test method for boiling range distribution of petroleum fractions by gas chromatography, was coupled with atomic emission detection (GC-AED) and was used to estimate the sulfur concentration in various fractions of jet fuel, namely 20, 50, and 60%. The estimations of sulfur concentration were verified by comparing them to analyzed sulfur concentrations in several fractions of physical distillations of the jet fuels according to a modified ASTM D-86, standard test method for distillation of petroleum products at atmospheric pressure. Sulfur analyses showed that for all fuels analyzed, the initial 20% boiling fraction of the fuel contained no more than approximately 5% of the total sulfur concentration. The initial 50% boiling fraction of the fuel contained no more than 25% of the total sulfur concentration, and in most cases contained significantly less (8-16%). The total concentration of sulfur in the jet fuels tested ranged from 260 to 1380 μg/g, and there did not appear to be a direct relationship between total sulfur concentration and percentage of sulfur in each jet fuel boiling fraction.     

An h.p.l.e. and m.s. analysis of distillate fractions of neutral oil from hydrogenated Akabira coal to elucidate chemical structures

Akabira coal-derived neutral oil was separated into 25 narrow boiling range fractions covering 183–423 °C, and subsequently separated into compound class fractions : alkanes, monoaromatics, naphthalene-type diaromatics, fluorene-type diaromatics and tri- and/or tetraaromatics, by high performance liquid chromatography (h.p.l.c.). The compound type analyses of the distillate/h.p.l.c. fractions were performed using electron impact mass spectroscopy (e.i.m.s.) or field ionization mass spectroscopy (f.i.m.s.). Aromatic/hydroaromatic compound types and the alkyl side-chain carbon distribution of the distillate/h.p.l.c. fractions were clarified, based on the separation behaviour of h.p.l.c. and the type analyses according to Z value by m.s. By the distillation/h.p.l.c./m.s. method, coal-derived oil was characterized in terms of the distribution of the numbers of aromatic rings, naphthenic rings and carbons of alkyl groups attached to these rings. The variations in chemical structure in a compound class with distillation temperature are discussed in terms of these chemical structural factors.     

Characterization of high-boiling petroleum distillate fractions by proton and 13C nuclear magnetic resonance spectrometry

High-boiling (535–675 °C) distillate fractions of Wilmington (Calif. USA) and Gach Saran (Iran) crude oils were separated into saturate, monoaromatic, diaromatic and polyaromatic-polar fractions by passage through a silica-gel—alumina dual packed chromatography column. These fractions were further separated on the basis of molecular volume by gel-permeation chromatography (g.p.c.). Select g.p.c. fractions were then analyzed by ¹H and ¹³C n.m.r. spectroscopy. The fraction of aromatic carbons (Ar-C) of the total carbon content of a given series of g.p.c. fractions, obtained directly from the ¹³C n.m.r. spectra, showed a significant range of values (e.g. 13.2% to 29.2%) within each series. Furthermore, the values of %Ar-C within a series of g.p.c. fractions showed a maximum in each case. No such maximum was observed in the ¹H n.m.r. spectra for the fraction of aromatic proton (%Ar-H) content compared to the total proton content of any of the g.p.c. fraction series. Signals observed in the ¹³C n.m.r. spectra confirmed the presence of aliphatic chains attached to aromatic structures in the monoaromatic, diaromatic and polyaromatic-polar g.p.c. series of each distillate fraction. Well-defined signals, not attributable to straight-chain aliphatic material, were also observed in the ¹³C n.m.r. spectra. Comparison of the chemical shifts of these ¹³C n.m.r. signals with those spectra of model compounds obtained experimentally, and with appropriate systems in the literature, strongly suggested the presence of saturated terpenoid-like structures as well as the presence of methyl groups in sterically hindered positions on an aromatic ring system. Gated decoupling techniques and the use of a relaxation agent were used to overcome the deleterious effects of slow relaxation times and Nuclear Overhauser Enhancement (NOE) on the analytical quality of the ¹³C n.m.r. spectra.     

Depolymerization of Turkish lignites. 2. Effect of phenol concentration in a closed system

A lignite (C, 66.9 wt%) was depolymerized, using sulphuric acid as a catalyst, in a closed system in which the phenol/coal ratio was varied from 1.5 to 10. The products were separated by solvent extraction and silica gel chromatography. The i.r. and n.m.r. spectra, and the molecular weight of the products were measured. In the experiments with a phenol/coal ration of 10, complete depolymerization of the coal was seen provided the temperature of depolymerization was at least 210 °C. The products generally contained disubstituted aromatic structures connected by methylene bridges, it was found that as the phenol/coal ratio was increased there was a decrease in the number of methylene bridges connecting the aromatic structures. The molecular weights of the straight-chain pentane and benzene-soluble material were lower than the molecular weights of similar fractions in depolymerization experiments carried out in open systems. A method for the structural analysis of straight-chain pentane and benzene-soluble material based on i.r., ¹H n.m.r. and molecular weight measurements is suggested.     

Hydrotreating coal-derived liquid distillation fractions. 1. Study of single-stage treated products for transport fuel use

A coal-derived liquid distillate obtained from catalytic hydrogenation of Wandoan coal at Australian Coal Industry Research Laboratories has been fractionated into three main distillation fractions: naphtha, kerosine, and diesel. Compositional properties of each fraction are reported, particularly elemental, ¹H and ¹³C n.m.r. and h.p.l.c. results. Hydrorefining of each fraction was undertaken in a trickle-bed reactor at various conditions using commercial nickel-molybdenum hydrotreating catalysts. The hydrotreated liquid products were assessed for transport fuel use or as feedstocks for further processing.     

Transformation of petroleum asphaltenes in supercritical water

The transformation of petroleum asphaltenes in supercritical water was studied. The experiments were performed in autoclave at temperature 380 °C and pressure 226 atm with stirring for 3 h, medium density was about 0.33 g/cm³. The reaction resulted in the formation of gas products, about 4.3%, and an insoluble residue (coke) with about 48.6% yield. The remaining products were separated into fractions by consecutive dissolution in hexane (30.0%), benzene (10.6%), and chloroform (5.7%). The properties of the obtained products were studied with FT-IR spectrometry and ¹H NMR spectroscopy. The method of simulated distillation was used to demonstrate that the fractional composition of the hexane-soluble part of the products is close to the fractional composition of a mixture of the diesel fraction and vacuum gas oil of the corresponding oil in 1:1 ratio. The obtained data support the conclusion that asphaltene cracking proceeds in SCW, with most probable main processes being dealkylation of substituents in the aromatic fragments of molecules and aromatization. This leads to formation of gaseous products and hexane-soluble fraction consisting of lighter aliphatic and aromatic compounds, as well as carbonized solid residue.     

Chemical composition of the distillate fractions of coal tar from OAO Altai-Koks

The chemical composition of the distillate fractions with boiling points of to 180, 180–230, and 230–280°C separated from undehydrated coal tar from OAO Altai-Koks was studied by gas chromatography-mass spectrometry. A list of identified aromatic compounds (including N-, O-, and S-containing compounds) and their alkyl derivatives is given. It was found that, upon the complete processing of tar with the recirculation of residual raw materials at the stage of coking and its hydrogenation refining in the presence of suspended Mo- and Ni-containing catalysts and a hydrogen donor (tetralin), the yields of chemical products were the following (wt %): coke, 50–55; absorption oil, 9–12; benzene, naphthalene, tetralin, dimethylnaphthalenes, and other hydrocarbons, 25–30; BTX fraction 4–5; and C₁-C₄ and CO₂, 10–12.     

Liquid products of the hydropyrolysis of brown coal form the Lena basin

Liquid hydrocarbon products were obtained by the hydropyrolysis of brown coal from a deposit in the northern Lena basin on an iron-containing catalyst. The individual and group compositions of gasoline and diesel fractions were determined with the use of capillary chromatography and chromatography-mass spectrometry. The gasoline fraction with a boiling point to 180°C was characterized by a high octane number; it mainly contained monocyclic aromatic hydrocarbons and normal alkanes. The diesel fraction mainly consisted of bi- and tricyclic aromatic hydrocarbons and C₁₃–C₁₉ n-alkanes.