Open access peer-reviewed chapter

Kinetics and Thermodynamics of Oil Extracted from Amaranth

Written By

Chinedu M. Agu and Albert C. Agulanna

Submitted: 22 March 2019 Reviewed: 02 July 2019 Published: 18 March 2020

DOI: 10.5772/intechopen.88344

From the Edited Volume

Nutritional Value of Amaranth

Edited by Viduranga Y. Waisundara

Chapter metrics overview

1,250 Chapter Downloads

View Full Metrics

Abstract

This chapter deals with the kinetics of solvent extraction of oil from Amaranth, as well as the thermodynamics of the extraction process. Brief introduction of Amaranth and Amaranth oil yields and compositions were given. The justifications of the choice of extraction method, as well as the solvent used in the kinetics and thermodynamic studies, were discussed. Known kinetic models used to model vegetable oils extraction process, were discussed, with the view of evaluating the feasibility of fitting the obtained experimental data into the models. The extraction kinetic models considered are the parabolic diffusion, power law, hyperbolic, Elovich’s and pseudo second order models. The thermodynamics of oil extraction process were also considered. Hence, the thermodynamic parameters, enthalpy, entropy and Gibb’s free energy change of the process were also discussed.

Keywords

  • kinetics
  • thermodynamics
  • Amaranth
  • oil extraction
  • solvent extraction method

1. Introduction

Amaranth plant is a strong and fast-growing pseudocereal that is nutritious and is presently used as food crop. The common species of Amaranth grains are Amaranthus cruentus, Amaranthus caudatus, and Amaranthus hypochondriacus [1]. It has lot of nutritional and health benefits due to its fiber content, tocols, high protein content, squalene, as well as diverse bioactive compounds. Amaranthus sp. grain also contains high concentration of minerals, vitamins, specially tocotrienols lysine amino acids and fatty acids [2]. Various species of Amaranth are planted in several parts of the world, such as South America, Africa, India, China and United States [3]. Composition of seeds from the several species of Amaranthus have been reported to contain protein, starch and oil, that are of high quality for food and animal feed purposes [4].

Amaranth grains have been reported by number researchers to contain about 6–9% oil [1, 4, 5, 6]. Although the oil yield of Amaranth is low, it is often not extracted from the seeds, though there are situations where it would be advantageous to extracted and use the oil [4]. This is because the oil is very rich in squalene, compared to other vegetable oils, like olive, rice bran, corn, peanut, rapeseed, cottonseed and sunflower [5, 6, 7, 8, 9]. The oil of Amaranth is reported to contain high quantity of squalene, of up to 7.3–11.2% [1, 3, 10]. Oil from Amaranthus sp., also contains other important substances like crude fat and some essential fatty acids [11].

It is important to know that the fatty acids present in Amaranth seeds oil, are similar to those present in other cereals, like cottonseed and sesame oils [1]. For instance, the oil of Amaranthus cruentus, have been reported to contain 6.3% crude fat, 38.2% linoleic acid, 33.3% oleic acid, 4% stearic acid, 1% linolenic acid, and 20% palmitic acid [11]. In Amaranth oil, the major carbon number present ranges from C50 to C54. This value is in the range reported for corn and cottonseed oils [12]. In addition, Amaranth oil has high amount of unsaponifiable matter of about 8%. This value is higher than the values of other oils, like sunflower (0.3–1.2), soybean (0.6–1.2) and olive (0.4–1.1) [1, 13]. Furthermore, Amaranth seeds oil contains other lipid components other than squalene. These components are phospholipids, glycolipids and sterols [14].

Of the lipid and oil components of Amaranth, squalene is of very high importance. This is because of its applications in various industrial products, hence, the need to briefly highlight it. Squalene is a type of unsaponifiable lipid which functions as a biosynthetic precursor, to all steroids (phytosterols and cholesterol) in both plants and animals [6, 15]. It is a triterpene (C30H50), often found in tissues of plants and animals [15]. Many research works have shown the biochemical importance squalene as antioxidant [15, 16, 17, 18], as well as chemopreventive agent [19]. The economic and industrial importance of squalene cannot be overemphasized, due to its numerous applications. For instance, commercially, about 93 million dollars is the value of just 2500 tons of squalene that was produced in 2013 [15]. Industrially, it is used as an essential ingredient in skin cosmetics [1, 3, 10, 14, 15], due to it photoprotective ability, as well as a lubricant for computer disk [3, 10, 14], due to its thermostability [14]. Furthermore, in the area of health, squalene decreases different cancer(s) risk [10, 14], as well as reduces serum cholesterol levels [10].

From the forgoing, it could be seen that it is very important to extract oil from Amaranth seeds, especially due to the already highlighted vital industrial applications of its component, squalene. In other words, it is important to understand the extraction methods that could be used to extract oil from Amaranth, as well as justify the method to be used in the kinetics and thermodynamics studies of the extraction process. This chapter therefore, seeks to also look at the kinetics and thermodynamics of Amaranth seeds/grains oil extraction, using known extraction kinetics models. The models considered here are, parabolic diffusion, power law, hyperbolic, Elovich’s and pseudo second order models. Also, the thermodynamic parameters evaluated are, enthalpy, entropy and Gibb’s free energy change of the extraction process.

Advertisement

2. Methods of oil extraction from Amaranth seeds/grains

A number of very important factors affect extraction processes, irrespective of the substance being extracted (in this case Amaranth seeds), or the extraction method used. These factors include, but not limited to matrix properties of the material (plants, seeds, nuts, and leaves), solvent, extraction time, temperature, pressure [20, 21]. Oil extraction from seeds/nuts such as, Amaranth can be done using different methods. These extraction methods can be categorized into conventional (common) and non-conventional (new/novel techniques) methods [22, 23, 24].

Conventional (common) methods comprise of hydro-distillation (HD), steam distillation, cold pressing (CP), mechanical pressing, solvent extraction and simultaneous distillation-extraction methods, among others [23, 25]. On the other hand, non-conventional (novel) extraction methods include supercritical fluid extraction [26, 27, 28, 29], pressurized liquid extraction (PLE) or pressurized fluid extraction (PFE) or accelerated fluid extraction (ASE) or enhanced/accelerated solvent extraction (ESE) or high pressure solvent extraction (HPSE) [30, 31], microwave-assisted extraction (MAE) [32, 33, 34], ultrasound-assisted extraction (UAE) [35, 36, 37], pulsed-electric field extraction (PEF) [38, 39], enzyme-assisted extraction (EAE) [40, 41], among others [23, 24].

Though the conventional techniques have been used over the years for various extraction purposes, with Amaranth oil extraction inclusive, they have their peculiar shortcomings, such as, low extraction efficiency in case of cold pressing and hydro distillation. Also, in the mechanical pressing and steam distillation conventional methods, degradation of unsaturated, or ester compounds through thermal or hydrolytic effects, are the main disadvantages associated them. In the case of solvent extraction method, the likely residual toxic solvent in the extracts or oil is its major shortcoming [23].

As a result of these short comings associated with traditional conventional (hydro-distillation, steam distillation, cold pressing, mechanical pressing, solvent extraction and distillation) methods, several non-conventional techniques earlier stated, are currently in use for oil extraction and other extracts from seeds/nuts, plants, flowers, leaves etc. [23, 24]. These novel methods have the advantage of functioning efficiently at elevated operating conditions (temperatures and/or pressures), thus decreasing the extraction time, significantly [24].

Nonetheless, conventional extraction methods, such as solvent extraction using Soxhlet extractor, is still considered as one of the reference methods, to compare success with the newly developed non-conventional (novel) methods [22, 24]. Soxhlet extraction as a well-established technique is more efficient than other conventional extraction methods, except in limited applications like, the extraction of thermo labile compounds [24]. It is important to state that Soxhlet extractor was first proposed by German chemist, Franz Ritter Von Soxhlet in 1879. Initially, it was designed primarily for lipid extraction, but presently it is no longer limited to this purpose alone. Soxhlet extractor is now widely used for the extraction of valuable substances such as bioactive compounds, oils, etc. [22], with Amaranth oil not being left out.

Advertisement

3. Justifications for the choice of Soxhlet extractor and solvent(s)

In the operation of Soxhlet extractor, it uses solvent in its operation for the extraction of valuable substances from the solute. In this case, for extraction of oil from Amaranth seeds/grains. For the operation of the extractor, different types of solvents, which can be used for extraction purposes, exist. These solvents will yield different quantities of the Amaranth oil. However, the most widely-used solvent for the extraction of oils from plants, seeds and nuts, irrespective of whether is Amaranth or any other seed/nut, is hexane. Hexane has a fairly narrow boiling point range of approximately 63–69°C, and it is an excellent solvent for oil extraction, especially in terms of solubility and ease of recovery [24].

Over the years, solvent extraction (by Soxhlet apparatus) using different solvents, have been used to extract oil from Amaranth seeds. For instance, He and Corke [6] successfully used Soxhlet apparatus to extract oil from Amaranthus grain, using petroleum ether (boiling point range 40–60°C) as the extracting solvent. They obtained an average Amaranth oil yield of 5.0%. Similarly, Ortega et al. [14] used Soxhlet apparatus in the extraction of Amaranth oil, using hexane as the solvent. In the work of Krulj et al. [2], Soxhlet apparatus was also used for Amaranthus sp. grain oil extraction, using petroleum ether (boiling point range 40–60°C), with obtained oil yield of 70–75.7 g/kg weight. Even as early as 1987, Lyon and Becker [4] had used Soxhlet apparatus for oil extraction from Amaranth seed, using hexane as solvent, and obtained oil yield of 7.01%. Several authors have also used this Soxhlet apparatus for oil extraction from Amaranth seeds.

The benefits of Soxhlet apparatus have also attracted its use for other vegetable oils extraction, from a wild number of other seeds/nuts, using different solvents. For instance, in the extraction of oil from African star apple (Chrysophyllum albidum) using Soxhlet extractor, Adebayo et al. [42] used hexane solvent and 10.71% yield was recorded. In case of oil extraction from Hibiscus cannabinus L. seed, Chan and Ismail [43] obtained a yield of 24.81%, using hexane; while Mariod et al. [44] got a yield of 62.38% using the same solvent. Furthermore, in the extraction of oil from Plukenetia volubilis seed using petroleum ether, Niu et al. [45] reported an oil yield of 39% using Soxhlet apparatus. Omeh et al. [46] reported a yield of 65% for the extraction of oil from Irvingia Gabonensis seeds, using hexane. Lasekan and Abdulkarim [47] successfully extracted oil from tiger nut (Cyperus esculentus L.), using n-hexane and yield of 26.28% was obtained. In case of Terminalia catappa oil extraction using Soxhlet extractor, yields of 49, 60.45 and 61.98% were reported by Dos Santos et al. [48], Menkiti et al. [49] and Adepoju et al. [50], respectively, using hexane. Many other authors too numerous to mention, have also successfully used Soxhlet extractor for oil extraction from seeds/nuts, because of its benefits/advantages.

This extensive use of Soxhlet apparatus (in solvent extraction) method was possible due to a number of its advantages. The advantages of using conventional Soxhlet extraction method include: (1) the displacement of transfer equilibrium by repeatedly bringing fresh solvent in contact with the solid matrix, (2) maintaining a relatively high extraction temperature with heat from the distillation flask, (3) cheapness and simplicity in operating the Soxhlet apparatus, and (4) filtration is not required after leaching [24, 51]. That notwithstanding, solvent extraction method using Soxhlet apparatus, is not without a number of shortcomings. Some of the disadvantages of conventional Soxhlet extraction include: (1) large quantity of solvent is required, (2) lengthy extraction time, (3) inability to provide agitation in the device in other to speed up the process [24].

On the other hand, N-hexane has been extensively used over the years as the preferred solvent for oil extraction from Amaranth seeds [4, 5, 14], as well as other seeds/nuts [49, 65], compared to other solvents [2, 6]. This was attributed to its nonpolar nature (low polarity index of 0.0), compared to the polarity indexes of other nonpolar solvents, like petroleum ether [49]. Table 1 shows the oil yield, boiling point, polarity/polarity index of solvents, used in the preliminary evaluation of solvents effects on the oil yield of Terminalia catappa kernel (source, Menkiti et al. [49]). Also, its high boiling point 63–69°C, when compared to other solvents like petroleum ether, benzene, chloroform, methanol etc., is another added advantage [24, 49]. Lately, new solvents have been tested in extraction processes. Some of the tested solvents include but not limited to acetone, ethanol and isopropanol [52, 53, 54, 55, 56]. Nevertheless, only ethanol, isopropanol and occasionally acetone are permitted for use as solvents in the food industry, due to their minimal waste generation [57]. Thus, the advantages of hexane still supersede those of these solvent. Therefore, Soxhlet apparatus and hexane were used for ease of discussion of the kinetics and thermodynamics of Amaranth seed oil extraction.

Table 1.

Oil yield, boiling point and polarity/polarity index of solvents used in Terminalia catappa kernel oil extraction (source, Menkiti et al. [49]).

Advertisement

4. Kinetics and kinetic models that could be used to model oil extraction from Amaranth seeds/grains

During solvent extraction using Soxhlet extractor, it is important to determine the rate at which equilibrium is attained between a miscella and oil and solvent, within the particles, irrespective of the seeds/nuts [58, 59]. There is therefore need to study the kinetics of Amaranth seed oil extraction, prior to evaluation of the existing kinetic models, that could be used to fit the obtained extraction kinetics data. Within the knowledge disposal of the author, there is no published article on the results of the kinetics of oil extraction from Amaranth seeds, hence, the need to evaluate the possible kinetic models that could be used to fit its oil extraction data, when obtained.

Therefore, due to the importance of kinetics with respect to oil extraction, a number of kinetic models have been proposed to analyze the kinetics of oil extraction processes for different seeds/nuts. Some of these seeds, nuts and kernels include but not limited to, partially dehulled sunflower [60], rapeseed [61, 62], confectionery, oilseed and wild sunflower [63], sunflower collets [64], Terminalia catappa [49], Colocynthis vulgaris Schrad [65] and olive cake [66].

These kinetic models can be classified into physical and empirical ones. Physical models are the models that are based on the physical phenomena of mass transfer, through the seeds/nuts particles and from external solid surfaces, into the bulk of the liquid phases [49, 67, 68]. On the other hand, empirical models are the models that describe mathematically variations of extractive substance amount in either seeds/nuts material or liquid extract with time [49, 68].

However, the empirical models would be treated in this section. These empirical models are ordinarily simpler than physical ones, and are also suitable for engineering purposes [49, 67]. Some examples of these models includes: power law model, hyperbolic model, parabolic diffusion model, Elovich’s model, Weibull’s model, pseudo second order model, and pseudo first order model [49, 67, 68]. These empirical kinetic models have been successfully used to model oil extraction from a number of seed/nuts. For instance, Menkiti et al. [49, 68], used power law, parabolic diffusion, hyperbolic, Elovich’s and pseudo second order models, for Terminalia catappa kernel oil extraction kinetics study.

Similarly, Agu et al. [65] used these five models to study the kinetics of oil extraction from Colocynthis vulgaris Schrad seed. They reported that with the exception of power law model, all the other models gave relatively good fit to the experimental extraction kinetic data. This can be clearly seen in Figure 1. Figure 1 shows the nonlinear kinetic plots of the experimental data, as well as the studied models, at varying particles sizes and at 55°C, for the extraction of oil from Colocynthis vulgaris Schrad seed (source, Agu et al. [65]). In the work of Menkiti et al. [49], they found that hyperbolic, Elovich’s and pseudo second order models studied, gave good fit to the experimental kinetic data, with pseudo second order models as the best. However, in the work of Menkiti et al. [68], they found that in the nonlinear fitting of the extraction kinetics data into these five models, that it was only hyperbolic and pseudo second order models, that gave well fit to the extraction data. In their separate studies on safflower seed oil extraction, Han et al. [69] and Ayas and Yilmaz [70], used the Sovova’s extended Lack’s Model (SLM) alone, to model the extraction process and reported that the model gave good fit to the experimental data.

Figure 1.

Nonlinear kinetic plots at varying particle sizes (0.5 and 2.5 mm) at 55°C for Colocynthis vugaris Shrad seeds oil extraction (source, Agu et al. [65]).

Several researchers too numerous to mention have successfully used different extraction models to fit oil extraction kinetic data of a number of oil seeds/nuts. Over time, most researchers have modeled the extraction process they studied, using the pseudo second order model. This is because pseudo second order model has always fitted best to most solid-liquid extraction processes, as evident from some of the works earlier mentioned [49, 65, 68]. There is therefore need for researchers to direct their research interest, into the evaluation of the kinetics of Amaranth seed oil extraction, using these models.

Some of these known empirical kinetic models used to model solid-liquid extraction are briefly descried. The five two-parametric empirical kinetic models often used to model oil extraction from seeds/nuts are: parabolic diffusion, power law, hyperbolic, Elovich’s and pseudo second-order models. Kinetic parameters of these models could be generated using both linear [49] and non-linear [65, 68] equations of the models. Prior to the empirical modeling of the extraction process, for Amaranth seed oil extractions, following assumptions are made on the basis of the empirical models:

  • seed particles are isotropic and of equal size;

  • distribution of extractive substances (oil) within the seed particles is uniform and varied only with time;

  • neto diffusion occurs only towards the external surface of the seed particles;

  • diffusion coefficient of extractive substances (oil) is constant.

However, for some models, there could be additional, specific assumptions that are introduced [49, 65, 68]. Table 2 shows the linear and nonlinear forms of the extraction kinetic models equations that could be used to fit Amaranth seed oil kinetic data. These models equations are briefly described sequentially.

Table 2.

Models names, nonlinear and linear forms of equations that can be used to model Amaranth seed oil extraction data.

4.1 Parabolic diffusion model

The generalized form of the parabolic diffusion model equation is shown in Eq. (1).

q¯=A0+A1t1/2+A2tE1

In the case of application of Eq. (1), for seed particles extraction, where chemical reaction is not involved, Eq. (1) can then be simplified to obtain Eq. (2) [71].

q¯=A0+A1t1/2E2

Eq. (2) is known as the parabolic diffusion equation. This model corresponds to the simple two-step extraction mechanism that consists of washing, followed by diffusion. The expression for A0 is given in Eq. (3), while the constant A1 is the diffusion rate constant. A0 represents the extraction oil yield recovered instantaneously as the seed/nut material (Amaranth) is submersed into the solvent (i.e. at t = 0), and is called the washing coefficient [67].

A0=q¯wq¯0E3

Where q¯w is the amount of extractive substance (oil) washed away instantaneously as the sample material (Amaranth seed) is submersed into the solvent, q¯0 is the amount of extractive substance in the sample material (Amaranth seed). Both q¯w and q¯0 are expressed as g/100 g of the sample material. From Eq. (2), a plot of % yield, q¯ verses t1/2, gives A0 as the intercept, and A1 as the slope.

4.2 Power law model

This model equation was used to reveal the mechanisms that governed the diffusion of any active agent through non-swelling devices [67]. In terms of modeling oil extraction from seeds, Menkiti et al. [68] and Agu et al. [65], successfully fitted the obtained experimental kinetic data, from Terminalia catappa kernel and Colocynthis vulgaris Schrad seed extractions, respectively, into power law model equation. As such, this model can also be used successfully to model oil extraction from Amaranth seeds/grains. Eq. (4) is the generalized form of power law model equation.

q¯=BtnE4

Where, B is a constant incorporating the characteristics of the carrier-active system, and n is the diffusional exponent, indicative of transport mechanism. For extraction of materials (such as Amaranth seed), it is n < 1. The extraction yield predicted by this equation does not approach to unity (1) with time [67].

Hence, Eq. (4) can be re-written and n, replaced with 1/2, since at any time, n must be <1. Therefore, Eq. (4) can now be written as Eq. (5).

q¯=Bt1/2E5

Eq. (5) is then linearized to obtain Eq. (6).

Inq¯=InB+nLntE6

By plotting Inq¯ against Int, the intercept is obtained as InB, while n is the slope.

4.3 Hyperbolic model

Hyperbolic model is a kinetic model that is often applied in food engineering science as pelegs model. This model has also been applied for oil extraction modeling from seeds/nuts. For instance, Menkiti et al. [49, 68], and Agu et al. [65], applied the nonlinear form of this model in oil extraction from Terminalia catappa kernel and Colocynthis vulgaris Schrad seed extractions, respectively. Eq. (7) is the general form of hyperbolic model [67, 72].

q¯=C1t1+C2tE7

The extraction is first-order at the beginning, and decreases to zero-order in the later phase of the process. When C2t << 1, Eq. (7), then reduces to Eq. (8).

q¯=C1tE8

On linearizing Eqs. (7) and (9) is obtained.

1q̅=1C1×1t+C2C1E9

The plot of 1/q¯ that is 1/yield against 1/t in Eq. (9), gives intercept as C2/C1 and the slope as 1/C1.

C1 and C2 are hyperbolic model parameters extraction rate at the beginning (min−1), and constant related to maximum extraction yield (min−1), q¯, respectively.

4.4 Elovich’s equation

The general form of Elovich’s equation written as a logarithmic relation is shown in Eq. (10) [71, 73]. Like in the other three models already discussed, Elovich’s model has also been applied to oil extraction modeling. In the works of Agu et al. [65], and Menkiti et al. [49, 68], Elovich’s model was applied using the nonlinear form of the model, for oil extraction modeling of Terminalia catappa kernel and Colocynthis vulgaris Schrad seed, respectively. Hence, Elovich’s model can also be applied to the modeling of Amaranth seeds oil extraction.

q¯=E0+E1IntE10

The equation is derived under the assumption that the rate of extraction (in this case Amaranth oil extraction), decreases exponentially with increasing extraction yield, as could be seen in Eq. (11).

dq̅dt=β×expαq̅E11

Where β=E1×expE0/E1 and α=1/E1. When q¯0, then dq¯/dtβ, thus β is the initial extraction rate. A plot of yield q¯ verse Int in Eq. (10), gives E0 as the intercept and E1 as the slope. Where, E0, and E1 are Elovich equation parameters (L).

4.5 Pseudo second order model

In the case of the second-order rate law, the dissolution rate of the oil contained in the solid (in this case Amaranth seeds), into the solvent can be described by Eq. (12). Pseudo second order model equation has also been used to fit oil extraction data, obtained from oil seeds/nuts. This model was also used in its nonlinear form in the works of Agu et al. [65], and Menkiti et al. [49, 68], to fit the experimentally obtained kinetic data of Colocynthis vulgaris Schrad seed and Terminalia catappa kernel extractions, respectively. This model can also be used to the model of Amaranth seeds oil extraction.

dCtdt=KCsCt2E12

where K is the second-order extraction rate constant (L g−1 min−1); Cs is the extraction capacity (concentration of oil at saturation in g L−1); Ct is the concentration of oil in the solution at any time (g L−1), t (min).

The initial extraction rate defined as h, when t and Ct approach 0, can be expressed as shown in Eq. (13).

h=KCs2E13

Considering the boundary conditions at t=0tot and Ct=0toCt, the integrated rate law for pseudo second-order extraction was obtained as Eq. (14).

q¯=Cs2Kt1+CsKtE14

The linearized form of Eq. (14), gives rise to Eq. (15).

tCt=tKCs2+tCsE15

The initial extraction rate, h, the extraction capacity, Cs and the pseudo second order extraction rate constant, k, can be calculated experimentally by plotting t/Ct versus t in Eq. (15) [74].

Advertisement

5. Thermodynamic studies of oil extraction from Amaranth seeds

It is very important to consider the thermodynamic of any oil extraction process. In the case of the thermodynamics of Amaranth seed oil extraction, there could be little or no information available. There is therefore need for researcher to carry out this research. Thermodynamic parameters like enthalpy (∆H), entropy (∆S) and Gibbs free energy (∆G) can be estimated using known thermodynamic equation [49].

The thermodynamic parameters (ΔH, ΔS and ΔG) for the extraction of oil from a particular seed, such as Amaranth seed, using n-hexane as solvent, can be estimated using Eqs. (16) and (17). However, Eq. (18) is used occasionally to calculate the equilibrium constant K.

G=RTInKE16
InK=GRT=HRT+SRE17
K=YTYu=mLmsE18

Where K is equilibrium constant, YT is the yield of oil at temperature T, Yu is the percentage of the unextracted oil. Similarly, mL is amount of a particular seed oil (in this case Amaranth oil) in liquid at equilibrium temperature T, while ms is amount of a particular seed oil (Amaranth oil) in solid at equilibrium temperature T. R is gas constant (8.314 J/mol K), while ΔH, ΔS and ΔG are the enthalpy, entropy and Gibbs free energy of extraction (KJ/mol K), respectively [75].

Eq. (17) is a Van’t Hoff relation, and plotting of InK against 1/T, is used to determine the values of ΔH, ΔS and ΔG. The plot gives ΔH/R as the slope and ΔS/R as the intercept. The values of K, ΔH, ΔS and ΔG for the extraction of a particular seed oil (e.g. Amaranth oil) using n-hexane can be calculated using Eqs. (16)(18).

It is important to know that the values of ΔG, ΔS and ΔH for the extraction of oil from seeds/nuts, using solvent extraction method, differ for different seeds/nuts. As such, the thermodynamic of oil extraction from Amaranth seeds needs to be evaluated by researchers, as limited or no research article in that regards is available. Due to the differences in the thermodynamic parameters of different seeds/nuts, several researchers have reported the thermodynamics of oil extraction for good number seeds/nuts.

For instance, the values of ΔG, ΔS and ΔH, respectively, were 10.94–13.35 kJ/mol, 33.10–39.57 J/mol K and 0.12–1.25 kJ/mol, for solid coconut waste oil extraction [76]. Amin et al. [77], reported that for Jatropha curcas, the ΔG, ΔS and ΔH values were, −4.928 kJ/mol, 15.275 J/mol K and 0.1586 kJ/mol, respectively. For fluted pumpkin extraction, the ΔG, ΔS and ΔH values were −3.902 to −8.909 kJ/mol K, 0.234 kJ/mol K and 78.84 kJ/mol, respectively [78]. In the work of Agu et al. [65], the values of ΔG, ΔS and ΔH, respectively, were −64.82 kJ/mol, 1.22 J/mol K and 333.40 kJ/mol, for Colocynthis vulgaris Schrad seed oil extraction. Furthermore, for sunflower oil extraction process, Topallar and Geҫgel [79], reported that the ΔG, ΔS and ΔH values were −1.07 kJ/mol, 36.75 J/mol K and 11.2 kJ/mol, respectively.

As earlier highlighted, the thermodynamic parameters for the extraction of oil from Amaranth seeds/grains could be evaluated by the plotting of InK against 1/T. Since there is no literature information on thermodynamics of Amaranth seeds oil extraction, figure from similar published work was used as an illustration. For instance, Figure 2, shows the plots of InK (equilibrium constant) verses 1/T, at different particle sizes, for Colocynthis vulgaris Schrad seed [65]. Finally, from the values of ΔG, ΔS and ΔH, obtained by the aforementioned authors, they indicated the spontaneity, irreversibility and endothermic nature of the extraction processes.

Figure 2.

Plot of In K (equilibrium constant) versus 1/T (temperature, K−1) for the five different particle sizes (source, Agu et al. [65]).

Advertisement

6. Conclusion

It could be concluded from this chapter that due to the industrial, economic and health/nutritional benefits of Amaranth seeds oil, the insight into research on the kinetics and thermodynamics of Amaranth seed oil extraction has be made. It has also been justified that Soxhlet apparatus, using solvent like hexane, is an excellent conventional method for Amaranth seed/grains oil extraction. This chapter has highlighted the importance of oil extraction kinetics, as well as fitting experimentally obtained kinetic data, into known empirical kinetic models. Also, the need for thermodynamics studies of oil extraction processes, especially with respect to Amaranth seed oil extraction process, has been emphasized. Finally, there is need for researchers to now direct their studies towards the kinetics and thermodynamics of Amaranth seed oil extraction process, since there is little, or no literature information in this regards.

References

  1. 1. Gamel TH, Mesallam AS, Damir AA, Shekib LA, Linssen JP. Characterization of Amaranth seed oil. Journal of Food Lipids. 2007;14:323-334
  2. 2. Krulj J, Brlek T, Pezo L, Brkljaca J, Popovic S, Zekovic Z, et al. Extraction methods of Amaranthus sp. grain oil isolation. Journal of the Science of Food and Agriculture. 2016;96:3552-3558
  3. 3. Dhellot JR, Matouba E, Maloumbi MG, Nzikou JM, Ngoma Safou DG, Linder M, et al. Extraction, chemical composition and nutritional characterization of vegetable oils: Case of Amaranthus hybridus (var 1 and 2) of Congo Brazzaville. African Journal of Biotechnology. 2006;5(11):1095-1101
  4. 4. Lyon CK, Becker R. Extraction and refining of oil from Amaranth seed. Journal of the American Oil Chemists’ Society. 1987;64:233-236
  5. 5. Sun H, Wiesenborn D, Rayas-Duarte P, Mohamed A, Hagen K. Bench-scale processing of Amaranth seed for oil. Journal of the American Oil Chemists’ Society. 1995;72:1551-1555
  6. 6. He H-P, Corke H. Oil and squalene in Amaranthus grain and leaf. Journal of Agricultural and Food Chemistry. 2003;51:7913-7920
  7. 7. Becker R. Preparation, composition, and nutritional implication of Amaranth seed oil. Cereal Foods World. 1989;34(11):950-953
  8. 8. Bruni R, Medici A, Guerrini A, Scalia S, Poli F, Muzzoli M, et al. Amaranthus caudatus seed oil, a nutraceutical resources from Ecuadorian flora. Journal of Agriculture, Food and Chemistry. 2001;49:5455-5460
  9. 9. Becker R. Amaranth oil: Composition, processing, and nutritional qualities. In: Paredes-Lopez O, editor. Amaranth Biology, Chemistry and Technology. Boca Raton: CRC Press; 1994. pp. 133-144
  10. 10. He H-P, Corke H, Cai J-G. Supercritical carbon dioxide extraction of oil and squalene from Amaranthus grain. Journal of Agricultural and Food Chemistry. 2003;51:7921-7925
  11. 11. Westerman D, Santos RCD, Bosley JA, Rogers JS, Al-Duri B. Extraction of Amaranth seed oil by supercritical carbon dioxide. Journal of Supercritical Fluids. 2006;37:38-52
  12. 12. Leon-Camacho M, Garcia-Gonzalez DL, Aparicio R. A detailed and comprehensive study of Amaranth (Amaranthus cruentus) oil fatty profile. European Food Research and Technology. 2001;213:349-355
  13. 13. Belitz HD, Grosch W. Food Chemistry. 2nd ed. Berlin, Heidelberg, Germany: Springer-Verlag; 1999. pp. 631-692
  14. 14. Ortega JAA, Zavala AM, Hernandez MC, Reyes JD. Analysis of trans fatty acids production and squalene variation during amaranth oil extraction. Central European Journal of Chemistry. 2012;10(6):1773-1778
  15. 15. Rosales-Garcia T, Jimenez-Martinez C, Cardador-Martinez A, Martin-del Campo ST, Galicia-Luna LA, Tellez-Medina DI, et al. Squalene Extraction by supercritical fluids from traditional puffed Amaranthus hypochondriacus seeds. Journal of Food Quality. 2017:1-9. DOI: 10.1155/2017/6879712
  16. 16. Aguilera Y, Dorado ME, Prada FA, Martınez JJ, Quesada A, Ruiz-Gutierrez V. The protective role of squalene in alcohol damage in the chick embryo retina. Experimental Eye Research. 2005;80(4):535-543
  17. 17. Kohno Y, Egawa Y, Itoh S, Nagaoka S-I, Takahashi M, Mukai K. Kinetic study of quenching reaction of singlet oxygen and scavenging reaction of free radical by squalene in nbutanol. Biochimica et Biophysica Acta (BBA)—Lipids and Lipid Metabolism. 1995;1256(1):52-56
  18. 18. Warleta F, Campos M, Allouche Y, et al. Squalene protects against oxidative DNA damage in MCF10A human mammary epithelial cells but not in MCF7 and MDA-MB-231 human breast cancer cells. Food and Chemical Toxicology. 2010;48(4):1092-1100
  19. 19. Rao CV, Newmark HL, Reddy BS. Chemopreventive effect of squalene on colon cancer. Carcinogenesis. 1998;19(2):287-290
  20. 20. Hernandez Y, Lobo MG, Gonzalez M. Factors affecting sample extraction in the liquid chromatographic determination of organic acids in papaya and pineapple. Food Chemistry. 2009;114(2):734-741
  21. 21. Majors RE. An overview of sample preparation methods for solid. LC-GC Europe. 1999;17(6):8-13
  22. 22. Azmir J, Zaidul ISM, Rahman MM, Sharif KM, Mohamed A, Sahena F, et al. Techniques forextraction of bioactive compounds from plant materials: A review. Journal of Food Engineering. 2013;117:426-436
  23. 23. Reyes-Jurado F, Franco-Vega A, Ramirez-Corona N, Palou E, Lopez-Malo A. Essential oils: Antimicrobial activites, extraction methods, and their modeling. Food Engineering Reviews. 2014. DOI: 10.1007/s12393-014-9099-2
  24. 24. Wang L, Weller CL. Recent advances in extraction of nutra-ceuticals from plant. Trends in Food Science and Technology. 2006;17:300-312
  25. 25. Edgar U, Marcia J, Jaime O. Effect of pretreatment with microwaves on mechanical extraction yield and quality of vegetable oil from Chilean hazelnuts (Gevuina avellana Mol). Innovative Food Science and Emerging Technologies. 2008;9(4):495-500
  26. 26. Reverchon E, Marco ID. Review: Supercritical fluid extraction and fractionation of natural matter. Journal of Supercritical Fluids. 2006;38(2):146-166
  27. 27. Verma A, Hartonen K, Riekkola ML. Optimization of supercritical fluid extraction of indole alkaloids from Catharanthus roseus using experimental design methodology—Comparison with other extraction techniques. Phytochemical Analysis. 2008;19(1):52-63
  28. 28. Zhao S, Zhang D. An experimental investigation into the solubility of Moringa oleifera oil in supercritical carbon dioxide. Journal of Food Engineering. 2014;138:1-10
  29. 29. Mezzomo N, Martinez J, Ferreira SRS. Supercritical fluid extraction of peach (Prunus persica) almond oil: Kinetics, mathematical modeling and scale-up. Journal of Supercritical Fluids. 2009;51:10-16
  30. 30. Erdogam S, Ates B, Durmaz G, Yilmaz I, Seckin T. Pressurized liquid extraction of phenolic compounds from Anatolia propolis and their radical scavenging capacities. Food and Chemical Toxicology. 2011;49(7):1592-1597
  31. 31. Nieto A, Borrulli F, Pocurull E, Marce RM. Pressurized liquid extraction: A useful technique to extract pharmaceuticals and personal-care products from sewage sludge. TrAC Trends in Analytical Chemistry. 2010;29(7):752-764
  32. 32. Alupului A. Microwave extraction of active principles from medicinal plants. UPB Scientific Bulletin, Series B: Chemistry and Materials Science. 2012;74(2):129-142
  33. 33. Asghari J, Ondruschka B, Mazaheritehrani M. Extraction of bioactive chemical compounds from the medicinal Asian plants by microwave irradiation. Journal of Medical Plants Research. 2011;5(4):495-506
  34. 34. Chiremba C, Rooney LW, Trust BJ. Microwave-assisted extraction of bound phenolic acids in bran and flour fractions from sorghum and maize cultivars varying in hardness. Journal of Chromatography A. 2012;1012(2):119-128
  35. 35. Goula AM. Ultrasound-assisted extraction of pomegranate seed oil—Kinetic modeling. Journal of Food Engineering. 2013;117:492-498
  36. 36. Yolmeh M, Najafi MBH, Farhoosh R. Optimization of ultrasound-assisted extraction of natural pigment from annatto seeds by response surface methodology (RSM). Food Chemistry. 2014;155:319-324
  37. 37. Zu G, Zhang R, Yang L, Ma C, Zu Y, Wang W, et al. Ultrasound-assisted extraction of carnosic acid and rosmarinic acid using ionic liquid solution from Rosmarinus officinalis. International Journal of Molecular Sciences. 2012;13(9):11027-11043
  38. 38. Lopez N, Puertolas E, Condon S, Alvarez I, Raso J. Effects of pulsed electric fields on the extraction of phenolic compounds during the fermentation of must of Tempranillo grapes. Innovative Food Science and Emerging Technologies. 2008;9(4):477-482
  39. 39. Delsart C, Ghidossi R, Poupot C, Grimi N, Vorobiev E, Milisic V, et al. Enhanced extraction of phenolic compounds from merlot grapes by pulsed electric field treatment. American Journal of Enology and Viticulture. 2012;63(2):205-211
  40. 40. Puri M, Sharma D, Barrow CJ. Enzyme-assisted extraction of bioactives from plants. Trends in Biotechnology. 2012;30(1):37-44
  41. 41. Gomez-Garcia R, Martinez-Avila GCG, Aguilar CN. Enzyme-assisted extraction of antioxidative phenolics from grape (Vitis vinifera L) residues. 3 Biotech. 2012;2:297-300. DOI: 10.1007/s13205-012-0055-7
  42. 42. Adebayo SE, Orhevba BA, Adeoye PA, Musa JJ, Fase OJ. Solvent extraction and characterization of oil from African star apple (Chrysophyllum albidum) seeds. Academic Research International. 2012;3(2):178-183
  43. 43. Chan KW, Ismail M. Supercritical carbon dioxide fluid extraction of Hibiscus cannabinus L. seed oil: A potential solvent-free and high antioxidative edible oil. Food Chemistry. 2009;114:970-975
  44. 44. Mariod AA, Ismail M, Mattha B. Comparison of supercritical fluid and hexane extraction methods in extracting Kenaf (Hibiscus cannabinus) seed oil lipids. Journal of the American Oil Chemists’ Society. 2011;88:931-935
  45. 45. Niu L, Li J, Chen M-S, Xu Z-F. Determination of oil contents in Sacha inchi (Plukenetia volubilis) seeds at different developmental stages by two methods: Soxhlet extraction and time-domain nuclear magnetic resonance. Industrial Crops and Products. 2014;56:187-190
  46. 46. Omeh YS, Ezeja MI, Ugwudike PO. The physiochemical properties and fatty acid profile of oil extracted from Irvingia gabonensis seeds. International Journal of Biochemistry and Biotechnology. 2012;2(2):273-275
  47. 47. Lasekan O, Abdulkarim SM. Extraction of oil from tiger nut (Cyperus esculentus L.) with supercritical carbon dioxide (SC-CO2). LWT—Food Science and Technology. 2012;47:287-292
  48. 48. Dos Santos ICF, De Carvalho SHV, Solleti JI, Ferreira dela Sellas W, Teixeira da Silva de La Sallesc K, Meneghetti SMP. Studies of Terminalia catappa L. oil: Characterization and biodiesel production. Bioresource Technology. 2008;99:6545-6549
  49. 49. Menkiti MC, Agu CM, Udeigwe TK. Extraction of oil from Terminalia catappa L.: Process parameter impacts, kinetics, and thermodynamics. Industrial Crops and Products. 2015;77:713-723
  50. 50. Adepoju TF, Okewale AO, Olalekan AP, Adesina OA. Optimization, physicochemical analysis, proximate composition, elemental contents and fatty acid profile of oil extracted from Terminalia catappa L. International Journal of Advanced Research. 2014;2(1):1-10
  51. 51. Luque de Castro MD, Gracia-Ayuso LE. Soxhlet extraction of solid materials: An outdated technique with a promising innovative future. Analytica Chimica Acta. 1998;369:1-10
  52. 52. Li H, Pordesimo L, Weiss J. High intensity ultrasound-assisted extraction of oil soybeans. Food Research International. 2004;37:731-738
  53. 53. Rout PK, Naik SN, Rao YR, Jadeja G, Maheshwari RC. Extraction and composition of volatiles from Zanthoxylum rhesta: Comparison of supercritical CO2 and traditional processes. The Journal of Supercritical Fluids. 2007;42:334-341
  54. 54. Cuevas MS, Rodrigues CEC, Meirelles AJA. Effect of solvent hydration and temperature in the deacidification process of sunflower oil using ethanol. Journal of Food Engineering. 2009;95:291-297
  55. 55. Aquino LP, Borges SV, Queiroz F, Antoniassi R, Cirillo MA. Extraction of oil from pequi fruit (Caryocar brasiliense, Camb.) using several solvents and their mixtures. Grasas y Aceites. 2011;62(3):245-252
  56. 56. Rodríguez-Rojo S, Visentin A, Maestri D, Cocero MJ. Assisted extraction of resemery antioxidants with green solvents. Journal of Food Engineering. 2012;109:98-103
  57. 57. De Oliveira RC, de Barros STD, Gimenes ML. The extraction of passion fruit oil with green solvents. Journal of Food Engineering. 2013;117:458-463
  58. 58. Fernández MB, Perez EE, Crapiste GH, Nolasco SM. Kinetic study of canola oil and tocopherol extraction: Parameter comparison of nonlinear models. Journal of Food Engineering. 2012;111:682-689
  59. 59. Matthäus B, Brühl L. Comparison of different methods for the determination of the oil content in oilseeds. Journal of the American Oil Chemists Society. 2001;78:95-102
  60. 60. Patricelli A, Assogna A, Casalaina A, Emmi E, Sodini G. Fattori che influenzano l’estrazione dei lipidi da semi decorticati di girasole. Rivista Italiana Delle Sostanze Grasse. 1979;56:136-142
  61. 61. So GC, Macdonald DG. Kinetics of oil extraction from canola (rapeseed). Canadian Journal of Chemical Engineering. 1986;64:80-86
  62. 62. Sasmaz DA. Evaluation of diffusion coefficient of rapeseed oil during solvent extraction with hexane. Journal of the American Oil Chemists’ Society. 1996;73(5):669-671
  63. 63. Perez EE, Carelli AA, Crapiste GH. Temperature-dependent diffusion coefficient of oil from different sunflower seeds during extraction with hexane. Journal of Food Engineering. 2011;105:180-185
  64. 64. Baümler ER, Crapiste GH, Carelli AA. Solvent extraction: Kinetic study of mayor and minor compounds. Journal of the American Oil Chemists’ Society. 2010;87:1489-1495
  65. 65. Agu CM, Kadurumba CH, Agulanna AC, Aneke OO, Agu IJ, Nonlinear Kinetics EJN. Thermodynamics, and parametric studies of Colocynthis vugaris Shrad seeds oil extraction. Industrial Crops and Products. 2018;123:386-400
  66. 66. Meziane S, Kadi H, Daoud K, Hannane F. Application of experimental design method to the oil extraction from olive cake. Journal of Food Processing and Preservation. 2009;33:176-185
  67. 67. Kitanović S, Milenovic D, Veeljkovic VB. Empirical kinetic models for the resinoid extraction from aerial parts of St John’s Wort (Hypericum Perforatum L.). Journal of Biochemical Engineering. 2008;41:1-11
  68. 68. Menkiti MC, Agu CM, Udeigwe TK. Kinetic and parametric studies for the extractive synthesis of oil from Terminalia catappa L. kernel. Reaction Kinetics, Mechanisms and Catalysis. 2017;120:129-147
  69. 69. Han X, Cheng L, Zhang R, Bi J. Extraction of safflower seed oil by supercritical CO2. Journal of Food Engineering. 2009;92:370-376
  70. 70. Ayas N, Yilmaz O. A shrinking core model and empirical kinetic approaches in supercritical CO2 extraction of safflower seed oil. Journal of Supercritical Fluids. 2014;94:81-90
  71. 71. Chauhan G, Pant KK, Nigam KDP. Conceptual mechanism and kinetic studies of chelating agent assisted metal extraction process from spent catalyst. Journal of Industrial and Engineering Chemistry. 2015. DOI: 10.1016/j.jiec.2015.01.017
  72. 72. Rakotondramasy RL, Haret JL, Porte C, Faudet H. Solid-liquid extraction of protopiine from Fumaria officinalis. L-analysis determination, kinetic reaction and model building. Separation and Purification Technology. 2007;54:253-261
  73. 73. Paterson IF, Chowdhry BZ, Leharne SA. Polycyclic aromatic hydrocarbon extraction from a coal tar-contaminated soil using aqueous solution of nonionic surfactants. Chemosphere. 1999;38(13):3095-3107
  74. 74. Muhammad HH, Hasfalina CM, Hishamuddin J, Zurina ZA. Optimization and kinetics of essential oil extraction from citronella grass by ohmic heated hydro distillation. International Journal of Chemical Engineering and Application. 2012;3(3):173-176
  75. 75. Liauw MY, Natan FA, Widiyanti P, Ikasari D, Indraswati N, Soetaredjo FE. Extraction of neem oil (Azadirachta indica A.) using n-hexane and ethanol. Study of oil quality, kinetics and thermodynamics. ARPN Journal of Engineering and Applied Sciences. 2008;3(3):1-6
  76. 76. Sulaiman S, Abdul Aziz AR, Arova MK. Optimization and modeling ofextraction of solid coconut waste oil. Journal of Food Engineering. 2013;114:228-234
  77. 77. Amin S, Hawash G, El Diwani S, Rafe E. Kinetics and thermodynamics of oil extraction from Jatropha curcas in aqueous acidic hexane solutions. Journal of American Science. 2010;6(11):293-300
  78. 78. Nwabanne JT. Kinetics and thermodynamics study of oil extraction from fluted pumpkin seed. International Journal of Multidisciplinary Science and Engineering. 2012;3(6):11-15
  79. 79. Topallar H, Geҫgel U. Kinetics and thermodynamics of oil extraction from sunflower seeds in the presence of aqueous acidic hexane solutions. Turkish Journal of Chemistry. 2000;24:247-253

Written By

Chinedu M. Agu and Albert C. Agulanna

Submitted: 22 March 2019 Reviewed: 02 July 2019 Published: 18 March 2020