Biodiesel is a renewable fuel alternative to petroleum Diesel, biodiesel has similar characteristic but with lesser exhaust emission. In this study, transesterification of Karaya oil is examined experimentally using a batch reactor at 100-140°C and 5 bar in subcritical methanol conditions, residence time from 10 to 20 minutes, using a mass ratio 6 methanol-to-vegetable oil. Methanol is used for alcoholysis and sodium hydroxide as a catalyst. Experiments varied the temperature and pressure, observing the effect on the yield and reaction time. In addition, biodiesel from corn oil was created and compared to biodiesel from karaya oil. Kinetic model proposed. The model estimates the concentration of triglycerides, diglycerides, monoglycerides and methyl esters during the reaction. The experiments are carried out at temperatures of 100°C and above. The conversion rate and composition of methyl esters produced from vegetable oils are determined by Gas Chromatography Analysis. It was found that the higher the temperature, the higher reaction rate. Highest yield is 97% at T=140°C achieved in 13 minutes, whereas at T=100°C yield is 68% in the same time interval. Ignition Quality Test (IQT) was utilized for determination of the ignition delay time (IDT) inside a combustion chamber. From the IDT cetane number CN inferred. In case of corn oil biodiesel, the IDT = 3.5 mS, leading to a CN = 58. Whereas karaya oil biodiesel showed IDT = 2.4 mS, leading to a CN = 97. The produced methyl esters were also characterized by measurements of viscosity (υ), density (ρ), flash point (FP) and heat of combustion (HC). The following properties observed: For corn biodiesel, υ = 8.8 mPa-s, ρ = 0.863 g/cm3, FP = 168.8 °C, and HC = 38 MJ/kg. For karaya biodiesel, υ = 10 mPa-s, ρ = 0.877 g/cm3, FP = 158.2 °C, and HC = 39 MJ/kg.

In this research, two-stage hydrotreating of bitumen-derived light gas oil (LGO) from Athabasca oil sands was studied. The objective was to catalytically upgrade the LGO by reducing the aromatics content and enhancing the cetane content via inter-stage removal of hydrogen sulfide. The impact of hydrogen sulfide inhibition on aromatics hydrogenation (HDA), hydrodenitrogenation (HDN) and hydrodesulfirization (HDS) activities was investigated. Experiments for this study were carried out in a trickle-bed reactor loaded with commercial NiMo/Al2O3 and lab-prepared NiW/Al2O3 in the stage I and stage II reactors, respectively. Temperature was varied from 350 to 390 oC at the optimum LHSV and pressure conditions of 0.6 h-1 and 11.0 MPa, respectively. The results from two-stage process showed significant improvement in HDA, cetane rating and HDS activities compared to the single-stage process after the inter-stage removal of hydrogen sulfide. Hence, the presence of hydrogen sulfide in the reaction retarded both the HDA and HDS processes in the single-stage operation. Negligible hydrogen sulfide inhibition was however, observed in the HDN process. <p>Prior to the two-stage hydrotreating study, single-stage hydrotreating reactions were carried out over commercial NiMo/Al2O3 catalyst to determine the optimum operating conditions for maximizing hydrogenation of aromatics. A statistical approach via the Analysis of Variance (ANOVA) technique was used to develop regression models for predicting the conversion of aromatics, sulfur and nitrogen in the LGO feed. Experiments were performed at the following operating conditions: temperature (340-390 oC); pressure (6.9-12.4 MPa) and liquid hourly space velocity, LHSV (0.5-2.0 h-1). Hydrogen-to-oil ratio was maintained constant at 550 ml/ml. The results showed that the two-level interaction between temperature and pressure was the only significant interaction parameter affecting HDA while interaction between temperature and LHSV was the most important parameter affecting both HDS and HDN activities. A maximum 63 % HDA was obtained at 379 oC, 11.0 MPa and 0.6 h-1. Experiments with NiW/Al2O3 were also performed in a single-stage reactor with LGO blend feedstock by varying temperature from 340-390 oC at the optimum pressure and space velocity of 11.0 MPa and 0.6 h-1, respectively. The following order of ease of hydrogenation was observed: poly- > di- >> monoaromatics. The order of ease of hydrogenation in other LGO feedstocks (atmospheric light gas oil, ALGO; hydrocrack light gas oil, HLGO; and vacuum light gas oil, VLGO) was studied and found to follow the order: VLGO > ALHO > HLGO. Studies on mild hydrocracking (MHC) in the gas oil feedstocks showed a net increase in gasoline with a corresponding decrease in diesel with increasing temperature. <p>Both the single and two-stage HDA and HDS kinetics were modeled using Langmuir-Hinshelwood rate equations. These models predicted the experimental data with reasonable accuracy. The degree of conversion of the gas oil fractions in ALGO, HLGO and VLGO via mild hydrocracking was best described by a pseudo-first order kinetic model based on a parallel conversion scheme.

In this research, two-stage hydrotreating of bitumen-derived light gas oil (LGO) from Athabasca oil sands was studied. The objective was to catalytically upgrade the LGO by reducing the aromatics content and enhancing the cetane content via inter-stage removal of hydrogen sulfide. The impact of hydrogen sulfide inhibition on aromatics hydrogenation (HDA), hydrodenitrogenation (HDN) and hydrodesulfirization (HDS) activities was investigated. Experiments for this study were carried out in a trickle-bed reactor loaded with commercial NiMo/Al2O3 and lab-prepared NiW/Al2O3 in the stage I and stage II reactors, respectively. Temperature was varied from 350 to 390 oC at the optimum LHSV and pressure conditions of 0.6 h-1 and 11.0 MPa, respectively. The results from two-stage process showed significant improvement in HDA, cetane rating and HDS activities compared to the single-stage process after the inter-stage removal of hydrogen sulfide. Hence, the presence of hydrogen sulfide in the reaction retarded both the HDA and HDS processes in the single-stage operation. Negligible hydrogen sulfide inhibition was however, observed in the HDN process. <p>Prior to the two-stage hydrotreating study, single-stage hydrotreating reactions were carried out over commercial NiMo/Al2O3 catalyst to determine the optimum operating conditions for maximizing hydrogenation of aromatics. A statistical approach via the Analysis of Variance (ANOVA) technique was used to develop regression models for predicting the conversion of aromatics, sulfur and nitrogen in the LGO feed. Experiments were performed at the following operating conditions: temperature (340-390 oC); pressure (6.9-12.4 MPa) and liquid hourly space velocity, LHSV (0.5-2.0 h-1). Hydrogen-to-oil ratio was maintained constant at 550 ml/ml. The results showed that the two-level interaction between temperature and pressure was the only significant interaction parameter affecting HDA while interaction between temperature and LHSV was the most important parameter affecting both HDS and HDN activities. A maximum 63 % HDA was obtained at 379 oC, 11.0 MPa and 0.6 h-1. Experiments with NiW/Al2O3 were also performed in a single-stage reactor with LGO blend feedstock by varying temperature from 340-390 oC at the optimum pressure and space velocity of 11.0 MPa and 0.6 h-1, respectively. The following order of ease of hydrogenation was observed: poly- > di- >> monoaromatics. The order of ease of hydrogenation in other LGO feedstocks (atmospheric light gas oil, ALGO; hydrocrack light gas oil, HLGO; and vacuum light gas oil, VLGO) was studied and found to follow the order: VLGO > ALHO > HLGO. Studies on mild hydrocracking (MHC) in the gas oil feedstocks showed a net increase in gasoline with a corresponding decrease in diesel with increasing temperature. <p>Both the single and two-stage HDA and HDS kinetics were modeled using Langmuir-Hinshelwood rate equations. These models predicted the experimental data with reasonable accuracy. The degree of conversion of the gas oil fractions in ALGO, HLGO and VLGO via mild hydrocracking was best described by a pseudo-first order kinetic model based on a parallel conversion scheme.

Six ã-Al2O3 supported metallic nitride and carbide catalysts were chosen for a scouting test for the production of a diesel fuel cetane enhancer from canola oil. The six catalysts chosen for study were ã-Al2O3 supported molybdenum (Mo) carbide and nitride, tungsten (W) carbide and nitride, and vanadium (V) nitride and carbide. All six catalysts were prepared by the impregnation method and characterized using various techniques. The six catalysts were screened for their affinity for oxygen removal, fatty acid conversion, alkane/olefin selectivity, hydrogen consumption, and gas-by product production from oleic acid. The scouting test was carried out at a reaction temperature of 390°C, a LHSV of 0.46 hr-1, and elevated hydrogen partial pressures of greater than 7000 kPa, in a laboratory microreactor in an upflow configuration. The scouting test revealed that the two molybdenum catalysts performed the best with oxygen removal near 100% and alkane/olefin content of greater than 30%. <p>Next, the supported molybdenum carbide and nitride catalysts were compared against one another over a wider range of operating conditions. A temperature range of 380 390°C, a LHSV range of 0.64 1.28 hr-1, and a hydrogen partial pressure of 7100 kPa were used. Both catalysts had the same metal loading of 7.4 wt% molybdenum. The two catalysts were compared on the basis of oxygen removal, alkane/olefin selectivity, diesel fuel selectivity, and hydrogen consumption, while using both triolein and canola oil as the feed. It was found that the supported molybdenum nitride was the superior choice for this process, specifically when using the more complex canola oil feed. The supported molybdenum nitride catalyst delivered oxygen removal of greater than 85%, alkane/olefin selectivity of greater than 20%, and diesel fuel selectivity of greater than 40%, for all conditions studied. <p>Finally, a preliminary catalyst and process optimization was carried out on the chosen ã-Al2O3 supported molybdenum nitride catalyst. The catalyst optimization consisted of varying the metal loading of the catalyst from 7.4 wt% to 22.7 wt%. The catalysts were examined over a temperature range of 390 410°C, a LHSV range of 0.9 1.2 hr-1, and a hydrogen partial pressure of 8300 kPa, with canola oil as the chosen feed. It was found that the increase in molybdenum loading on the catalyst delivered an average increase in the alkane/olefin selectivity of 43.2% and an average increase in the diesel fuel selectivity of 5.3 %. The process optimization studied a temperature range of 390 410°C, a LHSV range of 0.6 1.2 hr-1, and a hydrogen partial pressure range of 7800 - 8900 kPa, with canola oil as the chosen feed. Within the limits of the design, it was found that the optimum operating conditions were 395°C, 1.05 hr-1, and 8270 kPa. At these conditions the predicted yields of alkane/olefin products and diesel fuel are 47.3 and 50.5 g/100g liquid fed, respectively.

Six ã-Al2O3 supported metallic nitride and carbide catalysts were chosen for a scouting test for the production of a diesel fuel cetane enhancer from canola oil. The six catalysts chosen for study were ã-Al2O3 supported molybdenum (Mo) carbide and nitride, tungsten (W) carbide and nitride, and vanadium (V) nitride and carbide. All six catalysts were prepared by the impregnation method and characterized using various techniques. The six catalysts were screened for their affinity for oxygen removal, fatty acid conversion, alkane/olefin selectivity, hydrogen consumption, and gas-by product production from oleic acid. The scouting test was carried out at a reaction temperature of 390°C, a LHSV of 0.46 hr-1, and elevated hydrogen partial pressures of greater than 7000 kPa, in a laboratory microreactor in an upflow configuration. The scouting test revealed that the two molybdenum catalysts performed the best with oxygen removal near 100% and alkane/olefin content of greater than 30%. <p>Next, the supported molybdenum carbide and nitride catalysts were compared against one another over a wider range of operating conditions. A temperature range of 380 390°C, a LHSV range of 0.64 1.28 hr-1, and a hydrogen partial pressure of 7100 kPa were used. Both catalysts had the same metal loading of 7.4 wt% molybdenum. The two catalysts were compared on the basis of oxygen removal, alkane/olefin selectivity, diesel fuel selectivity, and hydrogen consumption, while using both triolein and canola oil as the feed. It was found that the supported molybdenum nitride was the superior choice for this process, specifically when using the more complex canola oil feed. The supported molybdenum nitride catalyst delivered oxygen removal of greater than 85%, alkane/olefin selectivity of greater than 20%, and diesel fuel selectivity of greater than 40%, for all conditions studied. <p>Finally, a preliminary catalyst and process optimization was carried out on the chosen ã-Al2O3 supported molybdenum nitride catalyst. The catalyst optimization consisted of varying the metal loading of the catalyst from 7.4 wt% to 22.7 wt%. The catalysts were examined over a temperature range of 390 410°C, a LHSV range of 0.9 1.2 hr-1, and a hydrogen partial pressure of 8300 kPa, with canola oil as the chosen feed. It was found that the increase in molybdenum loading on the catalyst delivered an average increase in the alkane/olefin selectivity of 43.2% and an average increase in the diesel fuel selectivity of 5.3 %. The process optimization studied a temperature range of 390 410°C, a LHSV range of 0.6 1.2 hr-1, and a hydrogen partial pressure range of 7800 - 8900 kPa, with canola oil as the chosen feed. Within the limits of the design, it was found that the optimum operating conditions were 395°C, 1.05 hr-1, and 8270 kPa. At these conditions the predicted yields of alkane/olefin products and diesel fuel are 47.3 and 50.5 g/100g liquid fed, respectively.

The Homogeneous Charge Compression Ignition (HCCI) engine is a promising engine concept that emits low concentrations of NOx and particulates and still has a high efficiency. Since the charge is auto-ignited, the auto-ignition quality of the fuel is of major importance. It has been shown in several studies that neither of the classical measures of auto-ignition quality of gasoline-like fuels, RON and MON, can alone describe this in all conditions in HCCI combustion. However, even in such cases it is possible to combine RON and MON into an octane index, OI, that describes the auto-ignition quality well in most conditions. The octane numbers are combined into the OI with the variable K according to the following equation: OI = (1-K)RON + K MON = RON – K S The OI of a sensitive fuel is the equivalent of the octane number of a primary reference fuel with the same resistance to auto-ignition in the tested condition. The K-value is dependent on the temperature and pressure history. A generic parameter Tcomp15, the temperature at 15 bar during the compression, was introduced to describe the temperature and pressure history. It was found that the K-value increases with increasing Tcomp15 and two linear equations have been suggested to describe this relationship. At high or low Tcomp15 it has been found that the sensitivity of the fuel octane quality on combustion phasing is small and the auto-ignition quality defined by the OI scale does no longer play a big role. NO affects the combustion phasing of gasoline-like fuels. This effect is most significant at low concentration where it advances the combustion phasing considerably. At higher conditions its influence is different for different fuels. A sensitive fuel is considered a good HCCI fuel since its OI changes in the same direction as the octane requirement of the engine, which would make the engine management easier. It is also likely that a sensitive fuel will enable a wider operating range. The auto-ignition quality of diesel-like fuels was studied in tests with three different strategies of mixture formation. In these tests it was found that the ignition delay increased with lower cetane number and that the cetane number described the auto-ignition quality well, even for fuels of significantly different physical properties. The experiments were, however, made at a limited range of operating conditions and low load. A good diesel-like HCCI fuel should be easy to vaporize to facilitate homogeneity. It should have a high resistance to auto-ignition, not necessarily the highest, one that allows both high and low loads at a given compression ratio. Finally, it should also function well with the injection system without a significant decrease in injection system life length. / QC 20100917

Experimental measurement of fuel properties are expensive, require sophisticated instrumentation and are time consuming. Mathematical models and approaches for predicting fuel properties can help reduce time and costs. A new approach for characterizing petroleum fuels called the functional group approach was developed by disassembling the innumerable fuel molecules into a finite number of molecular fragments or ‘functional groups’. This thesis proposes and tests the following hypothesis, Can a fuels functional groups be used to predict its combustion properties? Analytical techniques like NMR spectroscopy that are ideally suited to identify and quantify the various functional groups present in the fuels was used. Branching index (BI), a new parameter that quantifies the degree and quality of branching in a molecule was defined. The proposed hypothesis was tested on three classes of fuels namely gasolines, diesel and heavy fuel oil. Five key functional groups namely paraffinic CH3, paraffinic CH2, paraffinic CH, naphthenic CH-CH2 and aromatic C-CH groups along with BI were used as matching targets to formulate simple surrogates of one or two molecules that reproduce the combustion characteristics. Using this approach, termed as the minimalist functional group (MFG) approach surrogates were formulated for a number of standard gasoline, diesel and jet fuels. The surrogates were experimentally validated using measurements from Ignition quality tester (IQT), Rapid compression machine (RCM) and smoke point (SP) apparatus. The functional group approach was also employed to predict research octane number (RON) and motor octane number (MON) of fuels blended with ethanol using artificial neural networks (ANN). A multiple linear regression (MLR) based model for predicting derived cetane number (DCN) of hydrocarbon fuels was also developed. The functional group approach was also extended to study heavy fuel oil (HFO), a viscous residual fuel that contains heteroatoms like S, N and O. It is used in ships as marine fuel and also in boilers for electricity generation. 1H NMR and 13C NMR measurements were made to analyze the average molecular parameters (AMP) of HFO molecules. The fuel was divided into 19 different functional groups and their concentrations were calculated from the AMP values. A surrogate molecule that represents the average structure of HFO was then formulated and its properties were predicted using QSPR approaches.

To optimize biodiesel manufacturing, many reported studies have built simulation models to quantify the relationship between operating conditions and process performance. For mass and energy balance simulations, it is essential to know the four fundamental thermophysical properties of the feed oil: liquid density (Ï L), vapor pressure (Pvap), liquid heat capacity (CpL), and heat of vaporization (Î Hvap). Additionally, to characterize the fuel qualities, it is critical to develop quantitative correlations to predict three biodiesel properties, namely, viscosity, cetane number, and flash point. Also, to ensure the operability of biodiesel in cold weather, one needs to quantitatively predict three low-temperature flow properties: cloud point (CP), pour point (PP), and cold filter plugging point (CFPP). This article presents the results from a comprehensive evaluation of the methods for predicting these four essential feed oil properties and six key biodiesel fuel properties. We compare the predictions to reported experimental data and recommend the appropriate prediction methods for each property based on accuracy, consistency, and generality. Of particular significance are (1) our presentation of simple and accurate methods for predicting the six key fuel properties based on the number of carbon atoms and the number of double bonds or the composition of total unsaturated fatty acid methyl esters (FAMEs) and (2) our posting of the Excel spreadsheets for implementing all of the evaluated accurate prediction methods on our group website (www.design.che.vt.edu) for the reader to download without charge. / Master of Science

<p>The global oil refining industry with its present shift inproduct distribution towards fuels such as gasoline and dieselwill most likely hold the fort for many years to come. However,times will change and survival will very much depend onprocessing flexibility and being at the frontiers of refiningtechnology, a technology where catalysts play leading roles.Today oil refiners are faced with the challenge to producefuels that meet increasingly tight environmentalspecifications, in particular with respect to maximum sulphurcontent. At the same time, the quality of crude oil is becomingworse with higher amounts of polyaromatics, heteroatoms(sulphur and nitrogen) and heavy metals. In order to staycompetitive, it is desirable to upgrade dense streams withinthe refinery to value-added products. For example, upgradingthe fluid catalytic cracking (FCC) by-product light cycle oil(LCO) into a high quality diesel blending component is a veryattractive route and might involve a two-step catalyticprocess. In the first step the LCO is hydrotreated andheteroatoms are removed and polyaromatics are saturated, in thesecond step naphthenic rings are selectively opened to improvethe cetane number of the final product.</p><p>The present research is devoted to the second catalytic stepof LCO upgrading and was carried out within the framework of aEuropean Union project entitled RESCATS.</p><p>From the patent literature it is evident that iridium-basedcatalysts seem to be good candidates for ring-opening purposes.A literature survey covering ring opening of naphthenicmolecules shows the need for extending investigations toheavier model substances, more representative of the dieselfraction than model compounds such as alkylated mono C5 and C6-naphthenic rings frequently employed in academic studies.</p><p>Ring-opening catalysts, mainly Pt-Ir based, were synthesisedat KTH by two different methods: the microemulsion and theincipient wetness methods. Characterization of the catalystswas performed using a number of techniques including TPR,TEM-EDX, AFM and XPS etc. Catalytic screening at atmosphericpressure using pure indan as model substance was utilized todetect ring-opening activity and the magnitude of selectivityto desired cetane-boosting products. The development of suchring-opening catalysts is the topic of Paper I.</p><p>When designing a catalytic system aimed at refiningpetroleum, it is crucial to monitor the evolution of thesulphur distribution throughout the different stages of theprocess so that catalyst properties and reaction parameters canbe optimised. The final section of this thesis and Paper II arethus devoted to high-resolution sulphur distribution analysisby means of a sulphur chemiluminescence detector (SCD).</p><p><b>Keywords:</b>ring opening, naphthenes, cetane numberimprovement, indan, light cycle oil (LCO), Pt-Ir catalyst,catalyst characterization, aromatic sulphur compounds, GC-SCD,distribution, analysis.</p>

Aleksandro Stulginskio Universitete, Transporto ir Jėgos Mašinų Inžinerijos Institute, atliktais tyrimais nustatyta, kad vieno cilindro tiesioginio įpurškimo dyzelinis variklis (,,Oruva“ F1L511) maitinamas pagerintu, 0,08; 0,12; 0,20vol% cetaninį skaičių (CS) didinančiu priedu, rapsų aliejumi (RA), gali efektyviai veikti ir išskirti mažesnę, kai kurių emisijos komponentų dalį. Dyzelinio variklio išvystytas didžiausias efektyvusis slėgis siekė 0,57MPa, varikliui veikiant 2000 min-1 sūkių dažniu. Variklio minimaliosios lyginamosios efektyviosios degalų sąnaudos sumažėjo nuo 272g/kWh iki 268g/kWh tai yra 1,5% panaudojus 0,12vol% cetaninį skaičių didinantį priedą rapsų aliejuje. Deginių dūmingumas sumažėjo 45% vidutinės (pe=0,4MPa) ir 40% didžiausios (pe=0,57MPa) apkrovos srityje atitinkamai panaudojus 0,12vol% ir 0,20vol% cetaninį skaičių didinantį priedą rapsų aliejuje. Bandymų metu didžiausias ƞe=0,364 variklio efektyvusis naudingumo koeficientas buvo pasiektas variklį maitinant 0,12vol% cetaninį skaičių didinančiu priedu apdorotu rapsų aliejumi ir jam išvysčius 5,3 kW efektyviąją galią. Tačiau mažesnės ir didesnės variklio išvystomos efektyviosios galios srityse aukštesnis variklio efektyvusis naudingumas buvo bazinio rapsų aliejaus naudojimo atveju. / Studies conducted at Aleksandas Stulginskis University (ASU) of Transport and Power Machinery Engineering Institute showed that a single-cylinder, air-cooled, direct-injection diesel engine (" Oruva " F1L511 ) can be with rapeseed oil treated with 0.08vol%, 0.12vol% and 0.20vol% the cetane number (CN) improving agent. Diesel engine developed the maximum effective pressure of 0.57MPa when running at 2000 rpm speed. Using of 0.12vol% of the cetane number improving agent (2-ethylheksyl-nitrate) to rapeseed oil the brake specific fuel consumption reduced in the range 272 g/kWh to 268 g/kWh, i.e. 1.5% when running at moderate (pe=0.38MPa) load and 2000 rpm speed. As a result of 0.12vol% the smoke opacity decreased by 45% at moderate (pe=0.4MPa) and 40% at maximum (pe=0.57MPa) load. During the tests, the highest ƞe=0.364 effective efficiency engine was when running on rapeseed oil treated with 0.12vol% cetane improving agent developed at the power output of 5.3 kW.