Premium quality renewable diesel fuel by hydroprocessing of sunflower oil

Hydroprocessing of neat sunflower oil was carried out at 360-420 °C and 18 MPa over a commercial hydrocracking catalyst in a bench scale fixed bed reactor. In the studied experimental range, products consisted exclusively of hydrocarbons that differed significantly in composition. While the concentration of n-alkanes exceeded 67 wt.% in the reaction products collected at 360 °C, it decreased to just 20 wt.% in the product obtained at 420 °C. Consequently, the fuel properties of the latter product were very similar to those of standard (petroleum-derived) diesel fuel. Particularly, it exhibited excellent low-temperature properties (cloud point −11 °C; CFPP −14 °C). Reaction products obtained at 400 and 420 °C were blended into petroleum-derived diesel fuel in three concentration levels ranging from 10 to 50 wt.% and the fuel properties of these mixtures were evaluated. Diesel fuel mixtures containing the product of sunflower oil hydrocracking at 420 °C showed very good low-temperature properties including cloud point (−8 °C) and CFPP (−15 °C) that was further lowered to −25 °C due to addition of flow improvers.     

Hydroprocesssing of light gas oil — rape oil mixtures

Two series of experiments of hydroprocessing of light gas oil - rape oil mixtures were carried out. The reactor feed was composed of raw material: first series — 10 wt.% rape oil and 90 wt.% of diesel oil; second series — 20 wt.% rape oil and 80 wt.% of diesel oil.     

Synthesis and properties of boron-containing soybean oil based thermosetting copolymers

The first example of boron-containing soybean oil based copolymers was prepared from soybean oil, styrene, divinylbenzene and 4-vinylphenyl boronic acid by cationic polymerization using boron trifluoride etherate as initiator. Soxhlet extraction and NMR spectroscopy indicate that the copolymers consist of a crosslinked network plasticized with varying amounts of oligomers and unreacted oil. The thermal degradation mechanism was studied and the thermal, dynamomechanical and flame retardant properties of these materials were examined. Thermosets with glass transition temperatures ranging from 43 to 60 °C, which are thermally stable below 350 °C and with LOI values from 23.7 to 25.6 were obtained. The LOI tests indicate that the flame retardant properties of vegetable oil can be improved by adding boron covalently bonded to the polymer.     

The comparison of particle oxidation and surface structure of diesel soot particles between fossil fuel and novel renewable diesel fuel

Conventional fossil diesel fuel and renewable diesel fuel based on hydrotreated vegetable oils (HVO) were compared regarding the oxidation characteristics of the generated soot particulate. The comparison was performed by utilizing a high-temperature oxidation tandem differential mobility analyser in which monodisperse soot aerosol was first selected and then heated in a high-temperature furnace. The particle size reduction caused by oxidation during the furnace treatment was then measured as a function of furnace temperature. The results indicate that soot oxidation is very similar between the studied fuels. This is supported by the obtained HR-TEM images and EELS-spectra which were practically indistinguishable between different fuels and engine conditions. The similar oxidation properties and surface structure between fossil and HVO-based diesel fuels imply that the oxidative aftertreatment devices designed for fossil diesel should work well also with the studied renewable diesel fuel.     

植物油加氢制备高十六烷值柴油组分研究进展

介绍了植物油加氢制备柴油的主要化学反应、工艺方法以及该项技术的工业化状况,分析了植物油直接加氢、先加氢后异构、直接脱羧工艺以及植物油与矿物柴油掺炼工艺的特点,阐述了各工艺采用的催化剂类型、工艺条件以及产品属性。指出了该领域存在的问题和研究方向。     

Phase diagrams for vegetable oil/methanol mixtures

Based on the analysis of literature data, a number of vegetable oils most promising for biodiesel synthesis were selected. The studies of the phase state and calculations of the phase diagrams for methanol/oil were performed in a wide range of temperature, pressure and alcohol/oil molar ratios. The conditions to provide supercritical state of the reaction mixture at vegetable oil conversion were found.     

Catalytic deoxygenation of unsaturated renewable feedstocks for production of diesel fuel hydrocarbons

The liquid-phase deoxygenation reaction of unsaturated renewables has been investigated in a semi-batch reactor. The reactants examined were the monounsaturated fatty acid, oleic acid, the diunsaturated fatty acid, linoleic acid and the monounsaturated fatty acid ester, methyl oleate. The reactions were carried out over a Pd/C catalyst under constant pressure and temperature in the following domain, 15-27 bar and 300-360 °C, respectively. The influence of carrier gas was additionally investigated. The impact as solvent (mesitylene) was studied as well and reaction pathways were proposed. Furthermore, continuous deoxygenation experiments were conducted, facilitating understanding of the catalyst stability and catalyst deactivation. The deoxygenation catalyst was characterized by physisorption, temperature programmed desorption (TPD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM).     

Effects of oil type on products obtained by cracking of oils and fats

This paper deals with cracking of vegetable oils and animals fats in the presence of zeolite catalysts, the objective being preparation of liquid products similar in their properties to fossil diesel. The effects of oil/fat type on the liquid condensate yields and parameters were monitored. The tests were carried out with rapeseed, sunflower, soybean and jatropha oils as well as with used frying oils. Liquid condensates with yields of 85 to 90% relative to the input oil were obtained at temperatures of 350 to 440 °C applied for the period of 20 to 30 min in the presence of zeolite catalysts NaY and clinoptilolite. The input oil types had no significant effect on the yields and characteristics of the treated condensate. In this respect, used frying oils (UFO) as a feed material match other types of fresh oils and fats. Treated condensates blended with fossil diesel (5-7% of the condensate by volume) are compliant with the EN 590 standard and can thus be used as a component of diesel fuels.     

Storage stability and corrosion studies of renewable raw materials and petrol mixtures: A key issue for their co-processing in refinery units

Mixtures of renewable raw materials such as vegetable oils (crude palm and soybean oil and waste cooking oil) and animal fat unfit for human consumption with petrol feedstock were assessed for considering their co-processing in refinery units. Vacuum gasoil, hydrotreated vacuum gasoil and atmospheric residue were taken as petrol feedstocks. Ageing of these mixtures under storage conditions has been deeply studied. Significant changes in physical properties such as density, viscosity and acidity may promote some problems in the processability in the FCC unit. Moreover, potential polymers formed under storage conditions could lead to the deposit of gums in the tubes of the heat exchangers and the transfer lines previous to the FCC unit. Storage stability studies were performed by means of an accelerated oxidation process according to the UOP 174-84 method. Physical properties including density, viscosity and acidity were measured before and after oxidation treatment. In addition, distillation curve of the mixtures before and after treatment was determined by means of simulated gas chromatography (ASTM D-2887). Physical properties as well as distillation curve of samples were statistically unchanged after oxidation treatment. Likewise, presence of water in the raw feedstock and sediment content in the samples after thermal treatment were not evidenced. Hence, according to the UOP 174-84 method, the different mixtures under study can be considered stable in storage at 77 °C for periods of at least 180 days. Corrosion studies were also carried out to elucidate if the presence of free fatty acids in vegetable oils and animal fats might cause problems in storage systems of refinery units. The assays were performed following the UOP 174-84 method slightly modified by the presence of a carbon metal probe ASTM A 293 Gr C. The leaching of metallic species was monitored after thermal treatment. The results showed a negligible leaching of metallic species for pure petrol feedstock samples as well as for their mixtures with renewable materials.     

Quantitative determination of diesel oil in contaminated edible oils using high-performance liquid chromatography

A simple and reliable high-performance liquid chromatography method for the analysis of diesel oil in contaminated edible oils is described. Analysis performed using a diol column with a mobile phase of heptane and isopropanol (94∶6, vol/vol). Although baseline separation between diesel and other background fluorescent components was not achieved, quantitation was still possible using baseline integration. The method is linear over the range of 5–1000 μg/g with a correlation coefficient (r ²) of 0.9984. Average recoveries from spiked edible oils were 94.4–101.3%, with a limit of quantitation (LOQ) of 5 μg/g for sunflower oil, palm olein, and groundnut oil. Corn oil has a higher content of ester components, thus, LOQ was slightly worse (40 μg/g). The applicability of the method was confirmed by gas chromatography-mass spectroscopic detection to show the presence of diesel hydrocarbons in the suspected contaminated crude palm oil. This procedure provides a simple and sensitive method for determining diesel oil concentration in contaminated edible oils without prior sample cleanup or extraction.     

A review of conventional and renewable biodiesel production

The need for sustainable fuels has resulted in the production of renewables from a wide range of sources, in particular organic fats and oils. The use of biofuel is becoming more widespread as a result of environmental and economic considerations. Several efforts have been made to substitute fossil fuels with green fuels. Ester molecules extracted from processed animal fats and organic plant materials are considered alternatives for the use in modern engine technologies. Two different methods have been adopted for converting esters in vegetable oils/animal fats into compounds consistent with petroleum products, namely the transesterification and the hydro-processing of ester bonds for the production of biodiesel. This review paper primarily focuses on conventional and renewable biodiesel feedstocks, the catalyst used and reaction kinetics of the production process.     

Response surface modeling and optimization of biodiesel production from Cynara cardunculus oil

Cardoon (Cynara cardunculus L.) is a perennial spontaneous thistle grown in Mediterranean countries and well adapted to marginal lands, recently considered as a non‐food energy crop. Their seeds contain 24% of oil (dry basis). In this study, modeling and optimization of the production of fatty acid methyl esters (FAME) from cardoon oil for biodiesel uses was performed at laboratory scale, via response surface methodology, following a central composite rotatable design. FAME were obtained by transesterification of crude cardoon oil with methanol in the presence of a catalyst (sodium methoxide) for 120 min. The temperature ranged from 26 to 94 °C, the amount of sodium methoxide varied between 0.12 and 2.5 wt‐% and the molar ratio methanol/oil from 0.95 : 1 to 11 : 1. The estimated yield of FAME (97%) was obtained after 30 min, at 52 °C, for a molar ratio of 6.4 : 1 and 1.4 wt‐% of catalyst. In laboratory‐scale model validation experiments, 94% of FAME yield was obtained after 30 min of reaction. Transesterification was performed in a 30‐L reactor, under previously optimized conditions: A yield of 88% FAME was obtained after 90 min of reaction time, due to mass transfer limitations. After purification, the biodiesel showed high quality according to DIN EN 14214 standard specifications.     

生产清洁汽油和柴油催化技术进展

为面对新世纪清洁燃料生产的新机遇和新挑战,各种生产清洁燃料的催化技术正在竞相开发之中,尤其是生产低硫、超低硫汽油与柴油技术。其中,催化裂化（FCC）降硫催化剂和助剂、选择性加氢处理新催化剂及工艺、汽柴油吸附脱硫、柴油生物催化脱硫和选择性氧化脱硫等新技术尤其引人注目。我国应加快清洁燃料生产催化新技术的开发研究,为生产更清洁的汽油和柴油燃料提供技术储备。     

Combustion of rapeseed oil and diesel oil mixtures for use in the production of heat energy

The energy policy of both Europe and Spain considers biomass to be the renewable energy source with the greatest possibilities of growth, from both the point of view of forestry and energy crops. One alternative to energy crops is the use of rapeseed oil as the fuel in thermic processes.This paper studies the use of rapeseed oil and diesel oil mixtures as the fuel for producing heat in a conventional diesel installation.The paper is set out as follows: a) Characterization of the properties of rapeseed oil as fuel and of diesel oil, as well as the mixtures of both. b) Selection of the mixtures according to their physical–chemical properties and to how they adapt to a conventional installation consisting of a mechanical pulverization burner. c) Experimentation with the selected mixtures in a conventional combustion installation, allowing the main combustion parameters to be measured. d) A study is carried out of the yield of the combustion.The conclusions show that the use of rapeseed and diesel mixtures for producing heat energy in conventional equipment is feasible.     

间戊二烯C5石油树脂改性作为柴油降凝剂的研究

间戊二烯C5石油树脂在引发剂的作用下与马来酸酐发生接枝反应,再用直链烷烃醇进行酯化,制得梳状结构的柴油降凝剂。戊二烯C5石油树脂改性制备柴油降凝剂的最佳反应条件是:各物质质量比C5石油树脂∶马来酸酐∶引发剂∶混合醇∶溶剂(二甲苯)为100∶12∶1∶20∶8,混合醇用量比C12∶C16∶C18为0.4∶0.3∶0.3,反应温度80℃,反应时间4 h,所得到的改性石油树脂降凝剂与T 602C降凝剂复配(改性石油树脂降凝剂加入量为400μg/g,T 602C加入量为1 000μg/g)对柴油具有很好的降凝效果,可将抚顺石化公司生产的-10#柴油馏分的冷滤点降低7℃。     

Synthesis and characterization of modified cottonseed oil based polyesteramide for coating applications

Cottonseed oil fatty amide (CFA) was prepared in the laboratory by base catalyzed aminolysis of cottonseed oil. Further it was reacted with phthalic acid to obtain polyesteramide (CPEA) and modified by post reacting with vinyl acetate monomer in varying ratios of 4:1, 3:1 and 2:1 in the presence of t-butyl hydroperoxide as an initiator. The incorporation of vinyl acetate in CPEA was analyzed using FTIR, ¹H NMR and ¹³C NMR spectral techniques. The physico-chemical properties such as iodine value, specific gravity and refractive index were determined by standard laboratory test methods. Mechanical, chemical resistance and other coating properties of the coatings synthesized from CPEA and modified CPEA applied on mild steel substrates were also studied by standard methods. Thermal stability and curing behavior of modified CPEA were determined by thermo gravimetric analysis (TGA) and differential scanning calorimetric (DSC) techniques. It was observed that modification of polyesteramide improved the curing, mechanical and chemical performance of CPEA films. It was found that among the CPEA:vinyl acetate ratios, 2:1 ratio exhibited the best results.     

生产清洁汽油和柴油催化技术进展(续完)

为面对新世纪清洁燃料生产的新机遇和新挑战，各种生产清洁燃料的催化技术正在竞相开发之中，尤其是生产低硫、超低硫汽油和柴油技术。其中，催化裂化（FCC）降硫催化剂和助剂、选择性加氢处理新催化剂及工艺、汽柴油吸附脱硫、柴油生物催化脱硫和选择性氧化脱硫等新技术尤其引人注目。我国应加快清洁燃料生产催化新技术的开发研究，为生产更清洁的汽油和柴油燃料提供技术储备。     

Catalytic conversion of vegetable oils in a continuous FCC pilot plant

In this paper the influence of admixtures of rapeseed, soybean and palm oil into VGO on FCC performance has been studied. The oils were mixed in steps of 20 wt.% and tested in a fully continuous operated FCC pilot plant. The experiments show that the product distribution changes slightly. Higher ratios of vegetable oils hardly affect the gasoline yields but cause a decrease in cracking gas. Oxygen contained in the vegetable oils is converted predominantly to water. It has been demonstrated that the obtained gasoline is oxygen free and shows improved properties for RON and MON. The cracking gas contains high amounts of propene and ethene, which can be used as base materials for the production of synthetic materials from renewable sources.