Using comprehensive two-dimensional gas chromatography for the analysis of oxygenates in middle distillates I. Determination of the nature of biodiesels blend in diesel fuel

In the current energetic context (increasing consumption of vehicle fuels, greenhouse gas emission etc.) government policies lead to mandatory introduction in fossil fuels of fuels resulting from renewable sources of energy such as biomass. Blending of fatty acid alkyl esters from vegetable oils (also known as biodiesel) with conventional diesel fuel is one of the solutions technologically available; B5 blends (up to 5%w/w esters in fossil fuel) are marketed over Europe. Therefore, for quality control as well as for forensic reasons, it is of major importance to monitor the biodiesel origin (i.e. the fatty acid ester distribution) and its content when it is blend with petroleum diesel. This paper reports a comprehensive two-dimensional gas chromatography (GC x GC) method that was developed for the individual quantitation of fatty acid esters in middle distillates matrices. Several first and the second dimension columns have been investigated and their performances to achieve (i) a group type separation of hydrocarbons and (ii) individual identification and quantitation of fatty acid ester blend with diesel are reported and discussed. Finally, comparison of quantitative GC x GC results with reference methods demonstrates the benefits of GC x GC approach which enables fast and reliable individual quantitation of fatty acid esters in one single run. Results show that under developed chromatographic conditions, quantitative group type analysis of hydrocarbons is also possible, meaning that simultaneous quantification of hydrocarbons and fatty acid esters can be achieved in one single run.     

Decomposition and hydrocarbon growth processes for esters in non-premixed flames

Biomass fuels are a promising renewable energy source, and so, the mechanisms that may produce toxic oxygenated byproducts and aromatic hydrocarbons from oxygenated hydrocarbons are of interest. Esters have the form R-(C=O)-O-R' and are components of biodiesel fuels. The five specific esters studied here are isomers of C5H10O2. The experiments were performed in atmospheric pressure coflowing methane/air non-premixed flames. A series of flames were generated by separately doping the fuel mixture with 5,000 ppm of each ester. This concentration is sufficiently large to produce measurable changes in intermediate hydrocarbon concentrations, yet small enough to not disturb the overall flame structure. Since the overall structure is not perturbed, the measured changes in the intermediate hydrocarbons can be directly attributed to the reactions of the esters. Analysis of these changes reveals that unimolecular six-centered dissociation is the primary decomposition pathway for the three esters with molecular arrangements capable of undergoing that mechanism. The remaining two esters exhibited decomposition rates and products that are consistent with simple fission as the dominant decomposition mechanism, though we do not exclude other pathways from playing a significant role in their decomposition. All of the esters produce aromatic hydrocarbons at higher rates than the undoped fuel, and the molecular arrangement of the ester isomers plays a role in the degree of aromatic formation. Isomer variations also influence the type and quantity of toxic oxygenates that are produced in the flames.     

Method development for fingerprinting of biodiesel blends by solid-phase extraction and gas chromatography-mass spectrometry

A method based on the combination of solid-phase extraction (SPE) with gas chromatography-mass spectrometry (GC/MS) for detailed chemical fingerprinting of biodiesel/petrodiesel blends was developed in the present study. Forensic identification, commonly referred to as chemical fingerprinting, is based on the relative distributions of individual aliphatic hydrocarbons, aromatic hydrocarbons, fatty acid alkyl esters, and free sterols. Fractionation of fuel samples is optimized for the separation of fatty acid esters and free sterols from petroleum hydrocarbons into four fractions: aliphatic, aromatic, fatty acid ester, and polar components. The final recoveries of aliphatic and aromatic hydrocarbons were determined to be in the range of 65-103%, 73-105% for FAMEs, and 78-103% for free sterols in the polar fraction. Excellent separation with negligible crossover of components with different polarities between fractions was observed. Quantitative analysis of blend levels and individual chemical distribution were achieved. The method has great potential for the identification of biodiesel in diesel fuel blends and could form the basis of a method for characterization of biodiesel-contaminated environmental samples.     

Procedure for and results of simultaneous determination of aromatic hydrocarbons and fatty acid methyl esters in diesel fuels by high performance liquid chromatography

The content of aromatic hydrocarbons in diesel fuels is regulated by appropriate standards, and a further reduction in the allowed concentration of these hazardous substances in these fuels is expected. The content of aromatic hydrocarbons in diesel fuels is most often determined using standard methods EN-12916 or ASTM D-6591. The content of polycyclic aromatic hydrocarbons (PAHs) is determined from a single peak obtained using normal phase high-performance liquid chromatography (NP-HPLC), a column of the NH2 type, n-heptane as the eluent, refractive index detector (RID) and backflushing of the eluent. However, the methods mentioned above cannot be applied when the fuel contains fatty acid methyl esters (FAME), which lately has become more common. The content of FAME in diesel oils is determined using mid-IR spectrophotometry based on the absorption of carbonyl group. However, no standard procedure for the determination of classes of aromatic hydrocarbons in diesel fuels containing FAME is yet available. The present work describes such a modification of methods EN-12916/ASTM D-6591 that provides a simultaneous determination of individual groups of aromatic hydrocarbons, total content of polycyclic aromatic hydrocarbons and the FAME content in diesel fuels. The refractive index detector (RID) and n-heptane as the mobile phase are still used, but backflushing of the eluent is applied after the elution of all polycyclic aromatic hydrocarbons. Additionally, ultraviolet diode array detection is used for the exact determination of low contents of polycyclic aromatic hydrocarbons and to confirm the presence of FAME in the analyzed fuel.     

Quantification of trace fatty acid methyl esters in diesel fuel by using multidimensional gas chromatography with electron and chemical ionization mass spectrometry

Measurement of contamination of marine and naval diesel fuels (arising from product mixing or adulteration) with biodiesel or fatty acid methyl esters can be problematic, especially at very low levels. A suitable solution for this task for trace amounts of individual fatty acid methyl esters with resolution and quantification can be achieved by using a multidimensional gas chromatographic approach with electron and chemical ionization mass spectrometric detection. A unique column set comprising a 100 m methyl‐siloxane nonpolar first dimension column and high‐temperature ionic liquid column in the second dimension enabled identification of individual fatty acid methyl esters at below the lowest concentrations required to be reported in a diesel fuel matrix. Detection limits for individual fatty acid methyl esters compounds ranged from 0.5 to 5.0 mg/L, with excellent linearity up to 5000 mg/L and repeatability of the method from 1.3 to 3.2%. The method was applied to the analysis of diesel fuel samples with suspected biodiesel contamination. Contamination at 568 mg/L was calculated for an unknown sample and interpretation of the results permitted the determination of a likely source of the contamination.     

Reduced Kinetic Schemes of Complex Reaction Systems: Fossil and Biomass‐Derived Transportation Fuels

The kinetic modeling of the pyrolysis and combustion of liquid transportation fuels is a very complex task for two different reasons: the challenging characterization of the complex mixture of several hydrocarbon isomers and the complexity of the oxidation mechanisms of large hydrocarbon and oxygenated molecules. While surrogate mixtures of reference components allow to tackle the first difficulty, the complex behavior of the oxidation mechanisms is mostly overcome by reducing the total number of involved species by adopting a lumping approach. After a first investigation of the different liquid fuels (gasoline, kerosene, and diesel fuels), a short discussion on the lumping techniques allows to highlight the advantages of this approach. The lumped POLIMI pyrolysis and oxidation mechanism of hydrocarbon and oxygenated fuels is then used for generating several skeletal mechanisms for typical surrogate mixtures, moving from pure n‐heptane up to heavy diesel fuels. These skeletal models are simply reduced with a reaction flux analysis, and they involve between 100 and 200 species. While these sizes already allow detailed computational fluid dynamics (CFD) calculations in internal combustion engines, further reduction phases are necessary when the interest is toward more complex CFD computations. To maintain the standard structure of the skeletal mechanisms, successive reduction phases are not considered. Moreover, new regulations pushed toward a greater use of renewable fuels. For these reasons, the skeletal models are also extended to biogasolines including methanol, ethanol, and n‐butanol. Similarly, skeletal models of diesel and biodiesel fuels, including methyl esters, are also provided. Several comparisons with experimental data and complete validations in the operating range of internal combustion engines are also reported. The whole set of comparisons with experimental data obtained in a wide range of conditions not only validate the reduced models of specific transportation fuels but also the complete kinetic scheme POLIMI_1404.     

Cetane number and thermal properties of vegetable oil,biodiesel, 1-butanol and diesel blends

Vegetable oil derived fuels for diesel engines are becoming important as alternative to petroleum diesel fuels due to their environmental friendliness and availability. Ignition quality in compression ignition (CI) engines is influenced by thermal characteristics and fuel properties. In this study, the effects of vegetable oil transesterification and vegetable oil–1-butanol-diesel blends on fuel properties, cetane number (CN) and thermal characteristics were experimentally investigated. Methyl esters (biodiesel) and 10% vegetable oil–10% 1-butanol–80% diesel blends were prepared from croton oil (CRO), coconut oil (COO) and jatropha oil (JAO). CN was measured in a CFR F-5 engine, and a thermogravimetric analysis (TG), as well as the determination of fuel properties of vegetable oils, biodiesels and blends was carried out. It can be observed for vegetable oils that they possess low volatility characteristics, low CN and high viscosity different from those of biodiesels, blends and diesel fuel. It was observed that biodiesels and blends exhibit similarities with diesel in the fuel characteristics, CN and TG curves.     

Analysis of biodiesel/petroleum diesel blends with comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GCxGC) is used to analyze petroleum diesel, biodiesel, and biodiesel/petroleum diesel blends. The GCxGC instrument is assembled from a conventional gas chromatograph fitted with a simple, in-line fluidic modulator. A 5% phenyl polydimethylsiloxane primary column is coupled to a polyethylene glycol secondary column. This column combination generates chromatograms where the fatty acid methyl esters (FAMEs) found in biodiesel occupy a region that is also populated by numerous cyclic alkanes and monoaromatics found in petroleum. Fortunately, the intensities of the petroleum hydrocarbon peaks are far lower than the intensities of the FAME peaks, even for blends with low biodiesel content. This allows the FAMEs to be accurately quantitated by direct integration. The method is calibrated by analyzing standard mixtures of soybean biodiesel in petroleum diesel with concentrations ranging from 1 to 20% v/v. The resulting calibration curve displays excellent linearity. This curve is used to determine the concentration of a B20 biodiesel/petroleum diesel blend obtained from a local retailer. Excellent precision and accuracy are obtained.     

Catalysts on the basis of anion-modified metal oxides for production of ecologically pure components of motor fuels

Experimental evidence on the production, structure, and physiochemical properties of aluminum, zirconium, and titanium oxides modified with halides, sulfates, and boron and tungsten oxides. Information on the application of anion-modified metal oxides as catalysts in the production of ecologically pure components of motor fuels, with decreased contents of aromatic hydrocarbons and sulfur compounds. Therewith, along with traditional hydrocarbon oligomerization, isomerization, alkylation reactions, actual arene hydroisomerization processes and production of diesel fuels from vegetable materials are considered.     

Determination of methyl ester contents in biodiesel blends by FTIR-ATR and FTNIR spectroscopies

Partial last square regression (PLS) and artificial neural network (ANN) combined to FTIR-ATR and FTNIR spectroscopies have been used to design calibration models for the determination of methyl ester content (%, w/w) in biodiesel blends (methyl ester + diesel). Methyl esters were obtained by the methanolysis of soybean, babassu, dende, and soybean fried oils. Two sets of samples have been used: Group I, binary mixtures (diesel + one kind of methyl ester), corresponding to 96 biodiesel blends (0–100%, w/w), and Group II, quaternary mixtures (diesel + three types of methyl esters), corresponding to 60 biodiesel blends (0–100%, w/w). The PLS results have shown that the FTNIR model for Group I is more precise and accurate (±0.02 and ±0.06%, w/w). In the case of Group II the PLS models (FTIR-ATR and FTNIR) have shown the same accuracies, while the ANN/FTNIR models has presented better performance than the ANN/FTIR-ATR models. The best accuracy was achieved by the ANN/FTNIR model for diesel determination (0.14%, w/w) while the worthiest was that of dende ANN/FTIR-ATR model (0.6%, w/w). Precisions in Group II analysis ranged from 0.06 to 0.53% (w/w) and coefficients of variation were better than 3% indicating that these models are suitable for the determination of diesel–biodiesel blends composed of methyl esters derived from different vegetable oils.     

Analytical characterization of the persistent residues after microbial degradation of mineral oils

The residual fractions remaining after microbial degradation of diesel fuel, different deparaffinized raffinates and extracts from long-term contaminated soils were analyzed by liquid chromatography, gas chromatography, infrared spectrometry and mass spectrometry. The quantity of saturated hydrocarbons decreased after the microbial treatment, whereas the portion of polar compounds increased. The total content of aromatics changed only insignificantly. n-Paraffins < C26 were found to be no longer present in mineral oils degraded to exhaustion. Infrared spectrometry revealed oxygen compounds in the residues, mainly ketones, fatty acids and esters. Elementary analysis confirms the presence of nitrogen, oxygen and sulphur compounds in the degraded products. The gas chromatograms of high boiling oils, as well as of residues and extracts, consist mainly of a large base envelope (about 95% of the total area); thus gc/ms coupling reaches the limits of its applicability. However, mass spectrometry with direct inlet gives valuable information regarding hydrocarbon type analysis. The results revealed the preferable degradation of alkanes, 1-ring aliphatics and benzenes and an enrichment of condensed cycloaliphatics and aromatics. The latter compounds are known to be resistant to microbial attack.     

Characterization of fuel samples by on-line LC-GC with automatic group-type separation of hydrocarbons

Characterization of fuels by LC-GC is possible by use of automatic successive transfer (multiple transfer) of HPLC fractions to a GC via an on-column interface. This paper describes the instrumentation and the methodology for the HPLC separation of the hydrocarbons (aliphatic and aromatic) into separate groups and the on-line transfer of these groups to a capillary GC column. Two HPLC methods were used with the same valve configuration: single column (silica) with column back-flush to detector; and double column (silica and amino-bonded silica) with multiple fraction transfer and back-flush. The first method was used for the analysis of total saturated compounds and total aromatic compounds; the second was used for the separation of the one-, two-, three-, and four-ring aromatic compounds present in diesel fuels. Examples are shown of the characterization of diesel fuels, and the repeatability of the data.     

Electrochemical Determination of Organic Compounds in Automotive Fuels

This article critically reviews the electroanalytical methods devoted for the determination of organic compounds in automotive fuels that can range from contaminants to additives typically introduced into liquid biofuels and liquid fossil fuels. Contaminants such as aldehydes and ketones in bioethanol, free fatty acids and glycerol in biodiesel, and sulfur and nitrogen organic compounds in gasoline and diesel fuel, and additives such as colour markers and antioxidants added to fuels were determined by electroanalytical methods. Special focus is given to electrodes, electrochemical techniques, and sample preparation strategies. Future directions of research on electroanalysis of liquid fuels are presented.     

Soybean biodiesel methyl esters,free glycerin and acid number quantification by 1H nuclear magnetic resonance spectroscopy

Production of alternative fuels, such as biodiesel, from transesterification of vegetable oil driven by heterogeneous catalysts is a promising alternative to fossil diesel. However, achieving a successful substitution for a new renewable fuel depends on several quality parameters. ¹H NMR spectroscopy was used to determine the amount of methyl esters, free glycerin and acid number in the transesterification of soybean oil with methanol in the presence of hydrotalcite‐type catalyst to produce biodiesel. Reaction parameters, such as temperature and time, were used to evaluate soybean oil methyl esters rate conversion. Temperatures of 100 to 180 °C and times of 20 to 240 min were tested on a 1 : 12 molar ratio soybean oil/methanol reaction. At 180 °C/240 min conditions, a rate of 94.5 wt% of methyl esters was obtained, where free glycerin and free fatty acids were not detected. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of environmental benign biolubricant from wild castor seed by reactive extraction and optimization

Castor oil alkyl esters are a possible biolubricant since they contain 90% hydroxyl fatty acid, which improves the oil's lubricity. Due to the limitations of the conventional approach, castor oil propyl ester (COPE) from wild castor seed was synthesized by reactive extraction. The factors influencing yield of reaction was optimised by response surface methodology to obtain a high yield. The influence of amount of catalyst, propanol to oil proportion, temperature, and rotating speed on castor oil propyl ester yield was investigated using a central composite design.The optimised reaction condition is propanol to oil molar proportion of 275: 1 with 1.5 wt% of catalyst loading at 90 °C and rotating speed of 450 rpm with COPE yield of 78.6% in 3hrs. Physico-chemical properties of alkyl esters were determined. COPE can be employed as a bioadditive to ultra-low sulphur diesel fuels due to its high lubricity.     

Hyphenation of a carbon analyzer to photo-ionization mass spectrometry to unravel the organic composition of particulate matter on a molecular level

The carbonaceous fraction of airborne particulate matter (PM) is of increasing interest due to the adverse health effects they are linked to. Its analytical ascertainment on a molecular level is still challenging. Hence, analysis of carbonaceous fractions is often carried out by determining bulk parameters such as the overall content of organic compounds (OC) and elemental carbon (EC) as well as the total carbon content, TC (sum of OC and EC), however, no information about the individual substances or substance classes, of which the single fractions consist can be obtained. In this work, a carbon analyzer and a photo-ionization time-of-flight mass spectrometer (PI-TOF-MS) were hyphenated to investigate individual compounds especially from the OC fractions. The carbon analyzer enables the stepwise heating of particle samples and provides the bulk parameters. With the PI-TOF-MS, it is possible to detect the organic compounds released during the single-temperature steps due to soft ionization and fast detection of the molecular ions. The hyphenation was designed, built up, characterized by standard substances, and applied to several kinds of samples, such as ambient aerosol, gasoline, and diesel emission as well as wood combustion emission samples. The ambient filter sample showed a strong impact of wood combustion markers. This was revealed by comparison to the product pattern of the similar analysis of pure cellulose and lignin and the wood combustion PM. At higher temperatures (450 °C), a shift to smaller molecules occurred due to the thermal decomposition of larger structures of oligomeric or polymeric nature comparable to lignocelluloses and similar oxygenated humic-like substances. Finally, particulate matter from gasoline and diesel containing 10% biodiesel vehicle exhaust has been analyzed. Gasoline-derived PM exhibited large polycyclic aromatic hydrocarbons, whereas diesel PM showed a much higher total organic content. The detected pattern revealed a strong influence of the biodiesel content on the nature of the particulate organic material.     

Multivariate near infrared spectroscopy models for predicting the methyl esters content in biodiesel

Biodiesel is the main alternative to fossil diesel. The key advantages of its use are the fact that it is a non-toxic renewable resource, which leads to lower emissions of polluting gases. European governments are targeting the incorporation of 20% of biofuels in the general fuels until 2020.Chemically, biodiesel is a mixture of fatty acid methyl esters, derived from vegetable oils or animal fats, which is usually produced by a transesterification reaction, where the oils/fats react with an alcohol, in the presence of a catalyst. The European Standard (EN 14214) establishes 25 parameters that have to be analysed to certify biodiesel quality and the analytical methods that should be used to determine those properties.This work reports the use of near infrared (NIR) spectroscopy to determine the esters content in biodiesel as well as the content in linolenic acid methyl esters (C18:3) in industrial and laboratory-scale biodiesel samples. Furthermore, calibration models for myristic (C14:0), palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2) acid methyl esters were also obtained. Principal component analysis was used for the qualitative analysis of the spectra, while partial least squares regression was used to develop the calibration models between analytical and spectral data. The results confirm that NIR spectroscopy, in combination with multivariate calibration, is a promising technique to assess the biodiesel quality control in both laboratory-scale and industrial scale samples.     

Production of High-Density Jet and Diesel Fuels by Hydrogenation of Highly Aromatic Fractions

Physicochemical characteristics and hydrocarbon composition of highly aromatic wastes (light gas oil from catalytic cracking, pyrolysis tar, coal tar, coal gasification tar) as a feedstock for producing high-density jet fuels are considered. The hydrogenation reactions of polycyclic aromatic hydrocarbons, including mixtures of hydrocarbons with different numbers of rings, are described. Catalysts for hydrogenation of highly aromatic waste to obtain fuel fractions are considered. Particular attention is paid to catalyst deactivation in the course of processing of this feedstock. A separate section deals with the choice and implementation of procedures for processing highly aromatic feedstock to obtain jet and diesel fuels.     

Forensic identification of spilled biodiesel and its blends with petroleum oil based on fingerprinting information

A case study is presented for the forensic identification of several spilled biodiesels and its blends with petroleum oil using integrated forensic oil fingerprinting techniques. The integrated fingerprinting techniques combined SPE with GC/MS for obtaining individual petroleum hydrocarbons (aliphatic hydrocarbons, polyaromatic hydrocarbons and their alkylated derivatives and biomarkers), and biodiesel hydrocarbons (fatty acid methyl esters, free fatty acids, glycerol, monoacylglycerides, and free sterols). HPLC equipped with evaporative scattering laser detector was also used for identifying the compounds that conventional GC/MS could not finish. The three environmental samples (E1, E2, and E3) and one suspected source sample (S2) were dominant with vegetable oil with high acid values and low concentration of fatty acid methyl ester. The suspected source sample S2 was responsible for the three spilled samples although E1 was slightly contaminated by petroleum oil with light hydrocarbons. The suspected source sample S1 exhibited with the high content of glycerol, low content of glycerides, and high polarity, indicating its difference from the other samples. These samples may be the separated byproducts in producing biodiesel. Canola oil source is the most possible feedstock for the three environmental samples and the suspected source sample S2.     

Isomer-specific fuel destruction pathways in rich flames of methyl acetate and ethyl formate and consequences for the combustion chemistry of esters

The influences of fuel-specific destruction pathways on flame chemistry are determined for two isomeric ester fuels, methyl acetate, CH3(CO)OCH3, and ethyl formate, H(CO)OC2H5, used as model representatives for biodiesel compounds, and their potential for forming air pollutants is addressed. Measurements are presented of major and intermediate species mole fractions in premixed, laminar flat flames using molecular-beam sampling and isomer-selective VUV-photoionization mass spectrometry. The observed intermediate species concentrations depend crucially on decomposition of the different radicals formed initially from the fuels. The methyl acetate structure leads to preferential formation of formaldehyde, while the ethyl formate isomer favors the production of acetaldehyde. Ethyl formate also yields higher concentrations of the C2 species (C2H2 and C2H4) and C4 species (C4H2 and C4H4). Benzene concentrations, while larger for ethyl formate, are at least an order of magnitude smaller for both flames than seen for simple hydrocarbon fuels (ethylene, ethane, propene, and propane).