Non-hydrocarbon Compounds Research Articles

Abundant non-hydrocarbons in crude oils from the western Qaidam Basin, northwest China

The non-hydrocarbon fraction of immature-low maturity crude oils from the western Qaidam Basin which were formed in the source beds deposited in highly saline and strongly reducing environments were analyzed by GC-MS to determine their compositions. Abundant fatty acids, alkanols, fatty acid glycerol monoesters, and stenols were identified. Geochemical analyses suggested that these compounds were largely originated from the oil source rocks. The linear compounds consist primarily of the short-chain homologues (C10–C20). The C27–C29 sterols detected were dominated by C27 stenols. The molecular characteristics suggest that algae and bacteria were the major source organism. The presence of abundant fatty acid glycerol monoesters suggests that the biological lipids, particularly bacterial phospholipids were important contributors to the formation of the crude oils studied. The existence of abundant unsaturated linear compounds, stenols and high CPI values of linear non-hydrocarbon compounds is consistent with the low maturity of these crude oils.

Correlation of Liquid Thermal Conductivity Using Molecular Connectivity Indices

Correlations for the thermal conductivity of liquids at 0.1 MPa and saturated liquids were proposed for hydrocarbons and non-hydrocarbon compounds separately in this work. The proposed correlations require only structural descriptors, that is, molecular connectivity indices and the number of heteroatoms, as input parameters. Since molecular connectivity indices can be calculated once the molecular structure of the substance concerned is known, the correlations based on them are predictive in nature. The new correlations were compared with existing correlations, and for the 65 hydrocarbons and the 192 non-hydrocarbon compounds adopted in this work, the average absolute deviations are 4.02 and 4.31%, respectively.

The Technical Case for Eliminating the Use of the TPH Analysis in Assessing and Regulating Dissolved Petroleum Hydrocarbons in Ground Water

AbstractIn many states, the total petroleum hydrocarbons (TPH) analysis based on gas chromatography‐flame ionization detection (GC‐FID) is still being used to assess and regulate ground water quality at petroleum release sites. The soluble fraction of fresh crude oil or fresh products that could potentially be dissolved into the ground water is limited to relatively few petroleum hydrocarbon constituents (primarily the C6 to C14 aromatics). Research by numerous investigators has shown that the reported TPH concentrations of ground water samples frequently do not represent dissolved petroleum hydrocarbons but rather represent nondissolved petroleum or polar nonhydrocarbon compounds. Nondissolved petroleum is frequently entrained within a sample when sampling ground water within affected soil, and polar nonhydrocarbons are present in ground water as a result of petroleum biodegradation or other factors. These constituents are being measured because the TPH analysis does not include steps to remove nondissolved petroleum or a silica gel cleanup to remove polars.Many states have regulatory action levels for TPH in ground water that are in the 0.1 to 2 mg/L range. The technical basis for these action levels appears to be toxicity and/or organoleptic (taste and odor) properties of the dissolved petroleum hydrocarbons associated with fresh oil or fresh products. The presence of compounds measured as TPH that are not dissolved petroleum hydrocarbons has proven problematic for regulatory decision‐making because the comparison of concentration data to the regulatory criteria may not be correct. Because the TPH analysis does not reliably distinguish between dissolved petroleum hydrocarbons and other compounds, it should not be used to assess or regulate dissolved petroleum hydrocarbons, in ground water. We recommend that constituent‐specific analyses be used to assess and regulate ground water quality at petroleum hydrocarbon release sites. If TPH must be used due to regulatory requirements, samples should be cleaned up with silica gel to remove polars (and turbidity should be removed, if present) prior to analysis so that comparison to regulatory action levels that are based on properties of dissolved petroleum hydrocarbon constituents is technically appropriate.

Theoretical Bond Energies: A Critical Evaluation

The recently proposed scheme of Grimme (BE scheme) (J. Am. Chem. Soc. 1996, 118, 1529) to calculate intrinsic bond energies (BE's) of hydrocarbons, which define seminal equilibrium quantities of chemical structures, is evaluated critically. CH and regular CC bonds are treated well; the corresponding BE's are reliable and self-consistent. In contrast, the performance of the method is markedly reduced for bonds of unusual length, if the bond length is not determined by bond bending or by conjugation. Differences between BE's for CH bonds, which lie within the remarkably narrow range from ca. 103 to 110 kcal mol-1, and CH bond dissociation energies (BDE's, ca. 86−132 kcal mol-1, linear correlation, Rc = 0.9291) give a measure of radical (de)stabilization. BE's of spx−spy CC single bonds correlate linearly with the respective BDE's (Rc = 0.9987) and can be used for a reliable prediction of BDE's at almost no computational cost. Individual intrinsic bond energies are used to establish CC and CH bond length−bond energy−bond order correlations. In extension of Grimme's original report, the performance of the model is tested thoroughly for anions, cations, and radicals of hydrocarbons and it is shown that these species are treated less satisfactorily. Attempts to treat non-hydrocarbon compounds by the same procedure are also less successful with the exception of saturated silicon hydrides. Results of this work show that the relationships between bond length−bond order−bond energy as described by established models of the chemical bond can be related to the properties of the electron density at bond critical points. Despite the much greater angle distortion, cyclopropane has a strain energy only slightly larger than cyclobutane. This problem of the nearly equivalent strain energies is readdressed, leading to new estimates for the stabilization of cyclopropane due to CH bond strengthening (11.7 kcal mol-1) and to σ-aromaticity (11.3 kcal mol-1).

Method for quantifying the fate of petroleum in the environment

Petroleum is a complex mixture of a wide range of hydrocarbon and non-hydrocarbon compounds of various physical and chemical properties. In recent years, the research on the fate of petroleum in the environment has required analytical methods that can provide more detailed information on the components of petroleum than traditional standard methods. The analytical method presented for aqueous, sediment, and soil samples provides several levels of information on petroleum in the environment.The Total Extractable Materials (TEM) analysis provides a gross measure of petroleum in the environment using methylene chloride extraction and gravimetric analysis. Gross composition analysis separates the methylene chloride extract into a saturate hydrocarbon, an aromatic hydrocarbon, and a polar fraction each measured gravimetrically. In contrast, the target compound analysis provides a detailed measure by GC-MS of 62 specific compounds. Normalization to the conservative compound, 17α,2l -(H)Hopane, is incorporated into the method to reduce the effects of sample and site heterogeneity. Quality control and quality assurance procedures are integral parts of these analyses to assure the validity of the resulting data. A sample data set from a biological augmentation product evaluation was used only to illustrate the interpretation of the petroleum chemistry. In this example, conclusions were dependent on the criteria for evaluating the fate of petroleum. As the product evaluation progressed through the petroleum chemistry method, the conclusion on the their effectiveness changed. Therefore, proper interpretation of the petroleum chemistry, which is dependent on the method, is necessary to correctly evaluate the fate of petroleum in the environment.

Hydrocarbons ofNasutitermes acajutlae and comparison of methodologies for sampling cuticular hydrocarbons of caribbean termites for taxonomic and ecological studies

Using data from the arboreal nestingNasutitermes acajutlae (Holmgren), we propose standard collection and extraction methodology for characterization of cuticular hydrocarbons of termites under field conditions in the tropics. Specifically, we evaluated: (1) the effect of the duration and the number of extractions; (2) the effect of drying termites before extraction; (3) the effect of sample size; (4) the effect of solvents (ethanol versus hexane) on cuticular hydrocarbon profiles. Olefins comprise ca. 70% of the cuticular hydrocarbons ofN. acajutlae. Hydrocarbons consist of two distinct groups: early-eluting components, primarilyn-alkanes and methyl-branched alkanes, and late-eluting compounds, which consist almost exclusively of unsaturated components with one to six double bonds. Soldiers have more early-eluting compounds than workers or alates. Nests from the same island had qualitatively similar, but quantitatively dissimilar hydrocarbon mixtures. Brief extractions of 300 live workers in 10 ml of hexane for only 20 sec produced a hydrocarbon mixture equivalent to a 10-min extraction. Long-term extraction of 300 workers in hexane for two years resulted in different mixtures of hydrocarbons. Drying workers tended to enhance extraction of the less abundant unsaturated compounds such as C41.4 and C41.5. A single extraction of a minimum of 100 workers (live or dried), with hexane for 20 sec to 10 min is best; these extraction regimes resulted in mixtures of hydrocarbons that are quantitatively very similar. For quantitative comparisons, extracts from dried samples should not be compared to those from live samples. Storage in ethanol caused numerous unidentified, nonhydrocarbon compounds to be extracted either from the cuticle or from internal tissues.

Bacterial abundance and activity in hazardous waste-contaminated soil

The Office of Technology Assessment has estimated that there may be as many as 10,000 abandoned hazardous waste disposal sites across the United States, many of which have the potential to adversely impact drinking water supplies. Of the many options available for the remediation of these sites, the use of microorganisms to degrade organic chemicals offers many advantages in terms of speed, efficiency and cost. Bioremediation has been used with success to treat soils contaminated by kerosene and other hydrocarbon products. In these studies, the indigenous soil populations of the contaminated soils were effective in removing the spilled hydrocarbons and returning the soil to productivity. The effectiveness of bioremediation for nonhydrocarbon compounds or the complex mixtures of chemicals likely to occur at abandoned hazardous waste sites has received less attention. The present study was designed to determine the activity of indigenous microbial populations at a hazardous waste site, their degree of adaptation to toxic chemicals present in the waste mixture, and their ability to degrade toxic organic compounds, using phenol as a model substrate.

Rapid liquid chromatography of oils in the production of sulfonated additives

543.544.51 The most promising method for determining the group composition of crude oil fractions and residues is liquid column chromatography (LCC), in particular, reversed-phase high-performance liquid column chromatography. This latter method provides for the separation into groups of saturated, aromatic, and nonhydrocarbon compounds [1-3], as well as for the separation of aromatic hydrocarbons by ring number and other structural features of the molecules [2, 4]. NMR, mass spectrometry, IR spectroscopy, and other methods are used to identify some or all of the chromatographic peaks corresponding to the compounds isolated. Quantitative interpretation of the results of the separation is complicated by the need to introduce calibration coefficients [5, 6]; to determine these, parallel preparative LCC is performed to isolate the groups of compounds to be analyzed (standards for the calibration) - a complicated and not always reliable procedure. As a result, it is a problem of current interest to develop techniques incorporating advances made in HPLC [7-10] for separations (sample size 0.15 g or more) and group-type determinations that utilize a universal (gravimetric) method of monitoring the weight of the compounds isolated. In this article we describe a technique for the rapid LCC separation of crude Oils and neutral oils encountered in the production of sulfonate additives, and for the separate determination of the oils' contents of paraffin-naphthenic compounds, four groups of aromatic hydrocarbons, and nonhydrocarbon compounds. The separation takes place in a system consisting of four glass columns connected in series by metal capillary tubing, the columns being supported by metal jackets with bushings at the ends to ensure an hermetic seal (Fig. i). Column i is filled to a point halfway up

Fractionation of soluble portion of reductively alkylated bituminous coals

Five bituminous coals were reductively alkylated with potassium and 1-butyl iodide in THF. The benzene soluble portion of reductively butylated coals were separated into the saturates, aromatics, neutral heterocyclics, ethers and polar compounds on a silica gel column. From the saturates, the n-alkanes were isolated by the thin-layer and column chromatography on silica gel, and then analyzed by GC. The aromatics were fractionated on a dual packed SiO2/Al2O3 column. The mono- and diaromatic fractions obtained were studied by GC-MS method. The non-hydrocarbon and polar compounds were charcterized by elemental composition, VPO molecular weight and both IR and 1H NMR spectra. The asphaltenes from one reductively butylated coal were fractionated into basic and acidic/neutral parts after bubbling dry HCl gas through their benzene solution. A concept that benzene eluates collect C-alkylation products and diethyl ether + THF mixtures collect the products of O-alkylation was evolved. The ratio of C-alkylation to O-alkylation was found to be a function of the C content of the initial coals.

A method for the prediction of heats of vaporization of non-hydrocarbon compounds based on the Clausius-Clapeyron equation

A method for the prediction of heats of vaporization of non-hydrocarbon compounds based on the Clausius-Clapeyron equation

Oxidation of distillate engine fuels by permanganatometric method

Oxidation by potassium permanganate is widely used in testing fuels and lubricants. The precision of the permanganate oxidation method have been determined on tests on just fuels differing in production technology. The procedure was also used under refinery laboratory conditions to test many commercial batches of T-1 jet fuel, automotive gasolines, and diesel fuels. In this paper, the relative contribution of nonhydrocarbon compounds and aromatic hydrocarbons to the oxidation of jet fuel is shown. It is also illustrated how the results from oxidation of the hydrocarbon groups of fuels differ depending on their structures. The permanganate method has also been used to evaluate the stability of RT fuel in 5-year storage tanks. This experience in the method provides grounds for recommending it for widespread use in research on engine fuels.

Acidic and basic components in crude oils of West Siberia

Summary o 1. Acidic and basic components were separated from oils of various deposits of West Siberia. The content of non-hydrocarbon components in the deposit varies over one order of magnitude. 2. Statistical analysis failed to show any correlation between the physico-chemical characteristics of oils and their content of non-hydrocarbon components. However there is a close correlation between the content of various groups of non-hydrocarbon compounds. 3. The proportion of n-acids increases with increasing depth of occurrence of the oils and the MW maximum in the distribution of these acids is displaced from C 2 −C 28 to C 18 −C 22 . 4. The regularities between the composition of the petroleum acids appear to be related to the mechanism of biochemical transformation of the oils in their deposits.

The biological effects of the water-soluble fractions of a no. 2 fuel oil on the planktonic shrimp, Lucifer faxoni

The biological effects of water-soluble fractions (WSFs) of a No. 2 fuel (heating) oil on the planktonic shrimp, Lucifer faxoni, were investigated. Biological parameters used to assess toxicity were survival, respiration, feeding rate and degree of activity. In the survival and feeding studies two experiments were carried out, one with freshly prepared WSF (Exp. 1), the other with WSF exposed to air for 48 h (Exp. 2) before the animals were introduced. Based on survival data for fourteen days exposure, critical levels of toxicities in Exp. 1 were about 0·2 ppm, while in Exp. 2 they were around 2 ppm. A similar trend was found in studies of feeding and degree of activity. Unexposed extracts (Exp. 1) were more toxic and the effect on feeding was immediate and irreversible; exposed WSF was less toxic, the effect on feeding was delayed and reversible. The chemical composition of fresh WSF and of WSF exposed to air from 6 h to 5 days was determined. Alkyl benzenes, indans, and naphthalenes were rapidly lost from the exposed solution, with only negligible concentrations remaining after 24 h. In contrast, certain non-hydrocarbon compounds such as alkyl anilines, phenols, and indoles were generally present even after 5 days at greater than 50% of their initial concentration. The biological and chemical data appear to indicate that the higher toxicity of fresh WSF to L. faxoni was due to volatile aromatic hydrocarbons. It seems that the toxicity of oil spills could be markedly less than some laboratory results suggest because there is reduced toxicity following weathering by evaporation. Respiration rates of L. faxoni during an 8 h exposure to freshly prepared WSF rose with increasing concentrations up to 30% of WSF, then fell with further increases of concentration of WSF.

The Effect of Interfacial Films on the Displacement of Oil by Water Porous Media

Abstract Many crude oils contain surface active compounds that will collect at an oil-water interface to form a rigid film. Since interfacial forces are important in the displacement of oil by water in reservoir rock, the presence of rigid films in the reservoir could alter the recoverable oil by water invasion. Experimental work in water-wet Porous media indicates that the presence of interfacial films decrease the amount of recoverable oil in highly heterogeneous porous medial but usually has no effect in nearly homogeneous systems. Introduction It is generally accepted today that petroleum is derived from sedimentary organic matter. Meinschein, working with several soils and recent marine deposits, found that nonhydrocarbon organic compounds, similar to compounds found in living things, made up about 80 percent of the extracted organic material. Porphyrins, percent of the extracted organic material. Porphyrins, amino acids, and sulfur compounds were the main constituents found. Amino acids are the basic units of protein and, as such, are an essential part of all organisms. Erdman shows several possible reactions for the conversion of amino acids and carbohydrates to the common low molecular weight hydrocarbons. Baker, as well as Hodgson and Hitchon, gives evidence that complex natural organic compounds act as "solubilizers" to allow the movement of hydrocarbons by ground water from the source bed to the reservoir. Trace amounts of soluble polar organic compounds are usually found in reservoir water. Thus, the high molecular weight surface active material found in crude oils (such as the porphyrinmetal complexes, esters, ketones, aldehydes, porphyrinmetal complexes, esters, ketones, aldehydes, carboxylic acids and organic nitrogen compounds) are probably remnants of the organic matter from which the crude oil originated. With many crudes, the presence of significant quantities of surface active material can result in the formation of a rigid film at an oil-water interface. If the interfacial area is reduced, the film will often wrinkle, indicating the formation of a solid membrane. The presence of film material has an important effect in the formation and stability of oilfield emulsions, and in the deposition of paraffin in oilfield equipment. Fig. 1 is a paraffin in oilfield equipment. Fig. 1 is a photograph taken during a microscopic examination photograph taken during a microscopic examination of film material obtained after breaking a water-in-oil emulsion. Shown in the photograph are ruptured film sacs that once stabilized two droplets of water in the emulsion. Interfacial forces are important in the displacement of oil by water in reservoir rock, and the presence of rigid Elms could alter these forces. Since much of the available laboratory data on the displacement of oil by water in porous media was obtained using relatively pure water and oil, the effect of rigid films should be known if we are to apply these data to reservoir systems.

Effect of jet fuel hydrocarbon composition on thermal stability

1. The source of sediment formation when jet fuels are oxidized, apart from nonhydrocarbon compounds, is the aromatic hydrocarbons, particularly naphthalene derivatives and polycyclic naphthenic-aromatic hydrocarbons; by comparison, alkylbenzenes form much less sediment. 2. The paraffinic and naphthenic hydrocarbons present in jet fuels do not form any sediment when oxidized. The structure of the nonaromatic component has a substantial effect on the degree of coagulation of the aromati-chydrocarbon oxidation products, hence on the amount of sediment formed. 3. Maximum amounts of sediment are formed when aromatic-isoparaffinic blends are oxidized, minimum amounts with blends of aromatics with bicyclic naphthenes (e.g., decalin). As the side-chain length of the naphthenic hydrocarbons is increased, the amount of solid phase formed by blend oxidation also increases. 4. Thus, hydrocarbon fuels will have good thermal stability if they do not contain any polycyclic naphtheni-caromatic or aromatic hydrocarbons and if the nonaromatic portion consists primarily of naphthenes. If the naphthenes consist of at least 30–40% bicyclic naphthenes, a limited amount (up to 10–15%) of monocyclic aromatics may be allowed.

Chemical stabilization of hydrocracking distillates

1. Treatment of the hydrocracking distillate with either an aqueous solution of fresh sulfuric acid or with the spent acid after sulfuric acid alkylation ensures that a stabilized component of diesel fuel will be obtained without changing its initial hydrocarbon composition. 2. It was shown that the basic reason for the low chemical stability of the distillate from the hydrocracking of deasphaltizate is the increased concentration of nitrogen, oxygen, and sulfur compounds with an unstable structure in it. Upon their removal the distillate acquires the necessary stability. 3. The nonhydrocarbon compounds which are present in the hydrocracking distillate are characterized. It was shown that they consist of nitrogen, oxygen, and sulfur compounds, mainly cyclic in nature.

The Geochemistry of Petroleum Migration and Accumulation: ABSTRACT

Small quantities of a large variety of organic compounds enter the Recent marine sediments before burial. Petroleum, the only major organic and fluid substance in the consolidated rocks, however, contains mainly End_Page 406------------------------------ hydrocarbons. Experiments indicate that hydrocarbon compounds may travel through the sediments with the least restraint during intrastratal fluid flow. Most of the non-hydrocarbon compounds may be removed from the flowing phase by a selective filtration, i.e., chromatographic process. Chromatography is a physical-chemical method of separation of fluid mixtures in which the components to be separated are distributed between two phases. One is a stationary phase of a large surface area and the other one is the fluid phase that percolates through the stationary phase. Fine-grained mineral particles, organic inclusions and (or) immiscible liquid droplets in sedimentary rocks may constitute the stationary phase. The Martin and Synge chromatographic theory is applied for tracing fluid flow through the sedimentary rock strata. Petroleum contains colloidal particles, some of which are too large to have flowed through the smaller pore openings. Experiments show that oxidation and some other chemical reactions, taking effect after accumulation, may be responsible for the development of a part of the petroleum colloids. A regional study of the distribution patterns of organic constituents, combined with geological and geophysical data, can be useful information to the exploration geologist. End_of_Article - Last_Page 407------------

Geochemical Investigations of Athabasca Oil Sands: ABSTRACT

Analyses were performed to evaluate the organic composition and the mineral content of the McMurray oil sands in northeastern Alberta, Canada. The samples came from the Abasand Quarry near McMurray and from three bore holes, drilled along a southwest-northeast cross section in the Fort MacKay and Bitumount area. The bitumen content is related to the particle size of the rock. Impregnation is not restricted to one particular sediment type in the McMurray formation. For example, sandstone zones in the Bitumount core were found to contain as much as 17 per cent organic material soluble in methylene chloride; the bitumen content of the shale layers is lower. The elementary composition of the organic material was found to be uniform throughout the entire 246-foot section of the McMurray formation in the core. An organic sulphur content of approximately 5 per cent extends throughout the core. The aromatic character of the bitumen was shown by spectroscopic methods of analysis. The bitumen contains End_Page 1253------------------------------ approximately the same amount of those hydrocarbons that may be recovered by n-heptane elution on silica gel columns. The abundantly available Abasand samples were subjected to detailed analysis. These samples represent the lower portion of the McMurray formation, lying a few feet above the Devonian limestone. The bitumen was found to be a complex mixture of hydrocarbon and non-hydrocarbon compounds; the character of a few of which can be indicated. The bitumen was observed to be susceptible to contaminations by microorganisms; this required precautions during analysis. The chemical composition of the samples indicates that the Athabasca bitumen is basically a crude oil. End_of_Article - Last_Page 1254------------

COMPOSITION OF ORGANIC MATTER IN MARINE SEDIMENTS: PRELIMINARY DATA ON HYDROCARBON DISTRIBUTION IN BASINS OFF SOUTHERN CALIFORNIA

As part of a program to evaluate the influence of environment on the composition of organic matter in marine sediments and the changes in composition that occur in the upper zones of sediment, cores from several basins representing different environments off southern California were examined for extractable organic matter, hydrocarbon content, and certain other properties. The data are of particular interest in considerations of the early stages of petroleum formation. Hydrocarbon fractions were separated from extractable organic matter by chromatography on alumina. This technique permitted semiquantitative separations of a paraffin-naphthene hydrocarbon fraction and an aromatic fraction. The aromatic fraction, in the present work, contained large amounts of nonhydrocarbon aromatic compounds, and a more refined procedure seems necessary for a detailed study of aromatic hydrocarbon distribution. While the number of samples is too small to allow definite geologic conclusions, the following are indicated: (1) The sediment in the shallowest basin with the fastest sedimentation rate contains the highest proportion of material soluble in organic solvents and the highest hydrocarbon content even though this sediment is lowest in total organic matter. (2) Hydrocarbons comprise 2.3–18.6 per cent of the extractable organic matter and 0.05–0.64 per cent of the total organic matter in the three basins examined. The hydrocarbon content does not differ greatly in the different basins, nor with depth (to 4 meters) in a given basin. Variations with depth appear to be random. (3) Pyrolysis of sediments at 500° C (modified Fischer retort assay) shows only random variations with depth to 4 meters in a given basin, and the average yield of oil indicates about 7–9 per cent conversion of organic matter to oil. Compared to typical oil-shales, which give 50–75 per cent conversion, this low conversion indicates that basin sediments and oil-shales differ significantly either in the nature of the organic matter or in catalytic activity of the mineral components. (4) The average potential oil yield, computed from hydrocarbons extracted from the sediments, is about 10 times the eventual recovery from oil fields of the Los Angeles Basin, but is only one-tenth the yield of oil obtained by pyrolysis. (5) The proportions of hydrocarbons and more complex materials separated from the sediments differ from their proportions in petroleum. These differences may result from later changes and/or fractionation during migration from source beds.