Complex Mixture Of Hydrocarbons Research Articles

La cromatografía de gases acoplada a espectrometría de masas como herramienta de alta selectividad para caracterizar fósiles químicos en el petróleo

Petroleum molecular fossil (biomarker) determination constitutes a formidable analytical challenge, because it demands detecting and quantifying specific trace-level molecules within highly complex hydrocarbon mixtures. This article highlights certain results of importance to organic geochemistry, which have been possible thanks to the use of mass spectrometry as a highly sensitive and selective detection system, in conjunction with the high resolution provided by one-dimensional or comprehensive (GC × GC) gas chromatography. Representative examples of recent biomarker studies in petroleum and environmental geochemistry have been selected.

Irresolvable complex mixture of hydrocarbons in soybean oil deodorizer distillate

Aliphatic hydrocarbons (HCs) can be used as a fingerprint of a given seed oil. Only by characterization of aliphatic HCs could contamination by mineral oil in that seed oil be confirmed. During the isolation of squalene from soybean oil deodorizer distillate, a significant amount of unknown HCs, ca. 44 wt%, was obtained. These seemingly-easy-to-identify HCs turned out to be much more difficult to elucidate due to the presence of an irresolvable complex mixture (ICM). The objective of this study was to purify and identify the unknown ICM of aliphatic HCs from soybean oil deodorizer distillate. Purification of the ICM was successfully achieved by using modified Soxhlet extraction, followed by modified preparative column chromatography, and finally by classical preparative column chromatography. FT-IR, TLC, elemental analysis, GC/FID, NMR and GC-MS analyses were then performed on the purified HCs. The GC chromatogram detected the presence of ICM peaks comprising two major peaks and a number of minor peaks. Validation methods such as IR and NMR justified that the unknowns are saturated HCs. This work succeeded in tentatively identifying the two major peaks in the ICM as cycloalkane derivatives.

Surrogate fuels for premixed combustion in compression ignition engines

Simple surrogate fuels are needed to model practical fuels, which are complex mixtures of hydrocarbons. The surrogate fuel should match the combustion and emissions behaviour of the target fuel as much as possible. This paper presents experimental results using a wide range of fuels in both the gasoline and diesel auto-ignition range, but of different volatilities and compositions, in a single cylinder diesel engine. Premixed combustion in a compression ignition engine is defined, in this paper, to occur when the injection event is clearly separated from the combustion and the engine-out smoke is very low – below 0.05 FSN (filter smoke number). Under such circumstances, if the combustion phasing is matched for two fuels at a given operating condition and injection timing, the emissions are also comparable regardless of the differences in composition and volatility. For the experimental conditions considered, combustion phasing at a given operating condition and injection timing depends only on the octane index (OI), OI = (1-K)RON + KMON, where RON and MON are research and motor octane numbers and K is an empirical constant that depends on operating conditions. A mixture of iso-octane, n-heptane and toluene can be found to match the RON and MON of any practical gasoline and will be a very good surrogate for the gasoline since it will have the same OI. If the compression ratio is greater than 14, practical diesel fuels, with DCN (derived cetane number) between 40 and 60, will have comparable ignition delays ton-heptane, which is an adequate surrogate for such fuels. However, premixed combustion can be attained only at much lower loads at a given speed with diesel fuels compared to gasolines.

Simulating the Performance of a Catalytic Microsensor for Quantifying Ethanol in Inert and Reactive Environments

The selective detection of hydrocarbons using portable microsensors remains a fundamental challenge in materials and microsystem development. This work describes the functioning of a proposed thermoelectric catalytic microsensor using a metal oxide catalyst and a selective partial oxidation reaction for ethanol detection in complex hydrocarbon mixtures containing hundreds of hydrocarbons present in gasoline fuel. In the case where the competing hydrocarbons are nonreactive, 100% selectivity toward ethanol would be obtained and quantification is straightforward—this case is simulated using ethanol in an inert atmosphere. As an example of detection and quantification in the presence of other reactants, a two step detection sequence is presented for the identification of ethanol concentrations in a hydrocarbon mixture containing methanol. Two-dimensional COMSOL simulations are performed, using known kinetic parameters for ethanol and methanol partial oxidation to acetaldehyde and formaldehyde, respectively, ...

Modifying the response of a polymer-based quartz crystal microbalance hydrocarbon sensor with functionalized carbon nanotubes

This report compares the performance of polymer and carbon nanotube–polymer composite membranes on a quartz crystal microbalance (QCM) sensor for the detection of aromatic hydrocarbons (benzene, toluene, ethylbenzene, p-xylene and naphthalene) in aqueous solutions. Several different polymers (polystyrene, polystyrene-co-butadiene, polyisobutylene and polybutadiene) and types of functionalized carbon nanotubes (multi-walled and single-walled carbon nanotubes) were investigated at varying carbon nanotube (CNT) loading levels and film thicknesses. In a majority of instances, the difference in response between membranes comprising pure polymer and membranes containing 10% (w/w) carbon nanotubes were not statistically significant. However, a notable exception is the decreasing sensitivity towards p-xylene with increasing carbon nanotube content in a polybutadiene film. This variation in sensitivity can be attributed to a change in the sorption mechanism from absorption into the polymer phase to adsorption onto the carbon nanotube sidewalls. With much thicker coatings of 10% (w/w) carbon nanotube in polybutadiene, the sensitivity towards toluene was higher compared to the pure polymer. The increased toluene sensitivity may be partially attributed to an increase in the sorption capacity of a carbon nanotube polymer composite film relative to its corresponding pure polymer film. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) measurements were performed to understand the mechanism of sorption and these studies showed that the addition of functionalized CNT to the polymer increases the absorption of certain types of hydrocarbons. This study demonstrates that carbon nanotubes can be incorporated into a polymer-coated QCM sensor and that composite films may be used to modify the QCM response and selectivity during the analysis of complex hydrocarbon mixtures.

Chemical Sensor Array That Can Differentiate Complex Hydrocarbon Mixtures Dissolved in Seawater

Chemical Sensor Array That Can Differentiate Complex Hydrocarbon Mixtures Dissolved in Seawater

Assessing the Bioavailability of Complex Petroleum Hydrocarbon Mixtures in Sediments

Several experimental methods have been developed to assess the bioavailability of individual organic compounds. So far none of them has however been applied to complex mixtures, such as oil (petroleum hydrocarbons), which is an ubiquitous pollutant. In the present study, we tested the potential of five of these experimental methods and that of a model approach to predict bioaccumulation of oil in the aquatic worm Lumbriculus variegatus exposed to 14 field-contaminated sediments. Actual and predicted bioaccumulation were compared in terms of both total bioaccumulative petroleum hydrocarbon concentrations and the relative distribution pattern of separate boiling point fractions (hydrocarbon blocks). None of the experimental methods was able to directly assess bioaccumulation in L. variegatus and correction factors were needed to match predicted and actual concentrations. These factors appeared concentration-dependent for solid phase micro extraction (SPME) and extractions with Tenax and cyclodextrin, most probably due to artifacts. Moreover, the hydrocarbon block pattern produced by these methods considerably differed from the pattern observed for worms; an additional reason for disqualification also applying to headspace-SPME. In contrast, the pattern produced by polyoxymethylene solid phase extraction (POM-SPE) closely mimicked the worm pattern and a sediment, hydrocarbon block, and concentration-independent correction factor (17) could be derived, based on which actual bioaccumulation could be predicted within a factor of 3. Finally, the model predicted bioaccumulation directly within a factor of 2. The accompanying hydrocarbon block pattern however deviated significantly more from the worm pattern than the POM-SPE pattern did. We therefore conclude that POM-SPE may be the overall best approach for predicting bioaccumulation of complex hydrocarbon mixtures in aquatic worms, all the more since an experimental approach will implicitly capture all factors determining bioavailability, which may prove difficult through a modeling approach.

ChemInform Abstract: The Most Important Methods for Depollution of Hydrocarbons Polluted Soils

AbstractReview: 12 refs.

Revealing the properties of oils from their dissolved hydrocarbon compounds in water with an integrated sensor array system

This paper presents a system and method developed to identify a source oil's characteristic properties by testing the oil's dissolved components in water. Through close examination of the oil dissolution process in water, we hypothesise that when oil is in contact with water, the resulting oil-water extract, a complex hydrocarbon mixture, carries the signature property information of the parent oil. If the dominating differences in compositions between such extracts of different oils can be identified, this information could guide the selection of various sensors, capable of capturing such chemical variations. When used as an array, such a sensor system can be used to determine parent oil information from the oil-water extract. To test this hypothesis, 22 oils' water extracts were prepared and selected dominant hydrocarbons analyzed with Gas Chromatography-Mass Spectrometry (GC-MS); the subsequent Principal Component Analysis (PCA) indicates that the major difference between the extract solutions is the relative concentration between the volatile mono-aromatics and fluorescent polyaromatics. An integrated sensor array system that is composed of 3 volatile hydrocarbon sensors and 2 polyaromatic hydrocarbon sensors was built accordingly to capture the major and subtle differences of these extracts. It was tested by exposure to a total of 110 water extract solutions diluted from the 22 extracts. The sensor response data collected from the testing were processed with two multivariate analysis tools to reveal information retained in the response patterns of the arrayed sensors: by conducting PCA, we were able to demonstrate the ability to qualitatively identify and distinguish different oil samples from their sensor array response patterns. When a supervised PCA, Linear Discriminate Analysis (LDA), was applied, even quantitative classification can be achieved: the multivariate model generated from the LDA achieved 89.7% of successful classification of the type of the oil samples. By grouping the samples based on the level of viscosity and density we were able to reveal the correlation between the oil extracts' sensor array responses and their original oils' feature properties. The equipment and method developed in this study have promising potential to be readily applied in field studies and marine surveys for oil exploration or oil spill monitoring.

Molecular reconstruction of complex hydrocarbon mixtures: An application of principal component analysis

AbstractThree methods for reconstruction of the detailed molecular composition of complex hydrocarbon mixtures, based on their global properties, are compared: a method based on the Shannon entropy criterion, an artificial neural network and a multiple linear regression model. In spite of the broad range of naphthas included in the training set, the application range of the last two methods proved to be limited. Principal component analysis allowed to identify their three‐dimensional ellipsoidal application range. In this subspace, the artificial neural network is more accurate than the multiple linear regression model and the Shannon entropy method. However, outside its application range, the performance of the neural network, as well as the regression model, decreases drastically. In contrast, the performance of the Shannon entropy method is not influenced by the characteristics of the considered naphtha, but rather depends on the number of available commercial indices. The Shannon entropy method yields comparable results to the artificial neural network, provided that a sufficient amount of distillation data is available to supply information on the carbon number distribution. Combining the reconstruction methods with a fundamental simulation model illustrates the necessity of having accurate feedstock reconstruction methods since they allow to capture the full power of fundamental simulation models for the simulation of industrial processes. © 2010 American Institute of Chemical Engineers AIChE J, 2010

Determination of genetic damage and urinary metabolites in fuel filling station attendants

Fuel (diesel and petrol) constitutes a complex mixture of volatile flammable liquid hydrocarbons among them benzene (BZ), toluene (TOL), and xylene (XYL) are considered to be the most hazardous, predominantly BZ because of its carcinogenic potency. Exposure to these compounds may have an impact on the health of the exposed subjects. Hence, genotoxicity and quantitative analysis of these compounds was performed in blood and urine samples of 200 workers exposed to fuel in filling stations and compared to controls. The level of genetic damage was determined by micronucleus test (MNT) in buccal epithelial cells (BEC) and chromosomal aberrations (CA) assay in peripheral blood lymphocytes (PBL) of fuel filling station attendants (FFSA) and compared to a matched control group. Urine analysis for BZ and its metabolites, phenol (Ph), trans, trans-Muconic Acid (t, t-MA), and S-Phenyl Mercapturic Acid (S-PMA) was done in all the study subjects. The results of our study revealed that exposure to BTX in petrol vapors induced a statistically significant increase in the frequency of micronuclei (MN) and CA in the exposed subjects than in controls (P < 0.05). There was a significant rise in the levels of urinary BZ, Ph, t, t-MA, and S-PMA in the exposed subjects. Our study highlights the significance of MNT, CA, and urinary metabolites as potential biological exposure indices of genetic damage in FFSA. This study suggests the need for regular monitoring of FFSA for possible exposure to BTX as a precautionary and preventive step to minimize exposure and reduce the associated health risks.

Liquid fuel from waste polyolefins part I: Thermal and pressure degradation of waste polyolefins in tetralin as H-donor model system

In the paper, the results of the study on a laboratory process of thermal and pressure destruction of waste polyolefins in the presence of tetralin as a model hydrogen donor are presented. Waste polyolefins were termally cracked in the presence of a catalyst and hydrogen donor (tetralin) in a closed autoclave (volume: 1 dm 3) in the anaerobic atmosphere. The process temperature was maintained 400–500 °C. The pressure at the end of process, depending on the feed composition, was 10–15 MPa. As a result, a desirable liquid fraction was obtained. A product of waste polyolefin decomposition in the presence of tetralin is a complex mixture of hydrocarbons. The analysis of products has shown satisfactory decomposition of polymer chains as well as hydrogenation of unsaturated structures. Low sulphur and chlorine contents in the obtained fractions constitute a highly positive effect, especially in a fuel aspect. A significant disadvantage here is a considerable number of tetralin conversion reactions. The use of this hydrogen donor for technological purposes is not possible as the final fraction must be cleared from disproportionation products or hydrogen donor decomposition products.

High temperature AFM study of CAP 30/45 pen grade bitumen

Bitumen is a complex mixture of hydrocarbons for which microstructural understanding is incomplete. In an effort to detail this microstructure, a asphalt cement sample (CAP 30/45) was analysed by thermal phase detection atomic force microscopy. Phase contrast and topography images showed that sample morphology is highly dependent on temperature. The 'bee structure' changed considerably at temperatures between 50 degrees C and 56 degrees C. A decrease of the oscillation amplitude was observed upon heating and the 'bees' completely disappeared at temperatures above 57 degrees C. When the temperature was decreased after melting at 170 degrees C, the 'bees' began to nucleate gradually at temperatures of 57 degrees C and its evolution with time was followed. Changes in morphology were compared to thermal analysis results and a model for the 'bee' structure was proposed.

CO-exposure to mercury accelerates autoimmunity induced by trichloroethylene

Acute effects of individual and complex mixtures of polycyclic aromatic hydrocarbons (PAHs) are well documented in vertebrate species. Hypoxia in fish reduces metabolic rate and reproduction. However, less is known about the later life consequences stemming from early-life exposure to PAHs or hypoxia, particularly their co-exposure. To address this, medaka (Oryzias latipes) embryos were exposed to a complex PAH mixture sediment extract from the Elizabeth River, VA (ERSE) at concentrations of 0.1, 0.5, or 1.0% or to one of three different hypoxia scenarios: continuous, nocturnal, or late stage embryogenesis hypoxia. Co-exposures with 0.1% ERSE and each of the hypoxia scenarios were conducted. Results included decreased survival with ERSE, hatching delays with hypoxia, and higher occurrences of deformities with each. The continuous hypoxia scenario caused the most significant changes in all endpoints. These early-life exposures altered later-life growth, impaired reproductive capacity, and reduced the quality of their offspring. ERSE alone resulted in a female-biased sex ratio while continuous or nocturnal hypoxia produced significantly greater numbers of males; and co-exposure produced an equal sex ratio. Exposure to a PAH mixture and hypoxia during early life stages has meaningful later-life and next generational consequences.

Estimating molecular masses of petroleum-derived fractions: High mass (>2000 u) materials in maltenes and asphaltenes from Maya crude oil

Molecular mass ranges and average masses of fractions from a heavy Mexican crude oil (Maya) have been studied, using mainly size exclusion chromatography (SEC) and laser desorption-mass spectrometry (LD-MS). Method development focused on the use of planar chromatography and size exclusion chromatography (SEC), to isolate narrow bands of material from solubility-separated fractions of the crude oil. The procedure provides a planar chromatography based method for studying mass ranges in complex hydrocarbon mixtures. It allows the calculation of ‘best estimate’ values for number and mass-averages. These can then be used in average structural parameter (ASP) calculations, for studying structural features of the samples. The method is applicable to both coal and petroleum-derived samples. The molecular mass estimates arrived at in this work for petroleum-derived samples are considerably higher than those reported by other workers for similar samples. The results presented here provide strong evidence for the presence of ions approaching m/ z 10,000 in the Maya asphaltene. The maltene fraction was found to contain a small amount of ions with mass ( m/ z) in excess of 2000.

On-line analysis of complex hydrocarbon mixtures using comprehensive two-dimensional gas chromatography

This paper discusses the first setup for on-line qualitative and quantitative comprehensive two-dimensional gas chromatography (GC × GC) of complex hydrocarbon mixtures. A built-in 4-port 2-way valve allows switching between flame ionization detection (FID) and time-of-flight mass spectrometry (TOF-MS) between runs, without the need to cool down and vent the MS. Proper selection of GC carrier gas flow rates enables maximal agreement between the obtained chromatograms in both configurations. For on-line analysis of reactor effluents, a dedicated sampling system allows automatic sampling of the hot reactor effluent gases and immediate injection of the sample on the GC × GC. To determine a complete effluent composition in a single run of the GC × GC, a subzero oven starting temperature was employed. Modulation is started when the oven temperature reaches 40 °C, thus dividing the chromatogram in a conventional 1D and a comprehensive 2D part. This work illustrates the mature and robust character of GC × GC, extending its capabilities from mere laboratory use to on-line routine analysis for industrial processes in the (petro-)chemical industry.

Occurrence, production, and export of lipophilic compounds by hydrocarbonoclastic marine bacteria and their potential use to produce bulk chemicals from hydrocarbons

Petroleum (or crude oil) is a complex mixture of hydrocarbons. Annually, millions of tons of crude petroleum oil enter the marine environment from either natural or anthropogenic sources. Hydrocarbon-degrading bacteria (HDB) are able to assimilate and metabolize hydrocarbons present in petroleum. Crude oil pollution constitutes a temporary condition of carbon excess coupled to a limited availability of nitrogen that prompts marine oil-degrading bacteria to accumulate storage compounds. Storage lipid compounds such as polyhydroxyalkanoates (PHAs), triacylglycerols (TAGs), or wax esters (WEs) constitute the main accumulated lipophilic substances by bacteria under such unbalanced growth conditions. The importance of these compounds as end-products or precursors to produce interesting biotechnologically relevant chemicals has already been recognized. In this review, we analyze the occurrence and accumulation of lipid storage in marine hydrocarbonoclastic bacteria. We further discuss briefly the production and export of lipophilic compounds by bacteria belonging to the Alcanivorax genus, which became a model strain of an unusual group of obligate hydrocarbonoclastic bacteria (OHCB) and discuss the possibility to produce neutral lipids using A. borkumensis SK2.

Novel characterization of the aerosol and gas-phase composition of aerosolized jet fuel

Few robust methods are available to characterize the composition of aerosolized complex hydrocarbon mixtures. The difficulty in separating the droplets from their surrounding vapors and preserving their content is challenging, more so with fuels, which contain hydrocarbons ranging from very low to very high volatility. Presented here is a novel method that uses commercially available absorbent tubes to measure a series of hydrocarbons in the vapor and droplets from aerosolized jet fuels. Aerosol composition and concentrations were calculated from the differential between measured total (aerosol and gas-phase) and measured gas-phase concentrations. Total samples were collected directly, whereas gas-phase only samples were collected behind a glass fiber filter to remove droplets. All samples were collected for 1 min at 400 ml min−1 and quantified using thermal desorption–gas chromatography–mass spectrometry. This method was validated for the quantification of the vapor and droplet content from 4-h aerosolized jet fuel exposure to JP-8 and S-8 at total concentrations ranging from 200 to 1000 mg/m3. Paired samples (gas-phase only and total) were collected every ∼40 min. Calibrations were performed with neat fuel to calculate total concentration and also with a series of authentic standards to calculate specific compound concentrations. Accuracy was good when compared to an online GC-FID (gas chromatography–flame ionization detection) technique. Variability was 15% or less for total concentrations, the sum of all gas-phase compounds, and for most specific compound concentrations in both phases. Although validated for jet fuels, this method can be adapted to other hydrocarbon-based mixtures.

Characterization of a nose-only inhalation exposure system for hydrocarbon mixtures and jet fuels

A directed-flow nose-only inhalation exposure system was constructed to support development of physiologically based pharmacokinetic (PBPK) models for complex hydrocarbon mixtures, such as jet fuels. Due to the complex nature of the aerosol and vapor-phase hydrocarbon exposures, care was taken to investigate the chamber hydrocarbon stability, vapor and aerosol droplet compositions, and droplet size distribution. Two-generation systems for aerosolizing fuel and hydrocarbons were compared and characterized for use with either jet fuels or a simple mixture of eight hydrocarbons. Total hydrocarbon concentration was monitored via online gas chromatography (GC). Aerosol/vapor (A/V) ratios, and total and individual hydrocarbon concentrations, were determined using adsorbent tubes analyzed by thermal desorption–gas chromatography–mass spectrometry (TDS-GC-MS). Droplet size distribution was assessed via seven-stage cascade impactor. Droplet mass median aerodynamic diameter (MMAD) was between 1 and 3 μm, depending on the generator and mixture utilized. A/V hydrocarbon concentrations ranged from ∼200 to 1300 mg/m3, with between 20% and 80% aerosol content, depending on the mixture. The aerosolized hydrocarbon mixtures remained stable during the 4-h exposure periods, with coefficients of variation (CV) of less than 10% for the total hydrocarbon concentrations. There was greater variability in the measurement of individual hydrocarbons in the A-V phase. In conclusion, modern analytical chemistry instruments allow for improved descriptions of inhalation exposures of rodents to aerosolized fuel.

Synthesis of renewable jet and diesel fuels from 2-ethyl-1-hexene

An efficient method for the selective dimerization of the renewable feedstock, 2-ethyl-1-hexene, to a complex mixture of C16H32 hydrocarbons has been developed. To optimize the process, the activity of a variety of strongly acidic heterogeneous catalysts was investigated. Montmorillonite K-10 and sulfated zirconia readily isomerized 2-ethyl-1-hexene to a mixture of the cis- and trans isomers of 3-methyl-2-heptene and 3-methyl-3-heptene, but were inactive for the dimerization of 2-ethyl-1-hexene at temperatures up to 116 °C. In contrast, the cation exchange resins Amberlyst-15 and Nafion, readily dimerized 2-ethyl-1-hexene at elevated temperatures. For both sets of catalysts, the degree of hydration strongly affected the rate of isomerization/dimerization. After hydrogenation over PtO2 and fractional distillation, saturated dimer mixtures could be isolated in up to 90% yield. The dimers have a density of 0.78 g mL−1 and a freezing point <−60 °C, suggesting that they can be blended with renewable or conventional jet fuels, without adversely affecting the overall density and low temperature viscosity of the mixtures.