Prediction of higher heating values of biomass from proximate and ultimate analyses

Two new empirical correlations based on proximate and ultimate analyses of biomass used for prediction of higher heating value (HHV) are presented in this paper. The correlations have been developed via stepwise linear regression method by using data of biomass samples (from the open literature) of varied origin and obtained from different geographical locations. The correlations have been validated via incorporation of additional biomass data. The correlation based on ultimate analysis (HHV = 0.2949C + 0.8250H) has a mean absolute error (MAE) lower than 5% and marginal mean bias error (MBE) at just 0.57% which indicate that it has good HHV predictive capability. The other correlation which is based on proximate analysis (HHV = 0.1905VM + 0.2521FC) is a useful companion correlation with low absolute MBE (0.67%). The HHV prediction accuracies of 12 other correlations introduced by other researchers are also compared in this study.     

Quantitative structure-property relationships for normal saturated and unsaturated fatty acids

Quantitative structure-property relationships, a technique of deriving properties of compounds from knowledge of their structures, has been applied to aliphatic carboxylic acids, an industrially important group of compounds. Equations have been developed from the molecular connectivity of the first order and the molar refraction as inputs which, on testing with data of seven properties, yielded average absolute deviations ranging between 0.9 and 6.7%. The compounds studied ranged between C₁ and C₃₀ for saturated and C₃ to C₂₂ for unsaturated fatty acids. The properties studied are normal melting and boiling points, critical temperature and pressure, and heats of fusion, combustion and formation.     

Proximate analysis based multiple regression models for higher heating value estimation of low rank coals

In this paper, multiple nonlinear regression models for estimation of higher heating value of coals are developed using proximate analysis data obtained generally from the low rank coal samples as-received basis. In this modeling study, three main model structures depended on the number of proximate analysis parameters, which are named the independent variables, such as moisture, ash, volatile matter and fixed carbon, are firstly categorized. Secondly, sub-model structures with different arrangements of the independent variables are considered. Each sub-model structure is analyzed with a number of model equations in order to find the best fitting model using multiple nonlinear regression method. Based on the results of nonlinear regression analysis, the best model for each sub-structure is determined. Among them, the models giving highest correlation for three main structures are selected. Although the selected all three models predicts HHV rather accurately, the model involving four independent variables provides the most accurate estimation of HHV. Additionally, when the chosen model with four independent variables and a literature model are tested with extra proximate analysis data, it is seen that that the developed model in this study can give more accurate prediction of HHV of coals. It can be concluded that the developed model is effective tool for HHV estimation of low rank coals.     

Participation of free fatty acids in the oxidation of purified soybean oil during microwave heating

Effects of 0 to 1.0% levels of caprylic, capric, lauric, myristic, palmitic or stearic acid on the oxidative stability of purified soybean oil were investigated under microwave heating conditions. A prooxidative effect of the fatty acids introduced into the systems was established. The extent of this effect depended on the acyl chin and levels of added fatty acids. During microwave heating, the oxidative rate of purified soybean oil by the fatty acids was rapid compared to the addition of their corresponding hydrocarbons; the shorter the chainlength and the higher the levels of fatty acids, the more accelerated was the thermal oxidation in the oil. The results are explained on the basis of the catalytic effect of the carboxylic group on the formation of free radicals by the decomposition of hydroperoxides. Therefore, particular attention should be paid to the free fatty acid content, which affects the oxidative stability of purified soybean oil.     

Effects of the incorporation of saturated fatty acids on the mechanical and barrier properties of biodegradable films

The effects of saturated fatty acids at a concentration of 1.5% on the mechanical and barrier properties of starch‐based films were evaluated in films prepared with two concentrations of glycerol, 20 and 25%. The water vapor permeability (WVP) was determined at three ranges of relative humidity, RH, (0–33, 33–64 and 64–97%). In all cases, an increase in WVP values was observed with increasing RH. SEM images showed a more homogeneous and compact structure in the films with caproic and lauric acids. The films with fatty acids showed higher elongation and maximum stress, and they had Young's modulus values close to those of the control; thus, the addition of fatty acids did not impair the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Viscosities of some long-chain fatty acids and their relationship with chainlength

The densities and viscosities of octanoic, decanoic, dodecanoic and tetradecanoic acids were determined at temperatures ranging from 20 to 80°C. When the fluidities were plotted against the molal volumes of the acids, curves were obtained. The intrinsic volumes were determined by extrapolation to zero fluidity and compared with previously reported values. Based upon Hildebrand’s equation for non- associated liquids, semiempirical equations relating the fluidity with the carbon number were obtained. The equations predict the fluidities of fatty acids with carbon number ranging from 4 to 18 at 4 temperatures from 20°C to 75°C with reasonable agreement with the experimental values.     

Viscosities of vegetable oils and fatty acids

Data for viscosity as a function of temperature from 24 to 110°C (75 to 230°F) have been measured for a number of vegetable oils (crambe, rapeseed, corn, soybean, milk-weed, coconut, lesquerella) and eight fatty acids in the range from C₉ to C₂₂. The viscosity measurements were performed according to ASTM test methods D 445 and D 446. Several correlations were fitted to the experimental data. Correlation constants for the best fit are presented. The range of temperature in which the correlations are valid is from 24°C (75°F), or the melting point of the substance, to 110°C (230°F). The correlation constants are valuable for designing or evaluating such chemical process equipment as heat exchangers, reactors, distillation columns, mixing vessels and process piping.     

Surface tension of fatty acids and triglycerides

Surface tension as a function of temperature was measured for four fatty acids (lauric, myristic, palmitic, and oleic) and two triglycerides (tricaprylin and tripalmitin). These surface tension measurements were performed using a K12 vers. 3.1 (Krüss GmbH) tensiometer at temperatures from 20 (or the melting point of each substance) to 90°C. The constants for a van der Waals-type correlation as well as for a linear equation are presented. Both equations are quite accurate, presenting mean deviations not exceeding 0.570%. Such correlation constants are valuable in the design or evaluation of processing equipment, especially that involving gas-liquid contact such as distillation and stripping columns, deodorizers, reactors, and equipment for physical refining.     

Viscosities of fatty acids, triglycerides, and their binary mixtures

Viscosity data have been obtained as a function of temperature for seven fatty acids (pelargonic, capric, lauric, myristic, palmitic, stearic, and oleic) and four triglycerides (tricaprilin, tripalmitin, tristearin, and triolein) and their binary mixtures at temperatures from above their melting points to 90°C. The viscosity measurements were performed by using Cannon Fenske glass capillary kinematic viscometers. Modified versions of the Andrade equation were used to correlate the kinematic viscosities of pure fatty acids and pure triglycerides. The MacAllister method was used for their binary mixtures. The correlation constants are valuable for designing or evaluating chemical process equipment, such as heat exchangers, reactors, distillation columns, and process piping.     

Prediction of seasonal variation of butters by computing the fatty acids composition with artificial neural networks

The seasonal variation of the fatty acids composition of butters were investigated over three seasons during a 12‐month study in the protected designation of origin Parmigiano‐Reggiano cheese area. Fatty acids were analyzed by GC‐FID, and then computed by artificial neural networks (ANN). Compared with spring and winter, butter manufactured from summer milk creams showed an optimal saturated/un‐saturated fatty acids ratio (?8.89 and ?5.79%), lower levels of saturated fatty acids (?2.63 and ?1.68%) and higher levels of mono‐unsaturated (+5.50 and +3.45%), poly‐unsaturated fatty acids (+0.65 and +0.17%), and rumenic acid (+0.55 and +3.41%), while vaccenic acid had lower levels in spring and higher in winter (?2.94 and +2.91%). Moreover, the ANN models were able to predict the season of production of milk creams, and classify butters obtained from spring and summer milk creams on the basis of the type of feeding regimens. Practical applications: The investigation on variables that affect the milk fatty acids composition can improve the quality of milk across all systems, and the combination of chromatographic and computational techniques will ensure a secure traceability enabling producers to characterize dairy products.     

Viscosities of fatty acids and methylated fatty acids saturated with supercritical carbon dioxide

The viscosities of several types of lipids saturated with supercritical carbon dioxide (SC-CO₂) were measured with a high-pressure capillary viscometer. Oleic acid and linoleic acid were evaluated from 85 to 350 bar at 40 and 60°C. The more SC-CO₂-soluble methylated derivatives of these fatty acids were evaluated from 90 to 170 bar at 40 and 60°C. The complex mixture of anhydrous milk fat (AMF) was evaluated from 100–310 bar at 40°C. The viscosities of the methylated fatty acids saturated with SC-CO₂ decreased between 5 and 10 times when the pressure increased from 1 to 80 bar, followed by a further decrease by a factor of 2 to 3 when the pressure was increased from 80 to 180 bar. The viscosities of the fatty acids and AMF saturated with SC-CO₂ had viscosity reduction similar to the methylated fatty acids between 1 and 80 bar, but they decreased much less between 80 and 350 bar. At constant pressure, the viscosity of the fatty acids and AMF decreased with increasing temperature, whereas the viscosity of the methylated fatty acids increased with increasing temperature. The lipid/SC-CO₂ mixtures were Newtonian, and their viscosities were best interpreted by using the mass concentration of dissolved SC-CO₂ in the lipids and the pure component viscosities.     

乌桕脂脂肪酸提取和分离的研究

由油脂精细化工的理论和实践,提出乌桕脂脂肪酸提取和分离的清洁工艺,并与现有工艺比较,说明该工艺的优越性     

Solubility of fatty acids in subcritical water

A phase equilibrium apparatus was designed to determine the solubilities of stearic acid and palmitic acid in subcritical water at different temperatures and pressures. The dissolution equilibrium time was measured. The effect of an ultrasonic field on dissolution equilibrium was also studied. The results showed that the maximum solubilities of stearic acid and palmitic acid were 0.136 g/100 g and 0.178 g/100 g in subcritical water at temperatures of 180 °C and 160 °C, respectively, and a pressure of 15 MPa for 30 min. An ultrasonic field also clearly promoted the dissolution of fatty acids in subcritical water. The dissolution equilibrium time was shortened to 20 min using ultrasonic oscillation (250 W, 20 kHz).     

Solubility of fatty acids in supercritical carbon dioxide

The solubilities of lauric, linoleic, myristic, oleic, palmitic and stearic acid in supercritical carbon dioxide (SC-CO₂) at different pressures and temperatures were measured. The solubility values obtained in this work were compared with previously published data, and possible causes for observed discrepancies were discussed. The solubilities of the six fatty acids were modeled by Chrastil’s equation, and estimated model parameters were used to plot the solubility isotherms of fatty acids at 313, 323 and 333°K (40, 50 and 60°C) as a function of SC-CO₂ density. The comparison of solubility isotherms of fatty acids and vegetable oil suggests that separation of fatty acids from triglycerides might be possible by using SC-CO₂ at densities less than 700 kg/m³. From the effect of temperature on fatty-acid and vegetable-oil solubility, it seems that the extraction yield could be increased without sacrificing the selectivity of SC-CO₂ for fatty acids by choosing a higher operating temperature. The data also suggest that fractionation of certain fatty acids might be possible by manipulating the processing conditions. Given the values of the constants, Chrastil’s equation could serve as a guideline for choosing appropriate processing conditions and predicting the effect of pressure and temperature of SC-CO₂ on solute solubility.