Showing papers in "Preprints-American Chemical Society Division of Petroleum Chemistry in 1989"

Source correlation and maturity assessment of select oils and rocks from the central Adriatic Basin (Italy and Yugoslavia)

Abstract: Etude de la composition chimique et de la maturation d'huiles provenant du Bassin Adriatique afin d'etablir des correlations entre la nature des huiles et les roches meres. L'etude experimentale est realisee en combinant l'utilisation de marqueurs biologiques et l'analyse des isotopes stables

Organically bound metals and biomarkers in the Monterey Formation of the Santa Maria basin, California

Abstract: Developpement d'un modele geochimique de la distribution des marqueurs biologiques (sterones, hopanes et steroides aromatiques) et des metaux organiquement lies (Cr, Mo, V, Ni) de la formation Monterey (Californie)

Assessing distillate fuel storage stability by oxygen overpressure at higher temperatures

Abstract: A new oxygen overpressure method has been used to purposely accelerate the reactions leading to insoluble sediments formation by forcing oxygen into solution in the fuel at a pressure of 100 psig and then stressing the fuel under conditions of accelerated storage at various temperatures from 43 to 100˚C. The method makes use of gravimetric determination of the total insolubles formed. In order to test the reliability of this higher temperature method, a mini-round robin was conducted using five middle-distillate fuels tested at four different laboratories at the same 90˚C/16 hr/100 psig conditions. Also, stability data for 26 marine gasoil and for 22 F-76 fuels from a world-wide fuel survey were obtained. The results are compared to results obtained from other standard tests. All results are tabulated in gravimetric form in mg of total insoluble sediment per 100 ml of fuel

Latest thoughts on the molecular nature of petroleum asphaltenes

Abstract: The conversion of heavy oils and residua is, essentially, a new art and is, of course, encountering problems that arise as a result of a lack of processing knowledge of these behavior feedstocks. The use of thermal and hydrothermal processes which are inherent in refineries designed to process lighter feedstocks have been a particular cause for concern and has brought about the evolution of processing schemes that will accommodate the heavier feedstocks. A key to increasing the conversion efficiency is to develop a better understanding of the chemistry of coking principally through an understanding of the principal coke-formers - the asphaltenes. Their current understanding of asphaltene character indicates that current, and future, chemical research should focus on (a) skeletal structure; (b) the size of the polynuclear aromatic systems; (c) the internuclear bonds that need to be thermally or catalytically cleaved to produce more manageable lower molecular weight fragments; (d) the heteroatom types and subsequent ease, or difficulty of removal; (e) the metallic constituents and their occurrence in porphyrinic or non-porphyrinc locations; and (f) the actual physicochemical relationships that exist between the asphaltenes and the other constituents of the oil. It is the purpose of this paper to assemble and correlatemore » the relevant material that relates to defining the chemical nature of petroleum asphaltenes. This, of course, must also include studies of the separation of this fraction from crude oils since the nature of the final asphaltene fraction is highly dependent upon the method of separation.« less

Structural features of Athabasca bitumen related to upgrading performance

Abstract: Structural studies on asphaltenes and heavy ends have, until recently, only yielded information on some of the gross compositional features of these materials. Spectroscopic methods, for sample, are limited in the sense that even if several functional groups (e.g., aromatic or aliphatic carbon, carbonyl groups, etc.) can be identified, no information on the molecular environment can be deduced. Selective chemical degradative methods, on the other hand, offer more potential and this paper describes some of their recent results on the chemical degradation of asphaltene and heavy ends. Quantitative recoveries of alkyl side chains and bridging units attached to aromatic rings have been achieved, and some insights into the aliphatic framework have been gained. The results could be particularly helpful with regard to monitoring the dealkylation processes during thermal treatment of bitumens. The aliphatic framework of the asphaltene contains units of five- and six-membered ring sulfides and thermal breakdown of these units also contributes to depolymerization and the production of alkanes. Some of the heteroatom-containing classes of compounds identified in the asphaltene and resin fractions of Athabasca bitumen will be briefly discussed.

Octane enhancement in fluid catalytic cracking by operation in the overcracking regime

Abstract: This paper deals with the hydrocarbon chemistry involved in Research Octane Number and Motor Octane Number enhancement when operating a FCC unit under overcracking conditions, i.e., in the region of high catalyst/oil ratios, where gasoline tends to overcrack to lighter components such as LPG

Detailed structural characterization of the organic material in rundle Ramsay Crossing oil shale

Abstract: The difficulty of achieving quantitative and selective reactions of insoluble organic solids under mild conditions, and the scarcity of good methods for probing the structures of such materials, have discouraged attempts to characterize the molecular structure of the organic material in solid oil shales. Technical advances in solid state {sup 13}C- and {sup 29}Si-NMR now provide powerful new methods for characterizing hydrocarbon structure and heteroatom functionalities in the solid state. Although questions persist about the quantitative reliability of the cross-polarization NMR technique in coals, compositional effects responsible for non-quantitative data collection are less common in oil shales and in the bitumen and derivatized samples produced from these materials. Using mild and selective derivatizations with isotopically labelled reagents followed by solid state {sup 13}C- and {sup 29}Si-NMR analysis has enabled a comprehensive study to chemically characterize the organic functionalities in Rundle Ramsay Crossing oil shale (RXOS) Queensland, Australia. Combining these data with in-depth MS and NMR analyses on shale oils produced under mild conditions from RXOS led to the development of a detailed structural model of the organic material.

New aspects of the application of sterane isomerisation and steroid aromatisation to petroleum exploration and the reconstruction of geothermal histories of sedimentary basins

Abstract: Etude cinetique de l'isomerisation des steranes C 29 et de la transformation des steroides mono-aromatiques en steroides tri-aromatiques par simulation, c'est-a-dire par pyrolyse d'echantillons typiques de roche mere, en presence d'eau. Les donnees cinetiques de l'isomerisation du sterane sont utilisees pour reconstituer l'histoire geothermique du bassin Michigan (Etats Unis)

Comparison of isothermal and nonisothermal pyrolysis data with various rate mechanisms: implications for kerogen structure

Abstract: Evaluation experimentale de deux modeles cinetiques couramment utilises pour la pyrolyse du kerogene: le modele des reactions multiples paralleles et le modele des reactions en serie: kerogene-bitume-huile. Les reactions de pyrolyse, isotherme ou pas, sont realisees sur des schistes Green River (Colorado), des schistes du bassin Uinta (Utah) et des polymeres synthetiques. Les faiblesses des deux modeles sont etudiees et les implications des resultats sur la structure des kerogenes sont discutees

Chromium(II) and (III) pyrrolyl ethylene oligomerization catalysts. Synthesis and crystal structure of square planar Cr(NC4H4)4-2, and pentanuclear (Cr5(NC4H4)10(OC4H8)4)

Abstract: Le mecanisme des catalyseurs d'oligomerisation, du chrome et de la pyrrolyl d'ethylene, est decrit. Il est suivi par la synthese et la structure cristalline du Cr(NC 4 H 4 ) 4−2 et du Cr 5 (NC 2 H 4 ) 10 (OC 4 H 8 ) 4

Asphaltene characterization and diffusion measurements

Abstract: The problems of asphaltene characterization have been tackled from two directions: Fractions of relatively similar molecular weight were obtained by exclusion gel permeation chromatography (GPC) and analyzed for molecular weight, elemental compositions, and UV and H NMR spectroscopy; diffusion properties of these fractions as well as whole asphaltenes were measured by a dynamic adsorption test using both catalysts and porous glasses with discrete pore sizes

Separations and characterizations of fractions from Mayan, Heavy Arabian, and Hondo crude oils

Abstract: The results from hydrotreating the atmospheric residua of Hondo, Heavy Arabian, and Mayan crude oils have been reported recently. Over the same fixed-bed catalyst, the hydrosulfurization activities varied by a factor of two and the hydrodemetallation activities varied almost four-fold. Correlations among the relative activities and the elemental compositions of the feed oils showed a direct relationship between the hydrodemetallation activity and the metals content of the petroleum resins fractions, hereafter called polars. Thus, to discover chemical differences in feed oils and polars that may affect a catalysts activity, they have developed separation schemes to separate the oils into their component fractions and used various analytical techniques to characterize the fractions. The separation scheme developed is a modification and extension of the ASTM D2007 procedure. The sample is separated into saturates, aromatics, polars, and asphaltenes by precipitation/filtration and chromatography with Attapulgus cla and silica gel; then the polars are separated into various acids, bases, and neutral polars with macroporous ion exchange resins. This separation scheme has been applied to 650{degree}F + cut from Hondo (offshore California) crude. The fractions were characterized with carbon and hydrogen elemental analysis, XRF spectrometry for nickel, vanadium, and sulfur, chemiluminescence spectrometry for nitrogen. GC simulatedmore » distillations (saturates only), vapor pressure osmetry (number-average molecular weight) in toluene, flame emission spectrometry, and {sup 13}C-NMR spectroscopy.« less

Highly isospecific catalyst for propylene polymerization composed of TiCl4/MgCl2 and Cp2TiMe2 without donors

Abstract: Le premier objectif de cette etude est de preparer le MgCl 2 avec pour catalyseur le TiCl 4 de maniere a eviter la formation de specimens multi-nucleaires. Le second objectif est de clarifier les interactions avec le systeme catalyseur actif. En conclusion, il est demontre qu'un haut specimen de MgCl 2 , soutenu catalytiquement par le TiCl 4 ne contenant aucun donneur interne ou externe, peut etre obtenu en utilisant le Cp 2 TiMe 2 comme co-catalyseur

Hydrocarbon biological markers in Carboniferous coals of different maturities from the Ruhr area (northwest Germany)

Abstract: A great variety of biological markers has been found in Carboniferous coal samples Changes in the paleo-depositional environment are reflected by the distribution of bacterial derived hydrocarbons These biological markers contribute to a significant extent to the aliphatic hydrocarbon fraction of low-maturity coal samples; their absolute contribution to total organic matter has yet not been estimated Biological markers for gymnosperm were observed, which is in accordance with the phylogenetic evolution of the plant kingdom during the Carboniferous

Pillaring puckered layer silicates

Abstract: The present communication is concerned with aluminium polymer pillaring of KHSi 2 O 5 , either by direct exchange (of the potassium salt) or indirect exchange (through the alkylammonium intercalate). We used chemical analyses, surface area measurements, X-ray diffraction and MAS-NMR spectroscopy to study the pillared products

The effect of injection hold time on GC resolution and the effect of collision gas on mass spectra in geochemical biomarker]2 research

Abstract: Analyse d'un melange de sterane dans du petrole, par chromatographie en phase gazeuse et spectrometrie de masse tandems. Etude de l'influence du temps de sejours dans le chromatographe et du gaz de collision sur les performances de l'analyse

Hydrothermal stability and catalytic cracking performance of some pillared clays

Abstract: Some of our work on Al 2 O 3 -SiO 2 /Al 2 O 3 - and Ti-pillared smectites is discussed mainly from the point of hydro-thermal stability and cracking performance. Some initial results of a study on pillaring of regularly and randomly interstratified illite/montmorillonite mixed layer clays are also included

Fouling in jet fuels: a new approach

Abstract: CFDC modeling ofters the potential of sorting out the complex coupling between the chemistry, fluid mechanics, and heat transfer processes that make fouling difficult to understand. The initial attempt to calibrate a CFDC model was not fully successful but encouraging. At least two global Arrhenius rate expressions may need to be put into the model to cover a wide temperature range. Some capabilities of the model were illustrated for electrically heated tube experiments. The full potential of the model cannot be realized until additional chemistry and physics are implemented and data of local temperatures, velocities, particule size distributions and species concentrations are obtained experimentally

The chemical significance of carbon residue data

Abstract: All thermal upgrading processes, whether in the presence or absence of catalyst and/or hydrogen, produce coke. Some coke formation is essential in catalytic crackers in order to maintain the overall heat balance of the process; too much coke, however, can lead to excessive regeneration temperatures and destruction of the catalyst structure. Hydrogenation catalysts are poisoned by coke which blocks the pore structure and reduces catalytic activity. In non-catalytic processes, e.g. visbreaking, the deposition of coke in the reactor and product heat exchangers necessitates periodic plant shutdown for decoking maintenance. In-situ combustion for the recovery/conversion of tar sand deposits uses the coke formed as a result of thermal cracking reactions to fuel the combustion front through the reservoir and towards the production wells. The coking propensities of petroleum materials are measured by Conradson (ASTM D189 or IP13) and Ramsbottom (ASTM D524 or IP14) carbon residue test methods. Both tests determine the amount of carbonaceous residue left after destructive atmospheric distillation of the sample. The carbon residue data are intended to indicate the quantity of coke which will form under thermal stress, eg. in combustion chambers, burners, distillation towers, reactors and heat exchangers. Recently, an improved microcarbon residue (MCR) test has beenmore » introduced (ASTM D4530) which shows excellent correlation with Conradson carbon residue (CCR) data. No systematic study of the chemical significance of carbon residue data has been reported in the literature. The additivity of CCR data and its dependence on elemental composition are discussed in this paper in order to gain a better understanding of its chemical origins.« less

Niobium oxalate: a new precursor for the preparation of supported niobium oxide catalysts

Abstract: Etude experimentale de la formation d'oxyde de niobium a partir d'oxalate de niobium et caracterisation du catalyseur forme par spectrometrie Raman, diffraction des rayons X, spectrometrie photoelectronique et chimisorption de CO 2 . Le catalyseur prepare est sur un support alumine

The synthesis and catalytic applications of layered double hydroxides

Abstract: We have studied various methods for intercalating organic and inorganic anions into gallery regions and have found that appropriate treatment of calcined layered double hydroxides lead smoothly to the incorporation of fairly large organic anions, e.g. sebacic acid and p-toluene sulphonate anion. With these anions gallery heights of 11.5 and 12.2 A respectively result. We will describe this new route and discuss the implications of using such materials for catalytic reactions. The incorporation of photoactive molecules will also be discussed

Effects of gasoline composition on octane number

Abstract: This work describes the relationship between gasoline composition and octane number using a compositional octane model. Application to this model to FCC gasolines demonstrates catalytic strategies for octane enhancement

Hydrogenation of individual components isolated from Athabasca bitumen vacuum resid

Abstract: Etude de l'influence du silicium contenu dans un residu atmospherique Alaskan North Slope sur l'hydrodesulfuration et l'hydrodemetallation de ce dernier. Analyse de l'influence du silicium sur l'empoisonnement du catalyseur utilise (Co-Ni-Mo/Al 2 O 3 )

34 GHz EPR FTIR spectra of chromatographically separated Boscan asphaltene fractions

Abstract: Etude par spectrometrie FTIR, de trois fractions d'asphaltene Boscan, separees par chromatographie gel; identification dans ces fractions des coordinats du vanadium par spectrometrie RPF, FTIR et par combustion partielle

Evaluation of integration procedures for PNA analysis by C-13 NMR

Abstract: Carbon-13 NMR spectroscopy has become a useful tool in the analysis of crude oils and petroleum products. The determination of the relative percentages of paraffinic, naphthenic and aromatic carbon in crude oils and oil fractions by carbon-13 nuclear magnetic resonance spectroscopy has been shown to compare well with results from ASTM D2140 procedures. In the ASTM method, the PNA analysis is determined by the refractive index, the density and the molecular weight of the material. In carbon-13 NMR spectroscopy, the carbon types are observed directly and, under appropriate conditions, can be readily quantified. Aromatic carbon resonances are observed in the 110-170 ppm region of the 25-60 ppm region of the spectrum. The paraffinic carbon signals are seen as a band of overlapping resonances in the 0-25 ppm region and as sharp resonances in the 25-60 ppm region. The relative percentages of these three carbon types is calculated by the ratio of the area of the resonances for each carbon type over the total area, excluding the solvent and reference peak areas. To study the effects of the baseline subtraction and the baseline correction subroutines on the PNA results, a typical crude oil and its asphaltene fraction were selected as modelmore » compounds. Generally, asphaltene samples display poor sensitivity when analyzed by carbon-13 NMR, so this fraction was chosen to examine the abilities of the two subroutines under non-ideal conditions. As well, the effect of line broadening factors on the PNA results was studied. Line broadening will increase the signal to noise ratio, but also leads to a decrease in resolution.« less

Investigation of oil shale and coal structures by swelling in various solvents

Abstract: Etude de la structure du charbon et des schistes bitumineux a partir de leur gonflement en presence de solvant. Analyse de l'influence du type de kerogenes du type de solvant, de la taille des particules, de la concentration en matiere organique, du degre de pre-oxydation et du traitement de pre-extraction des schistes a l'aide de solvant

Can the D 2007-80 with asphaltene precipitation (SARA) separation, size exclusion chromatography with element specific detection, and hydrogen distribution by NMR help at all in predicting residuum processability?

Abstract: Etude experimentale de l'hydroconversion de residu atmospherique MAYA et analyse de la possibilite de caracteriser le degre de conversion d'un residu a partir de son fractionnement par la methode SARA, de l'analyse des elements par chromatographie gel et de la determination de la distribution en hydrogene par spectrometrie RMN

The cracking chemistry of naphthenes

Abstract: We report here a detailed study of the reactions of methylcyclohexane and methylcyclohexene over an ultrastable Y catalyst. The fundamental chemistry of these compounds should give us clues to the behavior of more complex naphthenes in gas oil cracking

Residue fractions from Saudi Arabian crude oils characterization and analysis

Abstract: Analyse des asphaltenes, des resines, des composes satures et aromatiques dans quatre fractions (extra legere, legere, moyenne et lourde) de residu de petrole provenant d'Arabie Saoudite, par spectrometrie RMN et IR

Isolation and spectroscopic characterization of metalloporphyrins from Venezuelan crude oils

Abstract: Les complexes de vanadium et de nickel de type porphyrine sont isoles dans des petroles bruts venezueliens par sublimation sous vide et par la methode SARA, d'extraction des fractions saturees, aromatiques et contenant des resines et des asphaltenes. Les porphyrines sont analysees par spectrometrie IR et specterometrie UV-visible