Hydrogenation Of Vegetable Oils Research Articles

Circulating concentrations and relative percent composition of trans fatty acids in healthy Canadian young adults between 2004 and 2010: a cross-sectional study.

Trans fatty acids (TFAs) produced from industrial partial hydrogenation of vegetable oils have been the subject of much research regarding their negative effect on the development of chronic diseases, and recommendations to label foods with partially hydrogenated vegetable oils and limit their levels were introduced in Canada in 2003 and 2007, respectively. Our aim was to determine temporal changes in circulating plasma TFAs in a population of young healthy Canadian adults after the introduction of the guidelines. In this study, circulating plasma concentrations and relative percent composition of individual TFAs over time (2004-2010) were determined in a cross-sectional cohort of young healthy Canadian adults as part of the Toronto Nutrigenomics study. A total of 1294 participants were included in the cohort. Relative to 2004, total TFA levels were significantly lower in 2005-2009 (p < 0.05), but not in 2010. Although levels of 16:1t9 and 18:1t11 declined after 2004, levels of 18:1t9 and 18:1t10 were significantly lower in 2005-2009 (p < 0.05), but not in 2010. Trans fatty acids were lower in 2009 relative to 2004, but not different in 2010, suggesting that young Canadians may remain vulnerable to partially hydrogenated vegetable oil exposure and that there is a need for further monitoring of specific food categories and vulnerable populations.

Reaksi transfer hidrogenasi minyak jarak kastor serta aplikasinya sebagai bahan pelunak kompon karet

Rubber plasticizer is used to improve rubber processability so as to shorten time and reduce energy consumption during compounding. In general, rubber plasticizer is nonrenewable and environmentally harmful petroleum derivatives due to the carcinogenic property. Environmentally friendly plasticizer can be produced by transfer hydrogenation of vegetable oil. The research was aimed to synthesize new rubber plasticizer from transfer hydrogenation of castor oil using diimide compound which was generated in situ by oxidation of hydrazine hydrate and hydrogen peroxide as well as the application of the new rubber plasticizer obtained on natural and synthetic rubbers compounding. The result showed that the optimum condition of transfer hydrogenation was achieved at a capacity of 1000 ml oil/batch, 40oC for 5 hours, and ratio hydrazine hydrate to hydrogen peroxide at 1:2 due to the hydrogenated castor oil (HCO) had the highest degree of hydrogenation and neutral pH. The application of 10 phr HCO had significant effect on the compounding of EPDM 6250 which was shown by shortest time and lowest energy of compounding, and also by the highest minimum torque modulus. In addition, the crosslink density of rubber vulcanizate which was formed during accelerated sulfur vulcanization was affected both by the addition of HCO and the saturation of the rubber being used. Keywords: environmentally friendly plasticizer, castor oil, diimide hydrogenation, rubber.

CHEMICAL EQUILIBRIUM STUDY OF SYSTEMS RELATED TO BIOFUELS – TEACHING EXPERIENCE WITH THERMODYNAMIC ANALYSIS OF HYDROGENATION OF VEGETABLE OILS

Total hydrogenation of vegetable oils to yield hydrocarbons is an emerging processfor production of biofuels. Some researchers have been chosen tristearate as amodel compound to represent vegetable oils in the calculations. The first problemis that its thermodynamic data were not available in literature, their values wereestimated by using the Joback’s contribution method. Based on the comparison toenthalpy of formation estimated in this work and in Smejkal et al., it was concludedthat the chosen method can influence in the result of thermodynamic data. In thiswork, we realised that the basic thermodynamic analysis of the reaction system wasperformed presenting some misconceptions and problems which must be betterdiscussed and checked. Calculations were done in classroom and as home-work,then the results have pointed out corrections.doi: https://doi.org/10.18540/2446941602022016095

Towards biolubricant compatible vegetable oils by pore mouth hydrogenation with shape-selective Pt/ZSM-5 catalysts

Pore mouth hydrogenation of vegetable oil with Pt/ZSM-5 is confirmed by the similar intermediately melting product selectivity for various crystal sizes.

Perlite as a potential support for nickel catalyst in the process of sunflower oil hydrogenation

Investigation was conducted in order to elucidate the possibility of using perlite as support for preparation of nickel based precursor catalyst, potentially applicable in vegetable oil hydrogenation process. On three differently prepared expanded perlite, nickel catalyst precursors with identical Ni/SiO2 = 1.1 and Ni/Mg = 10/1 ratios were synthesized by precipitation-deposition method. Different techniques, SEM micrography, He-pycnometry, calcimetry, Hg-porosimetry, N2-physisorption, H2-chemisorption and temperature programmed reduction, were used for characterization of obtained samples. Determining the precursor texture, morphology and reducibility shows a successfully deposited nickel phase on perlite support with promising properties for vegetable oil hydrogenation. Chosen precursor was reduced and passivated in paraffin oil and the obtained catalyst showed significant catalytic activity in the test of sunflower oil hydrogenation.

Cis and trans unsaturated phosphatidylcholine bilayers: A molecular dynamics simulation study

Trans unsaturated lipids are uncommon in nature. In the human diet, they occur as natural products of ruminal bacteria or from industrial food processing like hydrogenation of vegetable oils. Consumption of trans unsaturated lipids has been shown to have a negative influence on human health; in particular, the risk of cardiovascular disease is higher when the amount of trans unsaturated lipids in the diet is elevated. In this study, we first performed quantum mechanical calculations to specifically and accurately parameterize cis and trans mono-unsaturated lipids and subsequently validated the newly derived parameter set. Then, we carried out molecular dynamics (MD) simulations of lipid bilayers composed of cis or trans unsaturated lipids with and without cholesterol. Our results show that trans mono-unsaturated chains are more flexible than cis mono-unsaturated chains due to lower barriers for rotation around the single bonds next to the trans double bond than those next to the cis double bond. In effect, interactions between cholesterol and trans unsaturated chains are stronger than cis unsaturated chains, which results in a higher ordering effect of cholesterol in trans unsaturated bilayers.

Aging studies of biodiesel and HVO and their testing as neat fuel and blends for exhaust emissions in heavy-duty engines and passenger cars

Abstract An increasing use of renewable fuels in the transport sector reduces the dependency on fossil oil and lowers the emission of greenhouse gases. This is a prime political and economic goal in Europe and also in many other parts of the world. In the diesel fuel sector, especially fatty acid methylesters are introduced as renewable fuels. This so-called biodiesel is mostly added to common diesel fuel in amounts of up to 20%. A further increase of the biodiesel content in the fuel is prevented by the increase of engine oil dilution by biodiesel in vehicles equipped with a diesel particulate filter (DPF). Biodiesel in the engine oil can lead to oil sludge formation. Emissions on one hand as well as oil sludge formation on other hand are important issues in fuel research and for implementation of new fuels. Besides biodiesel, hydrotreated vegetable oil (HVO) was recently introduced into the market exemplified at a new fuel called Diesel regenerativ. Hydrogenation of vegetable oil produces a fuel free of sulfur and aromatics with a high cetane number. HVO and biodiesel were tested in aging studies with base oil, whereby biodiesel is lubricant itself. These laboratory studies were carried out in order to simulate the formation of oil sludge in the engine. Diesel regenerativ is a fuel consisting of HVO with an admixture of 7% biodiesel. The biodiesel has the tendency to coagulate. This can lead to oil sludge formation if the fuel enters the engine oil. The base oil examinations showed a faster oil sludge formation with biodiesel than with HVO. In addition to these investigations the effects of HVO on the regulated and non-regulated emissions had also been tested extensively on heavy-duty engines and in a passenger car fleet test. The emissions of HVO and biodiesel were compared using a Euro III and a Euro IV heavy-duty engine with and without exhaust gas aftertreatment system. Furthermore, three passenger cars (Euro 3, 5 and 6) were examined in a fleet test for regulated and non-regulated emissions. The results showed that all heavy-duty engine emissions were lowered with the usage of HVO, compared with diesel fuel. In comparison with biodiesel, HVO also shows lower NOX emissions. This trend could not be confirmed using the passenger cars. In this investigation nitrogen oxide emissions increased between 5% and 14% versus diesel fuel. The increase was independent of the exhaust treatment.

Experimental study of the deactivation of Pd on anodized aluminum monoliths during the partial hydrogenation of vegetable oil

Partial hydrogenation of sunflower oil was studied over Pd/Al2O3/Al catalysts in a monolithic stirred reactor. The catalyst showed similar or even better activity and selectivity than conventional Pd/Al2O3 catalysts. However, in consecutive runs, a continuous decreasing activity was observed. In order to understand the deactivation phenomena, fresh and spent catalysts were characterized using temperature programmed reduction, N2 adsorption isotherms, dynamic H2 chemisorption, transmission electron microscopy (TEM), atomic absorption spectroscopy, inductively coupled plasma spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, ultrasound adherence tests, and X-ray photoelectron spectroscopy. Furthermore, an extensive number of catalytic tests under different operating conditions were carried out. The loss in activity was proportional to the reduction in metal dispersion. The decrease in Pd dispersion was due to the coverage of the Pd surface. The deactivation occurred due to fouling with reaction residues most probably coming from polymerization and/or cross-linking reactions. The catalysts can be regenerated ex situ using a careful desorption–washing–calcination process, although this requires further research because the temperatures required are too high for Al.

Effect of Catalyst Preparation on the Selective Hydrogenation of Vegetable Oil Over Low Percentage Pd/Diatomite Catalysts

Hydrogenated vegetable oils contain high contents of &lt;em&gt;trans&lt;/em&gt;-fatty acids. Because of the increased health concern about &lt;em&gt;trans&lt;/em&gt;-fatty acids, new hydrogenations have been studied to seek ways for substantial reduction of the &lt;em&gt;trans&lt;/em&gt;-fatty acids in the hydrogenated products. In this research, activated diatomite has distinctive properties as a support for hydrogenation catalysts. Investigation of textural properties of raw and purified diatomite samples reveals that during acid activation surface area increases significantly. Although, acid activation of diatomite is a commonly chemical modification to enhance its adsorption capacity. We are preparing adsorption method to synthesize low percentage 0.2% of Pd/Diatomite catalyst. The activated diatomite and the obtained catalyst was characterized by using thermogravimetric analysis (TGA), Brunauer-Emmett-Teller surface area analysis (BET), scanning electron microscopy (SEMEDAX), transmission electron microscopy (TEM). It was utilized for hydrogenation of sunflower oil using the Parr reactor in laboratory testing a variety of temperature (70, 90, 110 ºC) and canola oil in industrial testing, at temperature 90 ºC and 0.5 MPa pressure and compared to commercial nickel catalyst (Pricat-9910) at 150 ºC, 0.5 MPa pressure agitation of 800 rpm for 160 min. The changes in iodine value, fatty acid composition, &lt;em&gt;trans&lt;/em&gt;-fatty acids, melting point and solid fat content were investigated on partial hydrogenated sunflower oil and canola oil. The experimentally obtained results show that the palladium catalyst is the most active compared to the commercial catalyst. Lower hydrogenation temperature used 0.2% Pd/Diatomite catalyst, significant reducing the formation of &lt;em&gt;trans&lt;/em&gt;-content by 13% in fat.

Development of palladium catalysts on carbon supports from the Sibunit family for vegetable oil hydrogenation processes

Studies on the synthesis of powdered Pd/C catalysts prepared by the supporting of Pd onto a mesoporous carbon material from the Sibunit family and the characterization of their properties in the process of the partial hydrogenation of sunflower oil are reported. The comparative tests of a 1.0 wt % Pd/Sibunit catalyst and Pricat and Nysosel commercial nickel catalysts in the hydrogenation sunflower oil were performed with the use of a Parr batch reactor. It was found that the Pd catalyst was superior to Ni analogs in activity, and it afforded sunflower oil partial hydrogenation products with reproducible characteristics.

Mathematical modeling of the partial hydrogenation of vegetable oil in a monolithic stirrer reactor

Experimental and theoretical studies on the partial hydrogenation of vegetable oil in a monolithic stirrer reactor are reported. A complete mathematical model of the reactor was developed, including hydrogenation and isomerization kinetics, catalyst deactivation, external gas–liquid and liquid–solid as well as internal mass transfer. The experimental studies were carried out in a Pd/Al2O3/Al monolithic stirrer reactor, at a wide range of temperatures (353–373 K), pressures (414–552 kPa), and catalyst loadings (0.00084–0.00527 kgPd,exp m−3). Based on this model, simulated data can be used to evaluate the catalyst (Pd/Al2O3/Al) and the hydrogenation process in consecutive catalytic tests under different operating conditions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3524–3533, 2014

On-line hydrogenation of biodiesel—Toward a reference method for the determination of glycerides and total glycerol

A reliable method with ensured traceability of the measurement results for free and bound glycerol (as monoacylglycerides, diacylglycerides and triacylglyerides) in biodiesel was developed, giving results beyond the state of the art of the current standard methodologies. The proposed method is based on an on-line hydrogenation using gas chromatography coupled to flame ionization detection and hydrogen as carrier gas. After sample introduction the hydrogenation takes place on a fused silica pre-column coated with a palladium catalyst. This approach allows an immediate and reliable hydrogenation of vegetable oils and biodiesels from different feedstocks. All glycerides are converted into their saturated analogues, resulting in simplified chromatograms with structurally clearly defined analytes, and increased sensitivity for trace amounts of compounds. The method has been successfully in-house validated and combined uncertainty values have been assigned to the final results, which were less than 8% for free glycerol, the sum of monoacylglycerides, the sum of diacylglycerides and the sum of triacylglycerides.

Investigations of Bio-gasoil Production

Liquid engine fuels are the main source of power for transportation in the passenger sector. It is the projection of the European Union (EU) to reach 10% utilisation of renewable fuels by 2020. To achieve this goal the EU created the 2003/30/EC and furthermore the 2009/28/EC Directives. For example, the feedstocks of these renewable engine fuels can be non-edible oil plant hybrids, such as rapeseed oils with high euric acid content obtained from special hybrids of rape (e.g. Brassica napus) waste lards (used cooking oil and slaughterhouse lards). If the preconditions of utilisation are given with respect to the sustainability and technical compatibility of motor engines and vehicle construction, these bio components can be blended with motor fuels in large quantities. Considering the properties of currently used first generation biofuels, the maximum amount of bio-component in engine fuels is approximately 7 (v/v)% fatty acidmethylester in diesel fuels. A reliable production technology of second generation biofuels, which can be blended into diesel fuels is the heterogenic catalytic hydrogenation of triglycerides and waste lards. Furthermore, isomerisation can improve the quality of a bio-paraffin mixture. In this context, we studied the isomerisation of bio-paraffin mixtures, which were obtained from the hydrodeoxygenation of vegetable oil. The characteristics of these products were favourable, such as their cetane number being higher than 75, for example. The actual EN590:2013 standard does not limit the blending ratio of the paraffinic bio-component in diesel fuels. Consequently, these products obtained by the catalytic hydrogenation of vegetable oils can be blended into gasoil by up to 10 % or even more to meet the above EU requirements with respect to the utilisation of renewable fuels.

SOLID-LIQUID EXTRACTION OF CHLOROPHYLL FROM MICROALGAE FROM PHOTOAUTOTROPH OPEN-AIR CULTIVATION

Liquid engine fuels are the main source of power for transportation in the passenger sector. It is the projection of the European Union (EU) to reach 10% utilisation of renewable fuels by 2020. To achieve this goal the EU created the 2003/30/EC and furthermore the 2009/28/EC Directives. For example, the feedstocks of these renewable engine fuels can be non-edible oil plant hybrids, such as rapeseed oils with high euric acid content obtained from special hybrids of rape (e.g. Brassica napus) waste lards (used cooking oil and slaughterhouse lards). If the preconditions of utilisation are given with respect to the sustainability and technical compatibility of motor engines and vehicle construction, these bio components can be blended with motor fuels in large quantities. Considering the properties of currently used first generation biofuels, the maximum amount of bio-component in engine fuels is approximately 7 (v/v)% fatty acidmethylester in diesel fuels. A reliable production technology of second generation biofuels, which can be blended into diesel fuels is the heterogenic catalytic hydrogenation of triglycerides and waste lards. Furthermore, isomerisation can improve the quality of a bio-paraffin mixture. In this context, we studied the isomerisation of bio-paraffin mixtures, which were obtained from the hydrodeoxygenation of vegetable oil. The characteristics of these products were favourable, such as their cetane number being higher than 75, for example. The actual EN590:2013 standard does not limit the blending ratio of the paraffinic bio-component in diesel fuels. Consequently, these products obtained by the catalytic hydrogenation of vegetable oils can be blended into gasoil by up to 10 % or even more to meet the above EU requirements with respect to the utilisation of renewable fuels.

Process Balances of Vegetable Oil Hydrogenation and Coprocessing Investigations with Middle-Distillates

The hydrogenation of vegetable oil is a promising technology for the production of highly valuable diesel components. Suitable production routes are the hydrogenation on sulfided NiMo catalysts with pure vegetable oil as feedstock or their coprocessing with middle distillates. To obtain the yields of all products for a complete process balance, experimental studies with rapeseed oil and jatropha oil were performed in a pilot scale test bench. IR spectroscopy and 13C NMR spectroscopy as well as gas chromatography were used for analyzing the liquid product. On the basis of a simplified reaction scheme, a procedure for the recalculation of specific yields and hydrogen consumption is presented and compared with the experimental values. The coprocessing experiments include the admixture of 5–20 wt % jatropha oil to a straight run middle distillate in the temperature range of 300–350 °C. It could be shown that the optimum reaction temperature for production of alkanes with nearly complete oxygen removal is significantly lower than that for the desulfurization of middle distillates down to 10 ppm sulfur. Concerning the cold flow properties, an admixture up to 15 wt % jatropha oil does not increase the Cold Filtration Plugging Point (CFPP) of the base middle distillate.

Hydrogenation of Vegetable Oil – Mechanism and Kinetics

AbstractExperimentelle Untersuchungen zur Hydrierung von Pflanzenölen für die Herstellung hochwertiger Dieselkraftstoffkomponenten in einem kontinuierlich arbeitenden Rieselbettreaktor werden vorgestellt. Anhand der experimentellen Ergebnisse wird der Reaktionsablauf diskutiert und ein globaler, strukturgruppenbasierter Reaktionsmechanismus postuliert. Darauf aufbauend wird ein formalkinetisches Modell vorgestellt, das auch die Bildung von Zwischenprodukten erfasst und als Grundlage für die Auslegung technischer Reaktoren verwendet werden kann.

Environmental impact of castor oil catalytic transfer hydrogenation

In the vegetable oil chemical industry, hydrogenation is one of the most important processes. An alternative method for vegetable oil hydrogenation is the use of catalytic transfer hydrogenation (CTH), which can utilize organic molecules as hydrogen donors at ambient pressure. These alternative processes should be optimized in relation to the variables required for a good conversion and impacts should also be known to be minimized. An assessment of the environmental impact of laboratory scale chemical processes is an important tool to improve the technological aspects of a process (increased yields, reduced production times, lower costs) and it can also lead to the creation of a cleaner technology. Using the Leopold Matrix, we have succeeded in developing a more efficient and cleaner process for the CTH of castor oil using Raney Ni as a catalyst and cyclohexene or isopropanol as a hydrogen donor solvent. The results of the technical and environmental assessments showed that the extent of conversion for the unsaturation reaction was high (>99 %), and the environmental impact of the process could be significantly reduced to create a cleaner technology. It was found, after process optimization, that the remaining environmental impacts were negative (67.48 %), local (78.95 %), temporary (95.33 %), direct (80.12 %), and reversible (95.32 %).

Hydrogenation of rapeseed oil for production of liquid bio-chemicals

The main objective of rapeseed oil hydrogenation tests was the production of liquid bio-chemicals to be used as renewable raw material for the production of several chemicals and in chemical synthesis to substitute petroleum derived stuff. As, hydrogenation of vegetable oils is already applied for the production of biofuels, the work done focused in producing aromatic compounds, due to their economic value. The effect of experimental conditions on rapeseed oil hydrogenation was studied, namely, reaction temperature and time with the aim of selecting the most favourable conditions to convert rapeseed oil into liquid valuable bio-chemicals. Rapeseed oil was hydrogenated at a hydrogen initial pressure of 1.10MPa. Reaction temperature varied in the range from 200°C to 400°C, while reaction times between 6 and 180min were tested. The performance of a commercial cobalt and molybdenum catalyst was also studied. The highest hydrocarbons yields were obtained at the highest temperature and reaction times tested. At a temperature of 400°C and at the reaction time of 120min hydrocarbons yield was about 92% in catalyst presence, while in the absence of the catalyst this value decreased to 85%. Hydrocarbons yield was even higher when the reaction time of 180min was used in the presence of catalyst, as the yield of 97% was observed. At these conditions hydrocarbons formed had a high content of aromatic compounds, around 50%. For this reason, the viscosity values of hydrogenated oils were lower than that established by EN590, which together with hydrogenated liquids composition prevented its use as direct liquid fuel to substitute fossil gas oil for transport sector. However, hydrocarbons analysis showed the presence of several valuable compounds that encourages their use as a raw material for the production of several chemicals and in chemical synthesis.

Investigation of the Catalytic Performance of a Novel Nickel/Kit-6 Nanocatalyst for the Hydrogenation of Vegetable Oil

Highly ordered mesoporous materials are opening the door to new opportunities in catalysis due to their extraordinary intrinsic features. In this study, Nickel was supported on highly ordered mesoporous silica (KIT-6) by the wet impregnation method, and its performance in the hydrogenation of edible vegetable oil was compared with that of Ni/Activated carbon prepared using the same method as well as with unsupported Nickel. The degree of conversion for the 50 : 50 Ni/KIT-6 was 81%, as compared to the 29% obtained with 50 : 50 Ni/Activated carbons. The conversion was found to improve with an increase in mass of supported Nickel on KIT-6 thus 20 : 80 Ni/KIT-6 and 30 : 70 Ni/KIT-6 produced conversions of 71% and 74%, respectively. Key among the benefits of KIT-6 when used as a support material is the very high surface area, open framework of the 3D bicontinuous interconnected channels, and the well-ordered mesopores which bestow on it an advanced mass transfer characteristics.

Effect of the support and the reduction temperature on the formation of metallic nickel phase in Ni/silica gel precursors of vegetable oil hydrogenation catalysts

Ni/SiO2 materials with identical composition (SiO2/Ni = 1.0) have been synthesized by precipitation of Ni(NO3)2 · 6H2O solution with Na2CO3 solution on the silica gel, obtained at three different pH values. The present investigation was undertaken in an endeavor to study the effects of the silica gel support type and the reduction temperature on the formation and dispersion of the metallic nickel phase in the reduced Ni/SiO2 precursors of the vegetable oil hydrogenation catalyst. The physicochemical characterization of the unreduced and reduced precursors has been accomplished appropriately by powder X-ray diffraction, infrared spectroscopy, temperature programmed reduction and H2-chemisorption techniques. It can be stated that the texture peculiarities of the silica gels used as supports influence on the crystalline state and distribution of the deposited Ni-containing phases during the preparation of the precursors, on the reduction temperature of the investigated solids as well as on the bulk size and surface dispersion of the arising metallic nickel particles. It was shown that two types of Ni2+-species are formed during the synthesis procedure, namely basic nickel carbonate-like and Ni-phyllosilicate with different extent of presence, location and strength of interaction. The different location of these species is supposed to result in various strength of Ni-O and Ni-O-Si interaction, thus determining the overall reducibility of the precursors. It was specified that the Ni2+-species are strongly bonded to the surface of the silica gel obtained at neutral pH value and weakly bonded to the surface of those prepared in acidic and alkaline conditions. It was established that the precursor, derivates from the silica gel obtained at alkaline conditions, demonstrates both significant reduction of the Ni2+ ions at 430°C and finely dispersed metallic nickel particles on its surface. High dispersion of the metallic nickel might be the crucial reason for achieving of high activity in the vegetable oil hydrogenation.