Temperature Dependence of HNE Formation in Vegetable Oils and Butter Oil

The temperature dependence of the formation of toxic 4-hydroxy-2-trans-nonenal (HNE) was investigated in high and low linoleic acid (LA) containing oils such as corn, soybean and butter oils. These oils contain about 60, 54 and 3–4% of LA for corn, soybean and butter oils, respectively. The oils were heated for 0, 0.5, 1, 2, and 3 h at 190 °C and for 0, 5, 15 and 30 min at 218 °C. HNE concentrations in the oils were analyzed by high performance liquid chromatography (HPLC). The maximum HNE concentrations in heated (190 °C) corn, soybean and butter oils were 5.46, 3.73 and 1.85 μg HNE/g oil, respectively. The concentration of HNE at 218 °C increased continuously for all the three oils, although they were heated for much shorter periods compared to the lower temperature of heating (190 °C). HNE concentration at 30 min reached the maximum of 15.48, 10.72 and 6.71 μg HNE/g oil for corn, soybean and butter oils, respectively. HNE concentration at higher temperature (218 °C) was 4.9, 3.7, and 8.7 times higher than at the lower temperature (190 °C) and 30 min of heating for corn, soybean and butter oils, respectively. It was found that HNE formation was temperature dependant in the tested oils.     

Aqueous Enzymatic Extraction of Oil and Protein Hydrolysates from Roasted Peanut Seeds

To evaluate the effects of the roasting process on the extraction yield and oil quality, peanut seeds were roasted at different temperatures (130–220 °C) for 20 min prior to the aqueous extraction of both oil and protein hydrolysates with Alcalase 2.4 L. Roasting temperatures did not significantly affect the yields of free oil, whereas the temperature of 220 °C led to a reduced recovery of protein hydrolysates. The color and acid values of peanut oils did not change significantly with roasting temperatures. The enzyme-extracted oil with roasting at 190 °C had a relatively low peroxide value, a strong oxidative stability, and the best flavor score. Using the same seed-roasting temperature (190 °C), quality attributes such as color, acid and peroxide values, phosphorus content and oxidative stability of the enzyme-extracted oil were better than those of the oil obtained by an expeller. After the peanut seeds were roasted at 190 °C for 20 min, with a seeds-to-water ratio of 1:5, an enzyme concentration of 2%, and an incubation time of 3 h, the yields of free oil and protein hydrolysates were 78.6 and 80.1%, respectively. After demulsification of the residual emulsion by a freezing and thawing method, the total free oil yield increased to 86–90%.     

Catalytic synthesis of triazine compounds using a flexible technology

Based on laboratory pilot studies, we have developed a flow sheet for the catalytic synthesis of triazine compounds from carbamide using a flexible technology and a catalyst for this process. The main process parameters are as follows: a carbamide melt is fed into the reactor under a pressure of 0.8 MPa at 140–160°C; the volume rate of feeding the circulating gas into the reactor is 500–750 h⁻¹, its temperature is 350–500°C, and the melt-to-gas mass ratio is 1: (7–9). The temperature of synthesis in the reactor is 350–450°C; the pressure in the reactor is 0.1–0.2 MPa. The sublimation temperature is 180–200°C. The conversion of carbamide is ∼98%. The content of the target component in the product is ∼98.8%. Depending on the composition of the circulating gas, it is possible to obtain products of melamine, cyanuric acid, or melamine cyanurate. A catalyst in the form of promoted active aluminum oxide with an inner surface of 300 to 400 m²/g and a technique for its preparation have been developed.     

Continuous slurry hydrogenation of soybean oil with copper-chromite catalyst at high pressure

Selective hydrogenation of soybean oil to reduce linolenic acid is accomplished better with copper than with nickel catalysts. However, the low activity of copper catalysts at low pressure and the high cost of batch equipment for high-pressure hydrogenation has precluded their commercial use so far. To evaluate continuous systems as an alternative, soybean oil was hydrogenated in a 120 ft × 1/8 in. tubular reactor with copper catalyst. A series of hydrogenations were performed according to a statistical design by varying processing conditions: oil flow (0.5 L/hr, 1.0 L/hr and 2.0 L/hr), reaction temperature (180 C and 200 C), hydrogen pressure (1,100 psig and 4,500 psig) and catalyst concentration (0.5% and 1.0%). An iodine value (IV) drop of 8–43 units was observed in the products whereas selectivity varied between 7 and 9. Isomerization was comparable to that observed with a batch reactor. Analysis of variance for isomerization indicated interaction between catalyst concentration and hydrogen pressure and between catalyst concentration and temperature. The influence of pressure on linolenate selectivity was different for different temperatures and pressure. Hydrogenation rate was significantly affected by pressure, temperature and catalyst concentration.     

Homogeneous catalytic hydrogenation of canola oil using a ruthenium catalyst

Dichlorodicarbonylbis (triphenylphosphine) ruthenium (II), RuCl₂ (CO)₂ (PPh₃)₂, was investigated as a catalyst for edible oil hydrogenation in a preliminary screening of potential catalysts for producing partially hydrogenated fats with lowtrans-isomer content. Refined, bleached and deodorized canola oil was hydrogenated using 1.77 × 10⁻⁵ − 6.64 × 10⁻⁴ mol/kg-oil of ruthenium catalyst equivalent to 1.79 × 10⁻⁴ − 6.71 × 10⁻³ wt% Ru. The effects of temperature (50–180 C) and pressure (50–750 psig) on reaction rate,trans-isomer content and fatty acid composition were examined. The activities of RuCl₂ (CO)₂ (PPh₃)₂ and nickel (Nysel HK-4 and AOCS standard nickel catalyst) were compared on a molar basis. At 4.40 × 10⁻⁴ mol/kg-oil (0.0026 wt/Ni or 0.0044 wt% Ru), 140 C and 50 psig, the nickel catalysts were completely inactive, but the ruthenium catalyst produced an IV drop of 40 units in 60 min. At 110 C, 750 psig and 1.34 × 10⁻⁴ mol/kg-oil (1.35 × 10⁻³ wt% Ru), a hydrogenation rate of 0.89 ΔIV/min and a maximumtrans-isomer content of 10.4% (IV=45.0) was obtained with the ruthenium catalyst.     

Column Fractionation of Canola Oil Deodorizer Distillate Using Supercritical Carbon Dioxide

Semi-continuous column fractionation of canola oil deodorizer distillate using supercritical CO₂ (SCCO₂) was carried out to determine the feasibility of value-added processing of this feed material for the recovery of bioactive components such as sterols and tocopherols and to determine the effect of operating conditions [pressure (20, 25 MPa using a temperature gradient of 70–100 °C), temperature (70, 100 °C) and a linear temperature gradient (70–100 °C at 25 MPa)] on extract yield and separation efficiency. Total extract yield increased significantly (p ≤ 0.05) with pressure, whereas at isobaric conditions (25 MPa) the highest yield was obtained at the lowest temperature tested (70 °C). Fractionation efficiency was reflected in the composition of fractions and was affected by operating conditions. Residue composition was determined by extract yield in addition to selectivity. Use of the thermal gradient (70–100 °C) decreased the content of volatiles, free fatty acids and tocopherols while increasing sterol content significantly (p ≤ 0.05) to a level of 40% (GC area %) in the residue obtained at 25 MPa. The findings indicate the potential of canola oil deodorizer distillate as a source of sterols and warrant further research on the countercurrent column fractionation to improve the separation efficiency.     

Selective hydrogenation of soybean oil: X. Ultra high pressure and low pressure1

Soybean oil was partially hydrogenated with copper-chromite catalyst at 170 C and up to 30,000 psig hydrogen pressure. Catalyst activity increased with increase in pressure up to 15,000 psig. The linolenate selectivity (S_Ln) of the reaction remained essentially unchanged over 50–1000 psig pressure range. A S_Ln of 5.5 to 5.6 was achieved at 15,000 to 30,000 psig pressure range. This value is somewhat lower than the selectivity at 50–1000 psig, but much higher than that obtained with nickel catalysts. Geometric isomerization increased as pressure increased up to 200 psig; above this pressure, the percenttrans remained the same up to 500 psig.trans Isomer content decreased when the pressure was increased to 30,000 psig. cis,trans Isomerization of linoleate was greater at 1000 psig and 15,000 psig than at 50 psig. At 15,000 psig, part of the linoleate in soybean oil was hydrogenated directly without prior conjugation, whereas at low pressures, all of the double bonds first conjugate prior to hydrogenation. This difference in mechanism might explain the lower selectivities obtained at high pressures. Conjugated diene isomers were found in the products up to 200 psig. Above this pressure conjugated diene was not measurable. No significant differences were found in the double bond distribution oftrans monoenes even though the amount oftrans monoene formed decreased as pressure was increased to 30,000 psig. 1 Presented at the AOCS meeting, San Francisco, May 1979.     

Preparation of anthracene fine particles by rapid expansion of a supercritical solution process utilizing supercritical CO<Subscript>2</Subscript>

The rapid expansion of a supercritical solution (RESS) process is an attractive technology for the production of small, uniform and solvent-free particles of low vapor pressure solutes. The RESS containing a nonvolatile solute leads to loss of solvent power by the fast expansion of the supercritical solution through an adequate nozzle, which can cause solute precipitation. A dynamic flow apparatus was used to perform RESS studies for the preparation of fine anthracene particles in pure carbon dioxide over a pressure range of 150–250 bar, an extraction temperature range of 50–70 °C, and a pre-expansion temperature range of 70–300 °C. To obtain fine particles, 100, 200 and 300 μm nozzles were used to disperse the solution inside of the crystallizer. Both average particle size and particle size distribution (PSD) were dependent on the extraction pressure and the pre-expansion temperature, whereas extractor temperature did not exert any significant effect. Smaller particles were produced with increasing extraction pressure and preexpansion temperature. In addition, the smaller the nozzle diameter, the smaller the particles and the narrower the PSD obtained.     

Polymerization of propylene with Ziegler–Natta catalyst: optimization of operating conditions by response surface methodology (RSM)

Optimization of operational conditions for the polymerization of propylene with Ziegler–Natta catalyst was carried out via RSM. Response surface methodology (RSM) based on a three-level, four-variable Box–Behnken design was used to evaluate the interactive effects of reaction conditions such as reaction temperature (60–80 °C), monomer pressure (5–8 bar), hydrogen volume (130–170 mL), and cocatalyst to catalyst ratio (Al/Ti, 340–500) on the catalyst activity and melt flow rate (MFR). The optimum reaction conditions derived via RSM were: temperature 70 °C, pressure 8 bar, hydrogen volume 151 mL, and cocatalyst to catalyst ratio 390. The experimental catalyst activity and MFR were 8 g polypropylene/mg catalyst and 10.9 g/10 min, respectively, under optimum conditions. Optimum values were determined from process cost point of view and offered better operational conditions.     

Lipase-catalyzed hydrolysis of canola oil in supercritical carbon dioxide

The effect of pressure, temperature, and CO₂ flow rale on the extent of conversion and the product composition in the enzyme-catalyzed hydrolysis of canola oil in supercritical carbon dioxide (SCCO₂) was investigated using lipase from Mucor miehei immobilized on macroporous anionic resin (Lipozyme IM). Reactions were carried out in a continuous flow reactor at 10, 24, and 38 MPa and 35 and 55°C. Supercritical fluid chromatography was used to analyze the reaction products. A conversion of 63–67% (triglyceride disappearance) was obtained at 24–38 MPa. Mono-and diglyceride production was minimum at 10 MPa and 35°C. Monoglyceride production was favored at 24 MPa. The amount of product obtained was higher at 24–38 MPa due to enhanced solubility in SCCO₂. Complete hydrolysis of oil should be possible by increasing the enzyme load and/or decreasing the quantity of the oil substrate. There was a drop in triglyceride conversion over a 24-h reaction time at 38 MPa and 55°C, which may be an indication of loss of enzyme activity. Pressure, temperature, and CO₂ flow rate are important parameters to be optimized in the enzyme-catalyzed hydrolysis of canola oil in SCCO₂ to maximize its conversion to high-value products.     

Reaction of NO and N2O gases with graphite in TGA

Thermal analyses were conducted in a thermogravimetric analyzer by isothermal techniques in order to characterize the carbon-nitrogen oxide reaction. The carbon samples employed in the present study were SP-1 graphite and Micro 450 graphite. Carbon-NO and carbon-N₂O reactions were carried out in a temperature range of 550–900 °C and 5–20 kPa of the partial pressure of reactant. In the NO reaction, reaction orders with respect to NO concentration and activation energy were 0.46-0.92 and 85–102 kJ/mol, respectively. The rate on the monolayer edge was higher than the rate on the multilayer edges. In the N₂O reaction, reaction orders with respect to N₂O concentration and activation energy were 0.55–1.35 and 167–190 kJ/mol, respectively.     

Production of dehydrated fuel ethanol by pressure swing adsorption process in the pilot plant

Fermented ethanol is gaining wide popularity as a car fuel additive. The pressure swing adsorption (PSA) process is attractive for the dehydration of bioethanol on the industrial scale, since its energy consumption is low and it is capable of producing a very pure product. 3 ? zeolite possesses micro-pores which, due to their small size, adsorb water molecules but not ethanol molecules. In this work, up to 2 kL/day of dehydrated ethanol (99.5% by weight) was successfully produced with 3 ? zeolite by the pressure swing adsorption process. The cycles of the PSA process were operated under the following variables: feed flow rate (27–62 Nm³/hr of 93.2% by weight), purge/feed ratio (30–24%), adsorption temperature (130–140 °C) and adsorption pressure (1.2 atm).     

Effects of temperature and temperature shift on docosahexaenoic acid production by the marine microalge Crypthecodinium cohnii

The effects of temperature and temperature shift on the fatty acid composition and docosahexaenoic acid (DHA, C22∶6n−3) content and productivity of the marine microalga Crypthecodinium cohnii ATCC 30556 were investigated. The microalga grew well over the entire range of temperatures (15–30°C) studied. High temperature favored the growth of the microalga with the highest specific growth rate of 0.092 h⁻¹ at 30°C. In contrast, low temperature favored the formation of polyunsaturated fatty acids. The highest DNA content was obtained at 15°C in the early stationary phase (i.e., 72h). In order to achieve high DHA productivity, a shift from high temperature to low temperature at a later stage of cultivation (i.e., 48h) was also attempted. A temperature shift from 25°C (for 48 h) to 15°C (for 24 h) resulted in an increase in cellular DHA content by 19.9% and productivity by 6.5% as compared to that maintained at 25°C (for 72 h).     

Syntheses of 12-aminododecanoic and 11-aminoundecanoic acids from vernolic acid

12-Aminododecanoic acid and 11-aminoundecanoic acid, monomer precursors for nylon-12 and nylon-11, respectively, have been synthesized from vernolic (cis-12,13-epoxy-cis-9-octadecenoic) acid via a reaction sequence that includes the formation of 12-oxododecanoic acid oxime. Saponification of vernonia oil, followed by a low-temperature recrystallization at −20°C, gave 51% vernolic acid (97% purity, m.p. 23–25°C). Hydrogenation afforded cis-12,13-epoxystearic acid (m.p. 52–54°C, lit. m.p. 52–54°C), which upon oxidation with periodic acid in tertiary butyl alcohol gave 12-oxododecanoic acid with an isolated yield of 71.0%. Reaction of the oxoacid with hydroxylamine hydrochloride gave 12-oxododecanoic acid oxime, which was catalytically reduced to give 12-aminododecanoic acid with a yield greater than 85% and a melting point of 184–186°C (lit. m.p. 185–187°C). 11-Aminoundecanoic acid was prepared from the 12-oxododecanoic acid oxime via a three-step reaction sequence that involved a Beckmann rearrangement, Hofmann degradation, and hydrolysis. Thus, the aldoxime acid was hydrolyzed in the presence of nickel acetate tetrahydrate to give 11-carbamoylundecanoic acid (48% yield, m.p. 129–131°C, lit. m.p. 129–130°C). The amide was then treated with a solution of sodium methoxide and bromine at 70–80°C to give 11-(methoxycarbonylamino)undecanoic acid at 75% yield (m.p. 84–86°C; elemental analysis, calculated for C₁₃H₂₅NO₄: C, 60.19; H, 9.73; N, 5.40; O, 24.68%; found C, 60.02; H, 9.81; N, 5.26; O, 24.91%), which upon alkaline hydrolysis and subsequent neutralization gave 11-aminoundecanoic acid at 34% yield (m.p. 189–192°C, lit. m.p. 190°C). Mass spectrometric and ¹³C nuclear magnetic resonance data of the previously unreported 11-(methoxycarbonylamino)undecanoic acid is provided.     

Heat transfer in a high temperature fluidized bed

The heat transfer characteristics between the bed and immersed tube in a high temperature fluidized bed (7.5 cm I.D.×70 cm H) were investigated with sand and iron ore particles. The heat transfer coefficients were measured at operating temperatures of 200–600°C and gas velocities of 1–10 U_mf. The bed emissivity measured by the radiation probe was found to be 0.8–0.9. The experimentally obtained radiative heat transfer coefficient was in the range of 30–80 W/m²K for the operating temperature of 400–800°C and the contribution of radiation to total heat transfer was about 13% and 18% for the operating temperatures of 400°C and 600°C, respectively.     

Supercritical Carbon Dioxide Extraction and Characterization of Argentinean Chia Seed Oil

Extraction of chia seed oil was performed with supercritical carbon dioxide (SC-CO₂). To investigate the effects of pressure and temperature on the oil solubility and yield, two isobaric (250 and 450 bar) and two isothermal (40 and 60 °C) extraction conditions were selected. The global extraction yield of chia oil increased with pressure enhancement, but temperature had a little influence on it. The maximum oil recovery using SC-CO₂ at a mass flow rate of 8 kg/h was 97%, which was obtained at 60 °C, 450 bar for a 138-min extraction. The results showed that solubility changed from 4.8 g oil/kg CO₂ at 60 °C–250 bar to 28.8 g oil/kg CO₂ at 60 °C–450 bar. The final extract obtained by SC-CO₂ under different conditions and Soxhlet extraction contained mainly α-linolenic (64.9–65.6%) and linoleic (19.8–20.3%) acids. SC-CO₂ extraction is an interesting alternative methodology because it is possible to achieve a chia oil yield close to that obtained by conventional extraction with a similar fatty acid composition using an environmentally friendly process.     

Silicon carbide refractory castables

Optimum formulations for castables intended for different service conditions are proposed. Silicon carbide castables containing ultradisperse particles of cement, silica fume, and electrofused corundum are developed. The castables do not weaken on heating and display superior operational properties: the compressive strength is 40–80 MPa at sintering temperature 400°C and 50–85 MPa at 1300°C, the strain onset temperature under a load of 0.2 MPa is 1700–1510°C; thermal stability (1300°C — water) is better than 45 heating/cooling cycles (1300°C — water); no change in linear and volume dimensions was observed on heating. The newly-developed castables can find application in various sectors of industry, in particular, as the refractory material for the lining of Whiting furnaces and porcelain kilns. __________ Translated from Novye Ogneupory, No. 12, pp. 36–39, December, 2005.     

The acetolysis of glycerides. I. Preliminary investigation and approximate kinetics

Below 120°C., direct acidolysis of fats by acetic acid is vanishingly slow, the observed reaction being a slow hydrolytic fat splitting to partial glycerides followed by a rapid acetylation. Water is an essential reactant, and strong acid catalysis of the reaction is effective only in its presence. The reaction is unimolecular with respect to the acid catalyst, and probably also to the ester linkages, but molecularity falls below unity with respect to water, which has strong effects on acid strengths in an acetic acid medium. The reaction velocity has a temperature coefficient of 1.6 per 10°C. over the range 77–118°C. Using a three-fold weight of 98% acetic acid, 1% of catalyst, and 12–24 hours' reaction at 100–118°C., fat splits of around 90% can be attained.     

Soybean seed composition under high day and night growth temperatures

High diurnal temperatures often affect development of soybean [Glycine max (L.) Merr.], but little is known about the relative influence of high day and night temperatures on the chemical composition of the seed. This study was conducted to determine the effects of combinations of high day and night temperatures during flowering and pod set (R1–R5), seed fill and maturation (R5–R8), and continuously during the reproductive period (R1–R8) on soybean seed oil, protein, and fatty acid composition. Day/night temperatures of 30/20, 30/30, 35/20, and 35/30°C were imposed on the soybean cultivar Gnome 85 in growth chambers. The day/night temperature combinations during R1–R5 had little effect on the oil and protein concentration and the fatty acid composition of seed produced. As mean daily temperature increased from 25 (30/20) to 33 (35/30)°C during R5–R8 and 25 (30/20) to 33 (35/30)°C during R1–R8, and oil concentration decreased and protein concentration increased. Increased day temperature during R5–R8 and R1–R8, averaged across the two night temperatures, increased oleic acid and decreased linoleic and linolenic acids. When night temperature was increased at 30°C day temperature during R5–R8 and R1–R8, oleic acid decreased and linoleic acid increased. When night temperature was increased at 35°C day temperature during R1–R8, oleic acid increased, and linoleic and linolenic acids decreased. These results indicate the importance of high day and night temperatures during seed fill and maturation in the oil, protein, and fatty acid composition of soybean seed.     

Production of low ash coal by thermal extraction with <Emphasis Type="Italic">N</Emphasis>-methyl-2-pyrrolidinone

Present study was conducted for the purpose of producing low ash coal from LRC (low rank coals) such as lignite and sub-bituminous coal through thermal extraction using polar solvent. Extraction from bituminous coal was also investigated for comparison. NMP as a polar solvent was used. The ratio of coal to solvent was adjusted as 1: 10. Experimental conditions were established which include the extraction temperature of 200–430 °C, initial applied pressure of 1–20 bar and extraction time of 0.5–2 hr were used. Extraction yield and ash content of extracted and residual coal were measured. The extraction yield increased with the increase of extraction temperature, and the ash content of extracted coal decreased below 0.4% at 400 °C from the raw coal samples that have the ash contents of 4–6%. According to the analysis of experiments results, fixed carbon and calorific value increased, and H/C and O/C decreased.