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.     

Hydrocracking of petroleum vacuum distillate containing rapeseed oil: Evaluation of diesel fuel

Hydrocracking of pure petroleum vacuum distillate and the same fraction containing 5 wt.% of rapeseed oil was carried out at 400 and 420 °C and under a hydrogen pressure of 18 MPa over commercial Ni-Mo catalyst. Reaction products were separated by distillation into kerosene, gas oil and the residue. Fuel properties of fractions suitable for diesel production were evaluated (gas oils and remixed blends of kerosene and gas oil). Gas oils obtained from co-processing showed very good fuel properties as the remixed distillates did. Gas oil obtained from co-processing at 420 °C showed also reasonable key low-temperature properties (cloud point: −23 °C, CFPP: −24 °C) similar to those of gas oil obtained from pure petroleum raw material processing.     

Thermal stability of gelatin gels: Effect of preparation conditions on the activation energy barrier to melting

10, 20, and 40 wt.% aqueous gelatin gels were prepared under isothermal (annealing at 15, 20, and 25 °C for 15 to 120 min) and nonisothermal (cooling at 1 °C min⁻¹) conditions. Isoconversional kinetic analysis of DSC data on gel melting (gel-sol transition) of all types of gels revealed significant variations in the activation energy throughout the process. Activation energy barrier to melting of isothermally prepared gels was in the range 160-190 kJ mol⁻¹ and found to increase with increasing the annealing temperature that was the major effect discovered. Activation energy barrier to melting of nonisothermally prepared gels was determined to be around 120-140 kJ mol⁻¹ and increase with increasing the concentration. Local reversibility of the gel melting was demonstrated by using temperature modulated DSC.     

Kinematic viscosity of biodiesel components (fatty acid alkyl esters) and related compounds at low temperatures

Biodiesel, defined as the mono-alkyl esters of vegetable oils and animal fats is, has undergone rapid development and acceptance as an alternative diesel fuel. Kinematic viscosity is one of the fuel properties specified in biodiesel standards, with 40 °C being the temperature at which this property is to be determined and ranges of acceptable kinematic viscosity given. While data on kinematic viscosity of biodiesel and related materials at higher temperatures are available in the literature, this work reports on the kinematic viscosity of biodiesel and a variety of fatty acid alkyl esters at temperatures from 40 °C down to −10 °C in increments of 5 °C using the appropriately modified standard reference method ASTM D445. Investigating the low-temperature properties of biodiesel, including viscosity, of biodiesel and its components is important because of the problems associated with the use of biodiesel under these conditions. Such data may aid in developing biodiesel fuels optimized for fatty ester composition. An index termed here the low-temperature viscosity ratio (LTVR) using data at 0 °C and 40 °C (divide viscosity value at 0 °C by viscosity value at 40 °C) was used to evaluate individual compounds but also mixtures by their low-temperature viscosity behavior. Compounds tested included a variety of saturated, monounsaturated, diunsaturated and triunsaturated fatty esters, methyl ricinoleate, in which the OH group leads to a significant increase in viscosity as well as triolein, as well as some fatty alcohols and alkanes. Esters of oleic acid have the highest viscosity of all biodiesel components that are liquids at low temperatures. The behavior of blends of biodiesel and some fatty esters with a low-sulfur diesel fuel was also investigated.     

DSC, dielectric and dynamic mechanical behavior of two- and three-component ordered polyurethanes

Liquid crystalline (LC) polyurethanes were made from two diisocyanates (flexible HMDI and stiff TDI) (DIs), mesogenic diol (D) and a polybutadiene-diol (B) with stoichiometric ratios of reactive hydroxy (OH) and isocyanate (NCO) groups ((NCO)_DI/((OH)_D+(OH)_B)=1/1). Two- (B/DIs, D/DIs) and three-component ((D+B)/DIs, D/B=1/1 by weight) polymers were prepared and their dielectric, dynamic mechanical and DSC behavior was investigated. For neat B, the glass transition temperature T_gB (∼−46 °C) was detected. Two-component B/HMDI and B/TDI polymers have exhibited a homogeneous structure with the glass transition temperatures T_gU∼−9 and 2 °C. On the other hand, for D/DI polymers on cooling from the melt and subsequent heating the glass transitions at T_gU∼41 °C (D/HMDI) and 58 °C (D/TDI) together with nematic and smectic mesophases were found. In three-component systems, additional glass transitions at T_gB∼−41 °C (B/D/HMDI) and −31 °C (B/D/TDI) were observed. This means that the polymers exhibit a distinct two-phase structure with soft polybutadiene (B) and hard polyurethane (D/DI) phases. In hard polyurethane phase, the glass transitions at T_gU and LC mesophases similar to those found in two-component D/DI polyurethanes were detected. Dielectric and dynamic mechanical results correlate well with DSC measurements.     

Study on the thermal behavior of a solution-cast liquid-crystalline polymer film by positron-annihilation lifetime spectroscopy

The thermal behavior of a solution-cast liquid-crystalline polymer (LCP) film was extensively studied by positron-annihilation lifetime spectroscopy (PALS). From the positronium (Ps) lifetimes of the first heating process from 40 to 250 °C at a heating rate of 2.5 °C/h, four characteristic temperatures (140, 170, 200, 235 °C) were observed. From a combined investigation with conventional differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA), the first three characteristic temperatures were found to correspond to reorientation, glass-transition, and softening temperatures, respectively. The fourth temperature was related to the commencement of crystallization, which was observed above about 235 °C from a decrease in the Ps lifetime. A low-temperature PALS experiment exhibited the γ-transition due to rotation of the phenyl moiety at about −53 °C.     

Biodiesel production from pomace oil and improvement of its properties with synthetic manganese additive

Renewable energy sources are attracting more attention due to lower cost and lower pollution relative to fossil fuels. The aim of this experimental work is the production of renewable and clean methyl ester from pomace oil as an alternative fuel. This oil was obtained from pomace which is the waste of olive oil plants. Optimum producing conditions were determined experimentally. The maximum yield was obtained at 30% of methanol/oil ratio, 60 °C temperature for 60 min with NaOH catalyst. The properties of the biodiesel thus obtained were compared with diesel fuel requirements. An organic based Manganese additive improved the biodiesel properties. Doping the fuel at a ratio of 12 μmol/l oil methyl ester led to a 20.37% decrease in viscosity, 7 °C fall in the flash point and reduced the pour point from 0 °C to −15 °C. This blend of pomace oil methyl ester-diesel fuel with manganese additive was tested in a direct injection diesel engine. The maximum effect of the new fuel blend and diesel fuel on engine performance was obtained at 1400 rpm.     

Improving the cold flow properties of biodiesel from waste cooking oil by surfactants and detergent fractionation

The use of surfactants and detergent fractionation to improve the cold flow properties of biodiesel from waste cooking oil (BWCO) was investigated. The effect of five types of surfactants, including sugar esters (S270 and S1570), silicone oil (TSA 750S), polyglycerol ester (LOP-120DP) and diesel conditioner (DDA) on the reduction of the cold filter plugging point (CFPP) of the BWCO, was evaluated, with the greatest reduction to the CFPP of the BWCO (from −10 °C to −16 °C) being was achieved by the addition of 0.02 wt% of polyglycerol ester (LOP-120P). Detergent fractionation of the BWCO was performed by first mixing partially crystallized biodiesel with a chilled detergent (sodium dodecylsulfate) solution accompanied by an electrolyte (magnesium sulfate), and then separating the mixture by centrifugation to obtain the BWCO liquid. An orthogonal experimental design was utilized to investigate the effects of the various parameters on detergent fractionation. The optimal parameters, as obtained by range analysis, were as follows: detergent loading 0.3 wt%, electrolyte loading 1.0 wt%, and water loading 150 wt%. The CFFP of the liquid biodiesel from waste cooking oil (LBWCO) was −17 °C with a yield of 73.1% when the detergent fractionation was performed under these conditions. A limited number of biodiesel physical and chemical properties were analyzed before and after the addition of surfactants and detergent fractionation.     

Synthesis, characterization and optical properties of fluorinated poly(aryl ether)s containing phthalazinone moieties

A series of novel fluorinated poly(aryl ether)s containing phthalazinone moieties (FPPEs) have been prepared by a modified synthetic procedure for optical waveguide applications. The obtained random copolymers exhibited excellent solubility in polar organic solvents, high glass transition temperatures (T_gs: 185-269 °C), good thermal stabilities (the temperatures of 1% weight loss: 487-510 °C) and good optical properties. By adjusting the feed ratio of the reactants, the refractive indices of TE and TM modes (at 1550 nm) could be well controlled in the range of 1.575-1.498 and 1.552-1.484, respectively. The optical losses of the FPPEs exhibited relatively low values (less than 0.27 dB/cm at 1310 nm). Additionally, the thermo-optic coefficient (dn/dT) values of the FPPEs at 1310 nm and 1550 nm (TE mode) ranged from −0.97 × 10⁻⁴ °C to −1.33 × 10⁻⁴ °C and from −0.96 × 10⁻⁴ °C to −1.29 × 10⁻⁴ °C, respectively.     

Roselle (Hibiscus sabdariffa L.) oil as an alternative feedstock for biodiesel production in Thailand

The production of biodiesel fuel from crude roselle oil was evaluated in this study. The process of alkali-catalyzed transesterification with methanol was carried out to examine the effects of reaction variables on the formation of methyl ester: variables which included methanol-to-oil molar ratios of 4:1-10:1, catalyst concentrations of 0.25-2.0% w/w of oil, reaction temperatures of 32-60 °C, and reaction times of 5-80 min. The methyl ester content from each reaction condition was analyzed by gas chromatography (GC), the optimum condition having been achieved at a methanol-to-oil molar ratio of 8:1, a catalyst concentration of 1.5% w/w of oil, a reaction temperature of 60 °C, and a reaction time of 60 min. The resultant methyl ester content of 99.4% w/w, plus all of the other measured properties of the roselle biodiesel, met the Thai biodiesel (B100) specifications and international standards EN 14214:2008 (E) and ASTM D 6751-07b, with the exception of a higher carbon residue and lower oxidation stability.     

Hybrid proton-conducting membranes for polymer electrolyte fuel cells: Phosphomolybdic acid doped poly(2,5-benzimidazole)—(ABPBI-H3PMo12O40)

The synthesis and characterization of a novel hybrid organic-inorganic material formed by phosphomolybdic acid H₃PMo₁₂O₄₀ (PMo₁₂) and poly(2,5-benzimidazole) (ABPBI) is reported. This material, composed of two proton-conducting components, can be cast in the form of membranes from methanesulfonic acid (MSA) solutions. Upon impregnation with phosphoric acid, the hybrid membranes present higher conductivity than the best ABPBI polymer membranes impregnated in the same conditions. These electrolyte membranes are stable up to 200 °C, and have a proton conductivity of 3 × 10⁻² S cm⁻¹ at 185 °C without humidification. These properties make them very good candidates as membranes for polymer electrolyte membrane fuel cells (PEMFC) at temperatures of 100-200 °C.     

Electrochemical behavior of ionically crosslinked polyampholytic gel electrolytes

An ionic complex of anionic and cationic monomers was obtained by protonation of (N,N-diethylamino)ethylmethacrylate (DEA) with acrylic acid (AAc). Free radical copolymerization of the ionic complex and acrylamide (AAm), yielded the ionically crosslinked polyampholytic gel electrolytes [poly(AAc-DEA-AAm), designated as PADA] using two types of organic solvents containing a lithium salt. The PADA gel electrolyte exhibited good thermal stability shown by the DSC thermogram. The impedance analysis at temperatures ranging from −30 to 75 °C indicated that the ionic conductivities of the PADA gel electrolytes were rather close to those of liquid electrolytes. The temperature dependence of the ionic conductivities was found to be in accord with the Arrhenius equation. Moreover, the ionic conductivities of PADA gel electrolytes increased with an increase of the molar ratios of cationic/anionic monomers. The ionic conductivities of PADA gels prepared in solvent mixtures of propylene carbonate, ethyl methyl ether and dioxolane (3:1:1, v/v) were higher than those of PADA gels prepared in propylene carbonate only. Significantly, the ionic conductivities of two kinds of PADA gel electrolytes were in the range of 10⁻³ and 10⁻⁴ S cm⁻¹ even at −30 °C. The electrochemical windows of PADA gel electrolytes measured by cyclic voltammetry were in the range from −1 V to 4.5 V.     

Operation characteristics of portable direct methanol fuel cell stack at sub-zero temperatures using hydrocarbon membrane and high concentration methanol

Cold start and operation of a direct methanol fuel cell (DMFC) are investigated at sub-zero temperatures by using a 10-cell stack. The stack is manufactured with a hydrocarbon membrane to minimize the methanol crossover problem, which can be caused by use of high concentration methanol solutions. The stack is heated up for the cold start and operation only by heat of the exothermic reactions without any heating device and additional insulation means, to examine operation characteristics of the DMFC stack at low temperatures. The concentration of methanol solutions is selected in the range of 3-8 M, considering the freezing points of the solution for corresponding operation temperatures (−5 to −15 °C). Although the DMFC stack undergoes a sharp voltage drop and a significant performance decrease at the initial stage of the frozen condition, the self-heating DMFC are successfully operated at −5 and −10 °C in both constant current or constant voltage modes. The cold start-up time also is nearly independent of the operating modes. In contrast, the stack at −15 °C is barely started up only by a constant voltage mode with some voltage fluctuation. The DMFC stack after the cold operation exhibits the performance loss of about 45%. Such performance loss is mainly caused by degradation of the electrocatalysts.     

Structure and properties of highly stereoregular isotactic poly(methyl methacrylate) and syndiotactic poly(methyl methacrylate) blends treated with supercritical CO2

The structure and properties of highly stereoregular isotactic poly(methyl methacrylate) (it-PMMA) and syndiotactic poly(methyl methacrylate) (st-PMMA) blends with crystalline stereocomplex formed by supercritical CO₂ treatment at temperatures ranging from 35 to 130 °C were investigated by means of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and dynamic mechanical analysis (DMA) measurements. The melting temperature, T_m, and the heat of fusion, ΔH_m, had maximum values at about 200 °C and 25 J/g, respectively. The degree of crystallinity evaluated by WAXD ranged in value from 32 to 38%. The fringed-micellar stereocomplex crystallites were formed in case of treatment temperatures below 90 °C, and the orderliness perpendicular to the helix axis of the fringed-micellar crystallites was considered to be increased with increasing treatment temperature. In case of treatment temperature of 130 °C, the fringed-micellar crystallites and the lamellar crystallites with high orderliness parallel to the helix axis coupled with the perpendicular orderliness were formed, and the respective double endothermic peaks, T_m¹ and T_m³, were observed in DSC due to the melting of the two kinds of stereocomplex crystallites. The it-PMMA/st-PMMA blends containing the fringed-micellar crystallites maintained high values of storage modulus, E′, up to higher temperature compared with the amorphous blends. The E′ of the blend treated with CO₂ at 130 °C decreased twice at temperatures corresponding to T_m¹ and T_m³.     

Fast isothermal calorimetry of modified polypropylene clay nanocomposites

Calorimetric experiments at cooling rates comparable to those during injection molding, as an example, are needed to study phase transitions under conditions relevant for processing. Ultra fast scanning calorimetry is a technique which provides a means to analyze the materials of interest under rapid cooling conditions and it is a promising technique by which the crystallization behavior of composite systems based on fast crystallizing polymers like isotactic polypropylene (iPP) can be studied. By combining conventional DSC and ultra fast chip calorimetry isothermal crystallization experiments were performed in the whole temperature range between glass transition and melting temperature of iPP. Because of the very small time constant of the calorimeter, isothermal crystallization processes with peak times down to 100 ms were investigated after cooling the sample from the melt at 2000 K/s. iPP grafted with maleic anhydride (PPgMA) - montmorillonite clay nanocomposites were studied. The influence of various clay loadings on the crystallization behavior of PPgMA at different temperatures was followed by ultra fast isothermal calorimetry. PPgMA clay nanocomposites showed a variation in crystallization peak times with different clay loadings at crystallization temperatures between 70 °C and 100 °C. No influence of clay loading was observed at lower crystallization temperatures. At these temperatures, where the mesophase is formed and homogeneous nucleation is expected, the contribution of the clay as a nucleating agent is negligible. For crystallization at about 80 °C, where the α-phase is formed, the nucleating effect of the clay is observed yielding complex crystallization kinetics. In the temperature range 75-85 °C in some nanocomposites a double peak during isothermal crystallization was observed corresponding to a fast and a slow crystallization processes occurring simultaneously. At higher temperatures, above 120 °C, the clay slightly retards the crystallization process.     

Production of lubricating base oil from slop wax by different subsequent refining techniques

Different subsequent refining techniques including solvent dewaxing and solvent extraction have been used to produce lubricating base oil from slop wax waste by-product. The solvent dewaxing technique was performed using two different solvent mixtures of methyl ethyl ketone and toluene with and without benzene at different dilution solvent ratios and at different dewaxing temperatures. The solvent extraction technique was carried out using N-methyl-2-pyrrolidone solvent at 90 °C and at constant dilution solvent ratio of 3:1 by weight. The resulting data revealed that the highest yield of lubricating base oil having the lowest pour point (−6 °C) and the highest iso- and cyclo-paraffins to n-paraffins ratio (5.11) is obtained by solvent dewaxing process only. While the lowest yield of lubricating base oil having the highest pour point (−1 °C) and the lowest iso- and cyclo-paraffins to n-paraffins ratio (4.08) is obtained using solvent dewaxing followed by solvent extraction process. These lubricating base oil products, especially the one that having the lowest pour point (−6 °C) matches the principal characteristics of AX 973853 type of premium low viscosity textile machinery oils obtained by Mobile Velocite Oil Company.     

Proton conducting membrane containing room temperature ionic liquid

A new proton conducting membrane containing room temperature ionic liquid: 2,3-dimethyl-1-octylimidazolium trifluoromethanesulfonylimide (DMOImTFSI) and polyvinylidenefluoride-co-hexafluoropropylene (PVdF-HFP) has been developed in the present work. The addition of bis(trifluoromethanesulphonyl)imide (HN(CF₃SO₂)₂) to this membrane results in an increase in conductivity by one order of magnitude at 25 °C. The membrane shows a conductivity of 2.74 × 10⁻³ S/cm at 130 °C along with good mechanical stability. The membrane was tested in a commercial fuel cell test station at 100 °C with dry hydrogen and oxygen gas reactants using Pt/C electrodes. The membrane containing the ionic liquid has been found to be electroactive for hydrogen oxidation and oxygen reduction at the platinum electrode and can be developed for use in proton exchange membrane fuel cell (PEMFC) under non-humid conditions at elevated temperatures.     

Effects of pore fractal structures of ultrafine coal water slurries on rheological behaviors and combustion dynamics

The ultrafine coal water slurry (CWS) with the particle size of 1-10 μm, ash content of 1-2%, solid concentration of 50% is a promising substitute fuel for diesel oil. The effects of pore fractal structures of three ultrafine CWSs on their rheological behaviors and combustion dynamics were studied in this paper. When the pore fractal dimensions of Yanzhou, Huainan and Shenhua ultrafine CWSs increase, their apparent viscosities all increase and the increase extents gradually enlarge with decreasing shear rates, while their ignition temperatures and apparent activation energies all decrease. For example, when the pore fractal dimension of Yanzhou coal increases from 2.31 to 2.43, the CWS apparent viscosity at a low shear rate of 12 s⁻¹ increases from 75 mPa s to 2400 mPa s, and that at a high shear rate of 100 s⁻¹ increases from 80 mPa s to 820 mPa s. Meanwhile, the ignition temperature of Yanzhou CWS decreases from 445 °C to 417 °C at a heating rate of 12.5 °C/min, and the apparent activation energy decreases from 104 kJ/mol to 32 kJ/mol.     

The influence of a new fabrication procedure on the catalytic activity of ruthenium-selenium catalysts

A new procedure has been introduced to enhance catalytic activity of ruthenium-selenium electro-catalysts for oxygen reduction, in which materials are treated under hydrogen atmosphere at elevated temperatures. The characterisation using scanning electron microscopy, energy dispersive spectroscopy or energy dispersive X-ray spectroscopy exhibited that the treatment at 400 °C made catalysts denser while their porous nature remained, led to a good degree of crystallinity and an optimum Se:Ru ratio. The half cell test confirms feasibility of the new procedure; the catalyst treated at 400 °C gave the highest reduction current (55.9 mA cm⁻² at −0.4 V) and a low methanol oxidation effect coefficient (3.8%). The direct methanol fuel cell with the RuSe 400 °C cathode catalyst (2 mg RuSe cm⁻²) generated a power density of 33.8 mW cm⁻² using 2 M methanol and 2 bar oxygen at 90 °C. The new procedure produced the catalysts with low decay rates. The best sample was compared to the Pt and to the reported ruthenium-selenium catalyst. Possible reasons for the observations are discussed.     

Performance of an anode-supported tubular solid oxide fuel cell (SOFC) under pressurized conditions

An anode-supported tubular solid oxide fuel cell (SOFC) with a 15-μm thick YSZ electrolyte and an active area of 100 cm² was successfully fabricated by co-firing process, and the cell performance was measured under both atmospheric and pressurized conditions. The experimental results showed that the cell performance was significantly improved under the pressurized condition. When the pressure was increased from 1 to 6 atm, the maximum power density increased from 135.0 to 159.0 mW cm⁻² at 650 °C, and from 266.7 to 306.0 mW cm⁻² at 800 °C. The maximum power density at 800 °C and 4 atm was decreased from 334.8 to 273.9 mW cm⁻² when increasing the fuel utilization from 10% to 90%. Under the test condition of 70% fuel utilization, 800 °C and 4 atm, the cell could run stably at 0.7 V and 350 mA cm⁻² for 50 h, almost without any performance loss.