Oil Extraction from Castor Cake Using Ethanol: Kinetics and

Article pubs.acs.org/IECR

Oil Extraction from Castor Cake Using Ethanol: Kinetics and Thermodynamics Rafael C. A. Amarante,* Patrick M. Oliveira, Franciele K. Schwantes, and Joaquín A. Morón-Villarreyes Universidade Federal do Rio Grande (FURG), School of Food and Chemistry, Av. Itália, km 8, Rio Grande-RS 96203-900, Brazil S Supporting Information *

ABSTRACT: In this study, the kinetics and thermodynamics of oil extraction from castor cake using ethanol were investigated. Castor cake had a total oil content of 14.78 ± 0.12% in mass and the average particle diameter was 0.446 mm. Oil extractions were carried out in a stirred batch extractor system at various temperatures (20, 30, 40, and 55 °C). The fit of three different kinetic models to the experimental data was tested, with a modified Fick’s Law model being the most appropriate to describe the extraction kinetics (r2 ≥ 0.960 and ARE ≤ 3.25%). Effective diffusion coefficients were determined, ranging from 4.52 × 10−13 m2 s−1 at 20 °C to 5.60 × 10−13 m2 s−1 at 55 °C. Change in Gibbs’ free energy (ΔG°) was determined to be negative (−4.55 kJ mol−1 at 20 °C to −6.56 kJ mol−1 at 55 °C), while changes in enthalpy (ΔH°) and entropy (ΔS°) were positive (12.27 kJ mol−1 and 57.41 J mol−1 K−1, respectively). NaOH and lead tetroxide as catalyzer at 280 °C,12 and is used in different applications, such as cosmetics, lubricants, and hydraulic fluids.2 The utilization of sebacic acid as a precursor of biodegradable hydrogels used as scaffolds for tissue engineering applications13 and as drug carrier systems14 is a developing research field in polymer science. Heptaldehyde and 10-undecenoic acid are obtained through pyrolysis of castor oil and are used as solvent in rubber and plastic industries,15 and as raw materials for production of antitumor agents,16 respectively. Currently, the application of castor oil derivatives in the production of polyurethanes and interpenetrating polymer networks is receiving great attention of the scientific community,17 mainly because castor oil is the only natural oil polyol that is commercially available at large quantities.2 Polyurethanes from castor oil are largely used as thermoplastic elastomers, foams, adhesives,5 and in nanoparticles that can be used in the pharmaceutical industry.18 Several applications of castor oil as raw material in interpenetrating polymer networks have been reported.19−21 The industrial importance of these networks span from ion-exchange resins and piezodialysis membranes to coating, adhesives, and vibration-damping materials.22 Despite its economic importance and growing application possibilities, there is a lack of available data and information about castor oil extraction using solvents. Kinetic modeling is important because it is a powerful engineering tool that is useful in the design, simulation, optimization, and control of chemical processes.23 In this work, we fitted three different kinetic models to the extraction data to verify which one best describes the kinetic behavior of the process. The effect of temperature on extraction kinetics and the thermodynamic parameters of oil extraction were also determined and compared to values for the

1. INTRODUCTION The castor oil plant (Ricinus communis) is a flowering, fast growing plant that can be found as a large shrub or tree. It is a member of the Euphorbiaceae family and originated in tropical regions of Asia and Africa.1,2 Even though it is classified as a xerophile and a heliophile, the plant is able to adapt relatively easily to different climate conditions.3 Due to its versatility, the castor oil plant is currently cultivated on commercial scale in various regions of the world, particularly in temperate zones.2 India is the world’s largest producer of castor beans, reaching 2.33 million tonnes in 2011, according to the Food and Agriculture Organization of the United Nations (FAO), and the country is also the biggest exporter of castor oil, holding 70− 90% of the world market. China, Brazil, Thailand, Ethiopia, and Philippines are other countries with substantial production of castor oil.2,4 Castor seeds stand out due to its high oil content, reaching an average of 46−55% by weight on most common varieties.5 Some rarer genotypes can reach close to 60% of oil by weight.6 About 90% of fatty acids composing castor oil are ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid),7 which gives castor oil unique properties among vegetable oils, like high viscosity, high lubricity, insolubility in aliphatic solvents2 and high solubility in alcohols.8 Industrial applications of castor oil revolve around these physical properties and the chemical structure of ricinoleic acid, as most important reactions and modifications, like hydrogenation, dehydration, epoxidation, and sulfation, involve either the double bond or the hydroxyl group present in ricinoleic acid.5 Castor oil is used in a wide range of applications, from direct use as lubricant in heavy machinery due to its very good high temperature lubrication properties to novel applications in polymer industry.2 Hydrogenated derivatives from castor oil are a starting point for the production of vinyl monomers,9 anhydrous calcium greases,10 and lipid emulsions used as drug carriers.11 Sebacic acid (decanedioic acid) is a very important raw material produced through alkali splitting of castor oil with © 2014 American Chemical Society

Received: Revised: Accepted: Published: 6824

February 4, 2014 April 2, 2014 April 4, 2014 April 4, 2014 dx.doi.org/10.1021/ie500508n | Ind. Eng. Chem. Res. 2014, 53, 6824−6829

Industrial & Engineering Chemistry Research

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Table 1. Models Used to Describe the Kinetics of Oil Extraction from Castor Cake model So-Macdonald

Fick’s Law Peleg

equation

R t = Re −

parameters

R ew ,

(R ew). e−k w . t

R ed1,

reference Meziane et al., 200824

R ed2

− (R ed1). e−kd1. t − (R ed2). e−kd2. t

k w , kd1, kd2

Rt = 1 − A . e−B1. t Re

A , B1

Perez et al., 201125

K1, K 2

Bucic-Kojic et al., 200726

Rt =

t K1 + K 2. t

The So-Macdonald model was proposed in 198627 as a modification of the Patricelli model, developed in 1979.28 This model, like the Patricelli model, accounts for two extraction mechanisms: (1) washing of oil on the solid surface and (2) diffusion of oil from within the solid to the solvent. However, the So-Macdonald model considers that two different types of diffusion occur during the extraction process, an unhindered diffusion of oil contained in ruptured cells, and a slower, hindered diffusion process that involves oil restrained in unruptured cells. In the equation shown in Table 1, Rt is the oil yield (g oil/100 g solids) at any time t; Re is the total oil yield at d2 equilibrium; Rwe , Rd1 e , and Re are hypothetical oil yields at equilibrium due to washing, unhindered diffusion, and hindered diffusion mechanisms, respectively; and kw, kd1, and kd2 are mass transfer coefficients for the different extraction mechanisms. Perez et al. (2011)25 proposed a modification of Fick’s Law of diffusion to account for the initial nondiffusive washing step of oil extraction. Details of the mathematical solution of the model can be found in the work by Perez et al. (2011) and Fernández et al. (2012).29 The final equation is shown in Table 1, where Rt and Re are oil yields at time t and at equilibrium (g oil/100 g solids), respectively; and A and B1 are model-fitting coefficients. The fitting coefficient B1 is defined as follows:

solvent extraction of other vegetable oils available on the literature.

2. MATERIALS AND METHODS 2.1. Raw Materials. Castor seed cake was obtained as a byproduct of mechanical extraction of castor seeds of the Guarany genotype. The cake was milled using a knife mill to reduce the particle size. The milled castor cake was screened, and the average particle diameter was determined to be 0.446 mm. The moisture content was determined by drying the milled seeds in a stove at 105 ± 2 °C for 24 h and was found to be 9.2 ± 0.8%. Average oil content, determined by exhaustive extraction in a Soxhlet apparatus with ethanol, was 14.78 ± 0.12%. All castor seed cake characterization experiments were repeated three times. Ethanol used as solvent was reagent grade (Synth, São Paulo). 2.2. ExtractionsKinetic Study. The extraction experiments were performed in a batch extractor system consisting of a 250 mL round-bottom flask with a three-necked top connected to a magnetic stirrer and a condenser to avoid solvent losses. The system’s temperature was controlled using an oil bath on a hot plate and a thermometer. In all experiments, the batch extractor was first filled with the solvent and heated to the desired temperature, while the raw material was also heated to the same temperature in an oven. When both materials reached the desired temperature, the castor cake was added to the extraction flask and extraction was carried out. The weight of milled castor cake used was 25 g in each run. After extraction, the mixture was vacuum-filtered using a Buchner funnel, the resulting miscella was distilled, and the solvent was recovered in a rotary vacuum evaporator. Any remaining amount of solvent in the extracted oil was removed in an oven at 105 °C. The flask was then cooled in a desiccator and weighted. This procedure was repeated until the sample weight was found to be constant. Oil yield was calculated with respect to the mass of castor cake used in the extraction. Oil extraction yield data was collected at four different temperatures (293, 303, 313, and 328 K) and at 21 different extraction times to evaluate the effect of temperature on castor oil extraction. The solvent-to-solids ratio was 9 mL ethanol/g solids in all experiments and stirring speed was kept constant at 200 rpm. The contact time range studied was from 30 to 35 000 s in the kinetic study. 2.3. Kinetic Models. Three different mathematical models for describing the oil extraction kinetics were considered in this study and their performance in adjusting the data for oil extraction from castor cake using ethanol was compared. The three models and their respective parameters are shown in Table 1.

B1 =

De . π 2 R p2

(1)

where Rp is the average particle radius (m), and De is the effective diffusion coefficient (m2s−1). The Peleg model was proposed as an empirical model to study the sorption process in foods,30 and its application in extraction kinetics modeling has been suggested because of the similar behavior of sorption and extraction kinetics curves.26 In the model’s equation, shown in Table 1, Rt is oil yield at a time t (g oil/100 g solids), and K1 and K2 are model-fitting parameters. The kinetic parameters were estimated by the fit of the three models with the experimental kinetic data through nonlinear regression. The Quasi-Newton method was used to perform the parameter estimation calculations. All calculations were carried using the software Statistic 7.0 (Statsoft, U.S.A.). The model fit quality for all three models was evaluated and compared through determination coefficient (r2) and average relative error (ARE), as showed in eqs 2 and 3. ⎡ n r 2 = ⎢ ∑ (R i ,obs − R̅ i ,obs)2 − ⎢⎣ i ⎡ n ⎤ × ⎢ ∑ (R i ,obs − R̅ i ,obs)2 ⎥ ⎢⎣ i ⎥⎦

n

⎤

∑ (R i ,obs − R i , model)2 ⎥ i

⎥⎦

−1

6825

(2)

dx.doi.org/10.1021/ie500508n | Ind. Eng. Chem. Res. 2014, 53, 6824−6829

Industrial & Engineering Chemistry Research ARE =

100 n

n

∑

Article

R i ,obs − R i ,model

i=1

R i ,obs

(3)

In the equations above, n is the number of experimental points, Ri,model is each value of oil yield predicted by the fitted model, Ri,obs is each value of oil yield experimentally observed and R̅ i,obs is the average of yields experimentally observed. 2.4. Thermodynamic Study. For determining the thermodynamic equilibrium constants at each temperature, exhaustive extractions were performed using the same system described for the kinetic study. Each extraction was carried out for 50 h to guarantee equilibrium between the oil concentration on the miscella and oil concentration still on the castor cake. The temperatures studied were also 293, 303, 313, and 328 K and all other parameters (solvent-to-solids ratio, stirring speed, and particle size) were the same as for the kinetic study. The extraction equilibrium constant is defined as the following (Meziane, 2008): K=

Figure 1. Experimental kinetic data of castor oil yield in different temperatures.

(R e)miscella (R e)solid

(4)

where K is the equilibrium constant at a temperature T(K), (Re)miscella is the equilibrium oil yield at the same temperature T(K) and (Re)solid is the oil that remains unextracted at said temperature. The value of (Re)solid is calculated with respect to the average total oil content of the cake (14.78%) by subtracting the value of (Re)miscella. The Van’t Hoff equation relates enthalpy change ΔH° (kJ· mol−1) and entropy change ΔS° (J.mol−1·K−1) to the natural logarithm of the equilibrium constant, as follows: ln K = −

ΔH ° ΔS° + RT R

(5) −1

−1

where R is the universal gas constant (J·mol .K ). Values of thermodynamic parameters ΔH° and ΔS° were determined by adjusting the Van’t Hoff equation to the equilibrium constant data. The change in Gibbs’ free energy ΔG°(kJ·mol−1) for the extraction process was then determined according to the following equation: ΔG° = ΔH ° − T ΔS°

(6)

3. RESULTS AND DISCUSSION 3.1. Extraction Kinetics. Experimental kinetic data for the oil extraction from castor cake using ethanol is presented in Figures 1 and 2. It is clear from the data that the beginning of the extraction process is dominated by a washing mechanism. In this stage, ethanol rapidly solubilizes the castor oil that is available on the particles’ surface, and the oil yield increases quickly with time. In the first 30 min of extraction, a yield of up to 8% (at 55 °C) is obtained, a value that corresponds to 64% of final oil yield. After this initial stage that lasts roughly 30 min, the extraction rate decreases substantially, as diffusion becomes the predominant process. Similar kinetic behavior has been reported for the oil extraction from olive cake,24,31 sunflower,25,28,32 canola,27,29 neem,33 thyme,34 Jatropha,35 coconut,36 and tobacco37 and also for polyphenols extraction from grape seeds26 and berries.38 The kinetic data obtained also show that the amount of extracted oil, as expected, increases with temperature. This is true for the beginning of the extraction process, when it is controlled by washing, as well as

Figure 2. Experimental data of castor oil yield for the initial stage of extraction in different temperatures.

for the remaining extraction time, when the prominent masstransfer mechanism is diffusion. The final oil yield changes from 11.78% to 12.75% by increasing the extraction temperature from 20 to 55 °C. The increase in temperature causes the solubility of castor oil in ethanol to increase and the viscosity of both oil and ethanol to decrease, facilitating the mass-transfer process. The So-Macdonald and modified Fick’s Law models showed very good fit to the experimental data, with determination coefficient values varying between 0.961 and 0.993 for the SoMacdonald model and between 0.960 and 0.991 for the modified Fick’s Law model. The latter model showed lower average relative error values, ranging from 1.87% to 3.25%, while the values for the So-Macdonald model varied between 2.67% and 5.02%. However, the Peleg model showed a worse fit than the other two models, with lower determination 6826



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Table 2. Model-Fitting Calculated Parameters for the Modified Fick’s Law Kinetic Model parameters

temperature (K)

A B1 (s−1) Re (%) r2 ARE (%)

293

303

313

328

0.4794 0.897 × 10−4 12.09 0.962 2.74

0.4763 0.924 × 10−4 12.33 0.960 2.34

0.4728 1.024 × 10−4 12.45 0.961 3.25

0.4379 1.111 × 10−4 12.51 0.991 1.87

coefficient values (r2 ≤ 0.964) and higher average relative error (ARE ≥ 3.97%). The modified Fick’s Law model was chosen as the most appropriate for describing the kinetics of oil extraction from castor cake due to its good fit and lower ARE values, in comparison to the other models. Calculated kinetic and fit quality parameters for the modified Fick’s Law model are shown in Table 2. Fit of the modified Fick’s Law model to the experimental data for the studied temperature range is shown in Figure 3.

are usually an order of magnitude greater than the ones predicted in this study for castor oil in ethanol. Reported values for canola oil extraction with hexane were in a range from 1.3 × 10−12 m2 s−1 to 3.0 × 10−12 m2 s−1,29 while the values for oilseed sunflower in hexane were found to be from 2.06 × 10−12 m2 s−1 to 5.03 × 10−12 m2 s−125 and the value of the diffusion coefficient for the extraction of essential oils from thyme using supercritical CO2 was 5.23 × 10−12 m2 s−1 at 40 °C and 10 MPa.34 The effective diffusion coefficient for peanut oil extraction also with hexane was determined to be in an interval of 3.7 × 10−13 m2 s−1 to 7.2 × 10−13 m2 s−1,39 closer values to the ones calculated for castor oil in ethanol. The lower diffusion coefficients determined for castor oil extraction with ethanol can be explained by the higher viscosity that castor oil possess relative to most vegetable oils. The high viscosity of castor oil is mostly due to hydrogen bonds formed between the hydroxyl groups from ricinoleic acid, the major component of castor oil, and carbonyl groups present in the fatty acids. A plot of the relationship between observed and predicted Rt/Re values is displayed in Figure 4. The experimentally observed values were distributed with no tendencies around the 1:1 line, denoting a good prediction of the extraction process.

Figure 3. Fick’s Law model’s fit to the experimental data at 273 K (■), 303 K (◆), 313 K (▲), and 328 K (●).

It can be seen in Table 2 that the values for the fitting coefficient B1, which is a function of the effective diffusion coefficient, increased with rising temperature. That means the diffusive coefficient, as expected, also increased with temperature. Values for the effective diffusion coefficient at different temperatures were calculated using eq 1 and are presented in Table 3. Calculated values for the diffusion coefficient ranged from 4.52 × 10−13 m2 s−1 at 20 °C to 5.60 × 10−13 m2 s−1 at 55 °C. Values of effective diffusion coefficients for other vegetable oils

Figure 4. Plot of relationship between experimentally observed Rt/Re values and Rt/Re values estimated by Fick’s Law model.

Table 3. Effective Diffusion Coefficients of Castor Oil in Ethanol at Different Temperatures temperature (K) 293 303 313 328

B1 (s−1) 0.90 0.92 1.02 1.11

× × × ×

10−4 10−4 10−4 10−4

particle diameter (mm) 0.446

3.2. Extraction Thermodynamics. Castor oil yield data at equilibrium was used to estimate the thermodynamic parameters of the oil extraction process. Table 4 shows the equilibrium oil yield, (Re)miscella, the unextracted oil still in the solid particle at equilibrium conditions, (Re)solid, and the thermodynamic constant, K, calculated using eq 4. The van’t Hoff equation (eq 5) was adjusted to the data with very good correlation (r2 = 0.9886), as can be seen in Figure 5, making it

effective diffusion coefficient De (m2s−1) 4.52 4.66 5.16 5.60

× × × ×

10−13 10−13 10−13 10−13 6827



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sunflower seed oil (−1.07 kJ mol−1 at 333 K)40 and Jatropha oil (−4.93 kJ mol−1 at 333 K)41 and very close to the range reported for olive cake oil, which was between −4.47 kJ mol−1 and −6.25 kJ mol−1 for temperatures ranging from 293 to 323 K.24

Table 4. Equilibrium Constant Data at Different Extraction Temperatures temperature (K)

(Re)miscella

(Re)solid

K

ln K

293 303 313 328

12.76 13.10 13.32 13.53

2.02 1.68 1.46 1.25

6.32 7.80 9.11 10.86

1.84 2.05 2.21 2.38

4. CONCLUSIONS In this work, the equilibrium, kinetics, and thermodynamics of oil extraction from castor cake using ethanol were studied. Between the kinetic models tested, the modified Fick’s Law model gave the best fit to the experimental data (r2 ≥ 0.960 and ARE ≤ 3.25%). The beginning of the extraction process (up to about 30 min) was dominated by a washing mechanism, while, after most of the oil present on the surface of the solid particles was extracted, the extraction rate diminished, and the process became controlled by the diffusion of oil contained inside the particles in the solvent. Effective diffusion coefficients increased with temperature, varying from 4.52 × 10−13 m2 s−1 to 5.60 × 10−13 m2 s−1 at temperatures ranging from 293 to 328 K. Thermodynamic analysis found negative values for change in Gibbs’ free energy and positive values for enthalpy and entropy changes, indicating that the oil extraction process is spontaneous, endothermic, and favorable. The determination of the kinetic behavior, diffusion coefficients, and thermodynamic parameters provide useful information for design or improvement of castor oil extraction processes.

possible to estimate the change in enthalpy and entropy that occurs in the castor oil extraction process.

■

ASSOCIATED CONTENT

S Supporting Information *

Model-fitting calculated parameters for the So-Macdonald, Fick’s Law, and Peleg kinetic models (Table S1). This material is available free of charge via the Internet at http://pubs.acs. org/.

Figure 5. Van’t Hoff equation fit to experimental thermodynamic data.

As shown in Table 5, enthalpy and entropy changes were determined to be positive, which signifies that the process is

■

Table 5. Thermodynamic Parameters for Extraction of Castor Cake Oil Using Ethanol temperature (K) 293 303 313 328

ΔH° (kJ mol−1)

ΔS° (J mol−1K−1)

12.27

57.41

AUTHOR INFORMATION

Corresponding Author

*Tel.: +55 53 3233 6966. Fax: +55 53 3233 8644. E-mail: [email protected].

ΔG° (kJ mol−1) −4.55 −5.12 −5.69 −6.56

Funding

CAPES (Brazilian Agency for Improvement of Graduate Student); CNPq (National Council of Science and Technological Development) Notes

The authors declare no competing financial interest.

endothermic and that there is a rise in the disorder of the solids−oil−ethanol system. This effect was expected because the oil in transferred from a solid phase (castor cake) to a liquid one (ethanol). Similar results were observed for extraction processes of other vegetable oils with different solvents. For the extraction of sunflower oil with acidic hexane, the value for enthalpy change was 11.2 kJ mol−1 and entropy change was 36.8 J mol−1 K−1;40 for coconut oil extraction with hexane the values were 36.73 J mol−1 K−1 for entropy change and 12.16 kJ mol−1 for enthalpy change;36 for extraction of Jatropha oil using acidic hexane, the reported ΔH° and ΔS° were 0.159 kJ mol−1 and 15.27 J mol−1 K−1,41 respectively; and, finally, the values determined for olive oil extraction with hexane were 12.91 kJ mol−1 for enthalpy variation and 59.33 J mol−1 K−1 for entropy change.24 The values for change in Gibbs’ free energy were calculated using eq 6 and are also given in Table 5. The results obtained indicate that the oil extraction process occurs spontaneously and are in agreement with reported ΔG° for the extraction of

■

ACKNOWLEDGMENTS The authors would like to thank CNPq (National Council of Science and Technological Development) and CAPES (Brazilian Agency for Improvement of Graduate Student) for the financial assistance and FURG (Universidade Federal do Rio Grande) for its support.

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REFERENCES

(1) Scarpa, A.; Guerci, A. Various Uses of the Castor Oil Plant (Ricinus communis L.) A Review. J. Ethnopharmacol. 1982, 5, 117−137. (2) Mutlu, H.; Meier, M. A. R. Castor Oil As a Renewable Resource for the Chemical Industry. Eur. J. Lipid Sci. Technol. 2010, 112, 10−30. (3) Azevedo, D. M. P.; Beltrão, N. E. M. O Agronegócio da Mamona ́ 2007. no Brasil; Embrapa: Brasilia, (4) Ramanjaneyulu, A. V.; Reddy, A. V.; Madhavi, A. The Impact of Sowing Date and Irrigation Regime on Castor (Ricinus communis L.) Seed Yield, Oil Quality Characteristics and Fatty Acid Composition 6828



Article

during Post Rainy Season in South India. Ind. Crops Prod. 2013, 44, 25−31. (5) Ogunniyi, D. S. Castor Oil: A Vital Industrial Raw Material. Bioresour. Technol. 2006, 97, 1086−1091. (6) Ramos, L. C. S.; Tango, J. S.; Savi, A.; Leal, N. R. Variability for Oil and Fatty Acid Composition in Castor Bean Varieties. J. Am. Oil Chem. Soc. 1984, 61 (12), 1841−1843. (7) Cvengros, J.; Paligova, J.; Cvengrosova, Z. Properties of Alkyl Esters Base on Castor Oil. Eur. J. Lipid Sci. Technol. 2006, 108, 629− 635. (8) Koutroubas, S. D.; Papakosta, D. K.; Doitsinis, A. Adaptation and Yielding Ability of Castor Plant (Ricinus communis L.) Genotypes in a Mediterranean Climate. Eur. J. Agron. 1999, 11, 227−237. (9) Krishnamurti, N. Vinyl Monomers from 12-Hydroxy Stearic Acid. Pigm. Resin Technol. 1980, 9, 15−17. (10) Ishchuk, Y. L.; Dugina, L. N.; Krasnokutskaya, M. E.; Godun, B. A. Influence of Composition of Technical 12-Hydroxy Stearic Acid on Properties of Anhydrous Calcium Greases. Chem. Technol. Fuels Oils 1986, 22, 402−405. (11) Jumaa, M.; Müller, B. W. Parenteral Emulsions Stabilized with a Mixture of Phospholipids and PEG-660-12-Hydroxy-Stearate: Evaluation of Accelerated and Long-Term Stability. Eur. J. Pharm. Biopharm. 2002, 54, 207−212. (12) Vasishtha, A. K.; Triverdi, R. K.; Das, G. Sebacic Acid and 2Octanol from Castor Oil. J. Am. Oil Chem. Soc. 1990, 67, 333−337. (13) Kim, J.; Lee, K. W.; Hefferan, T. E.; Currier, B. L.; Yaszemski, M. J.; Lu, L. Synthesis and Evaluation of Novel Biodegradable Hydrogels Based on Poly(ethylene glycol) and Sebacic Acid As Tissue Engineering Scaffolds. Biomacromolecules 2008, 9, 149−157. (14) Liang, Y.; Xiao, L.; Zhai, Y.; Xie, C.; Deng, L.; Dong, A. Preparation and Characterization of Biodegradable Poly(sebacic anhydride) Chain Extended by Glycol As Drug Carrier. J. Appl. Polym. Sci. 2013, 127 (5), 3948−3953. (15) Domsch, A. Chemistry and Application of Undecylenic Acid and Derivatives Thereof for Cosmetics. SÖ FW. 1994, 120, 322−329. (16) Van der Steen, M.; Stevens, C. V.; Eeckhout, Y.; De Buyck, L.; Ghelfi, F.; Roncaglia, F. Undecylenic Acid: A Valuable Renewable Building Block on Route to Tyromycin A Derivatives. Eur. J. Lipid Sci. Technol. 2008, 110, 846−852. (17) Petrovic, Z. S. Polyurethanes from Vegetable Oils. Polym. Rev. 2008, 48, 109−155. (18) Zanetti-Ramos, B. G.; Lemos-Senna, E.; Soldi, V.; Borsali, R.; Cloutet, E.; Cramail, H. Polyurethane Nanoparticles from a Natural Polyol via Miniemulsion Technique. Polymer 2006, 47, 8080−8087. (19) Nayak, P. L. Natural Oil-Based Polymers: Opportunities and Challenges. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 2000, 40, 1− 21. (20) Xie, H.; Guo, J. Room Temperature Synthesis and Mechanical Properties of Two Kinds of Elastomeric Interpenetrating Polymer Networks Based on Castor Oil. Eur. Polym. J. 2002, 38, 2271−2277. (21) Zhang, L.; Ding, H. Study on the Properties, Morphology, And the Applications of Castor Oil Polyurethane-Poly(methyl methacrylate) INPs. J. Appl. Polym. Sci. 1997, 64, 1393−1401. (22) Sperling, L. H.; Mishra, V. The Current Status of Interpenetrating Polymer Networks. Polym. Adv. Technol. 1996, 7, 197− 208. (23) Amendola, D.; De Faveri, D. M.; Spigno, G. Grape Marc Phenolics: Extraction Kinetics, Quality and Stability of Extracts. J. Food Eng. 2010, 97, 384−392. (24) Meziane, S.; Kadi, H. Kinetics and Thermodynamics of Oil Extraction from Olive Cake. J. Am. Oil Chem. Soc. 2008, 85, 391−396. (25) Perez, E. E.; Carelli, A. A.; Crapiste, G. H. TemperatureDependent Diffusion Coefficient of Oil from Different Sunflower Seeds during Extraction with Hexane. J. Food Eng. 2011, 105, 180− 185. (26) Bucic-Kojic, A.; Planinic, M.; Tomas, S.; Bilic, M.; Velic, D. Study of Solid−Liquid Extraction Kinetics of Total Polyphenols from Grape Seeds. J. Food Eng. 2007, 81, 236−242.

(27) So, G. C.; Macdonald, D. G. Kinetics of Oil Extraction from Canola (Rapeseed). Can. J. Chem. Eng. 1986, 64, 80−86. (28) Patricelli, A.; Assogna, A.; Casalaina, A.; Emmi, E.; Sodini, G. Factors Affecting the Extraction of Lipids from Shelled Sunflower Seeds. Riv. Ital. Sostanze Grasse. 1979, 56, 136−142. (29) Fernández, M. B.; Perez, E. E.; Crapiste, G. H.; Nolasco, S. M. Kinetic Study of Canola Oil and Tocopherol Extraction: Parameter Comparison of Nonlinear Models. J. Food Eng. 2012, 111, 682−689. (30) Peleg, M. An Empirical Model for the Description of Moisture Sorption Curves. J. Food Sci. 1988, 53 (4), 1216−1218. (31) Amarni, F.; Kadi, H. Kinetics Study of Microwave-Assisted Solvent Extraction of Oil from Olive Cake Using Hexane: Comparison with the Conventional Extraction. Innov. Food Sci. Emerg. Technol. 2010, 11, 322−327. (32) Baumler, E. R.; Crapiste, G. H.; Carelli, A. A. Solvent Extraction: Kinetic Study of Major and Minor Compounds. J. Am. Oil Chem. Soc. 2010, 87, 1489−1495. (33) Liauw, M. Y.; Natan, F. A.; Widiyanti, P.; Ikasari, D.; Indraswati, N.; Soetaredjo, F. E. Extraction of Neem Oil (Azadirachta indica A. Juss) Using n-hexane and Ethanol: Studies of Oil Quality, Kinetic and Thermodynamic. J. Eng. Appl. Sci. 2008, 3, 49−54. (34) Petrovic, S. S.; Ivanovic, J.; Milovanovic, S.; Zizovic, I. Comparative Analyses of the Diffusion Coefficients from Thyme for Different Extraction Processes. J. Serb. Chem. Soc. 2012, 77, 799−813. (35) Sayyar, S.; Abidin, Z. Z.; Yunus, R.; Muhammad, A. Extraction of Oil from Jatropha SeedsOptimization and Kinetics. Am. J. Appl. Sci. 2009, 6 (7), 1390−1395. (36) Sulaiman, S.; Abdul Aziz, A. R.; Aroua, M. K. Optimization and Modeling of Extraction of Solid Coconut Waste Oil. J. Food Eng. 2013, 114, 228−234. (37) Stanisavljevic, I. T.; Lazic, M. L.; Veljkovic, V. B. Ultrasonic Extraction of Oil from Tobacco (Nicotiana tabacum L.) Seeds. Ultrason. Sonochem. 2007, 14, 646−652. (38) Cacace, J. E.; Mazza, G. Mass Transfer Process during Extraction of Phenolic Compounds from Milled Berries. J. Food Eng. 2003, 59, 379−389. (39) Fan, H. P.; Morris, J. C.; Wakeham, H. Diffusion Phenomena in Solvent Extraction of Peanut Oil. Ind. Eng. Chem. 1948, 40, 195−199. (40) Topallar, H.; Geçgel, U. Kinetics and Thermodynamics of Oil Extraction from Sunflower Seeds in the Presence of Aqueous Acidic Hexane Solutions. Turk. J. Chem. 2000, 24, 247−253. (41) Amin, S. K.; Hawash, S.; El Diwani, G.; El Rafei, S. Kinetics and Thermodynamics of Oil Extraction from Jatropha curcas in Aqueous Acidic Hexane Solutions. J. Am. Sci. 2010, 6, 293−300.

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Oil Extraction from Castor Cake Using Ethanol: Kinetics and

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