Journal of Food Engineering 124 (2014) 105116

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Journal of Food Engineering

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Review

Experimental design of supercritical uid extraction A review

K.M. Sharif a, M.M. Rahman a, J. Azmir a, A. Mohamed b, M.H.A. Jahurul c, F. Sahena c, I.S.M. Zaidul a,
a

Faculty of Pharmacy, International Islamic University Malaysia, Kuantan Campus, 25200 Kuantan, Pahang, Malaysia Faculty of Pharmacy, Cyberjaya University College of Medical Sciences, 63000 Cyberjaya, Malaysia c School of Industrial Technology, Universiti Sains Malaysia, Minden, Penang 11800, Malaysia
b

a r t i c l e

i n f o

a b s t r a c t
Supercritical uid extraction (SFE), a sustainable green technology leads a wide range of applications since the past decade. Like many other processes, SFE is sometimes criticized for its large number of factors which need to be properly adjusted before every single run. Experimental design and proper statistical analysis with small number of trials in adjusting the SFE parameters become popular in this regard. This paper is aimed to review the common experimental designs that are frequently used in the SFE process. Utilizations of different experimental designs in SFE with the intention of either screening the most inuential factors or optimizing the selected factors are briey reviewed. Strategies and recommendation addressing the choice of appropriate design, constructing design matrix, experimental trial and data analysis are discussed in this paper. For more application oriented readers of SFE, an effective and easy chart on choosing proper experimental design and a list of experimental design software are also included. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 18 May 2013 Received in revised form 16 September 2013 Accepted 1 October 2013 Available online 11 October 2013 Keywords: Supercritical uid extraction Experimental design Screening design Optimization design

Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Screening design for SFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Factorial design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1. Full factorial design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.2. Factorial factorial design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. PlackettBurman design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Optimization design for SFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Taguchi design. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Central composite design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. BoxBehnken design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4. Other optimization designs for SFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Recommended Strategies of using experimental design in SFE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Stage 1: Appropriate experimental design selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Stage 2: Experimental designing software and preparation of design matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3. Stage 3: Experimental trials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4. Stage 4: Data analysis and interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Concluding remark . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 107 107 107 108 108 108 108 109 112 112 113 113 113 114 114 114 114

3.

4.

5.

1. Introduction Experimental designs are being frequently used for the optimization of different operating conditions of various processes and
Corresponding author. Tel.: +60 9 570 4841; fax: +60 9 571 6775.
E-mail address: zaidul@iium.edu.my (I.S.M. Zaidul). 0260-8774/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.jfoodeng.2013.10.003

for improving the chromatographic separation performance, as well as achieving high extraction efciency (Hibbert, 2012; Dejaegher and Vander Heyden, 2011; Hanrahan and Lu, 2006; Ferreira et al., 2007a). Theoretically, a number of factors have simultaneous effect on a process. However, application of experimental design is the most effective way to identify and optimize the signicant factors, and to achieve a competent result by few experimental trials.

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Table 1 Changeable parameters of SFE in compared with Soxhlet extraction method (adapted from Caude and Thibaut, 1999). SFE Solvent choice Temperature Pressure Extraction time Solvent ow rate Sample size Extraction time Use of modier Soxhlet extraction Solvent choice Particle size of sample Extraction time

Therefore, the experimental design can be dened as an approach to solve the problem systematically and, it is applied to collect data and to analyze data for obtaining information-rich result (Gooding, 2004). Optimum and valid results with a minimum effort, time and resources are the primary objectives of applying the experimental design in analytical process (Montgomery, 2004; Cornell, 2011; Myers and Montgomery, 2002). In an experimental design, investigators deliberately maneuver one or several predetermined factors to know their impact on experimental outcome. Supercritical uid extraction (SFE) is based on the solvating properties of supercritical uid (SF), which can be obtained by employing pressure and temperature above the critical point of a compound, mixture or element. Extraction by SF depends on some intrinsic tunable natures of supercritical uid like temperature, pressure and some extrinsic features like the characteristics of the sample matrix, interaction with targeted analysts and many environmental factors (Cavalcanti and Meireles, 2012; Pereira and Meireles, 2010). A single SFE condition cannot generate enough information addressing all the affecting factors of SFE process. To overcome this difculty, a large number of variables need to be carefully identied and investigated (Diaz and Brignole, 2009; Espinosa et al., 2000; Diaz et al., 2000). By proper controlling of SFE parameters, the extractability of supercritical uid can also be modied which enable this process to nd its eld from food to pesticide researches (Azmir et al., 2013; Khosravi-Darani, 2010; Brunner, 2010; Herrero et al., 2010). Moreover, a higher degree

of freedom can be obtained in extraction by SFE than the conventional methods, which means the number of tunable properties goes higher in SFE. Thus, the tunable properties of SFE make this process more unique, sensitive and specic in compared with conventional extraction methods. Table 1 shows a comparison of adjusting parameters of SFE with traditional Soxhlet extraction process. SFE is regarded as a green process because it does not use chemical solvents with drastic environmental impacts. Some applications of SFE have already been commercialized and some are emerging (Machida et al., 2011). But still now it is considered as a black box design of process, because of the complex interaction of affecting factors and lack of knowledge on the in-depth uid dynamics of supercritical uid in extraction (Wang et al., 2010). Simple approximations of experimental units are possible to construct in this black box design, but detail point-to-point process and extraction principle are beyond measurable. Thus, experimental designs are applicable to consider many inuential variables and to generate reasonable result of interest without considering the unknown principle of SFE process. A graphical illustration of the position of SFE regarding numerous inuential factors and the estimation of outcome by experimental design is shown in Fig. 1. According to Fig. 1, some controlling variables i.e. x1, x2, x3, x4; some response variables i.e. y1, y2, y3, y4 and some noisy variables i.e. z1, z2, z3, z4 co-exist in a black box process. The objective of experimental designs is to optimize the response variables of a certain sample by systematic modication of controlling variables. The design does not consider the variability in the responses due to uncontrolled noisy variables in the experiment. The choice of experimental design for SFE depends on the objectives of the study, investigators intention, feasibility of experiment, cost-effectiveness, time consumption and many other important factors. For example, to nd the most potent factors in a particular experiment, two level factorial designs can be the choice whereas to optimize the previously found inuential factors within a predetermined range, more complex designs like Central Composite or Box Behnken design are appropriate. Based on the objectives of an experiment, all of those designs can be categorized into two broad categories: Screening design and optimization design. Most

Fig. 1. Black Box Design of SFE (adapted from Del Castillo, 2007).

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commonly used experimental designs in SFE are Full Factorial design, Fractional Factorial design, PlackettBurman design as screening design and Taguchi design, Central Composite design and BoxBehnken design as optimization design. Choosing the convenient design, proper experimental design software, experimental trials, data analysis and interpretation are common stages in every experimental design. These four stages are also the most crucial to execute a fruitful use of experimental design in SFE. The basic principle of different experimental designs, their applications on screening or optimizing SFE parameters are critically discussed in the early stage of this review. A practical strategy of using experimental design in SFE and recommendation are provided in the later stage. 2. Screening design for SFE Although a huge number of factors inuence the SFE process, some of them do not have signicant effect on it. Screening the most inuential factors is the primary objectives of employing experimental design in SFE. Screening designs are used to determine the most important factors and their interactions from all potential factors. These kinds of designs can examine qualitative, quantitative and mixer-related factors simultaneously (Dejaegher and Vander Heyden, 2011). They are applied for improvement of separation techniques, formulations, products or processes of quality control and for robustness testing. Two-level full factorial, twolevel factorial factorial and Plackett-Burman design are often used for screening purposes (Vander Heyden et al., 2000; Dejaegher and Vander Heyden, 2009; Dejaegher et al., 2009; Montgomery, 2004; Dejaegher and Vander, 2008; Lewis et al., 1999; Vander Heyden and Massart, 1996; Dejaegher and Heyden, 2007). Table 2 summarizes some advantages and disadvantages of different screening designs. 2.1. Factorial design Factorial designs can study more than one factor at two or more levels. Two-level factorial designs are used for screening purposes that can give main and interaction effects of the considered factors with fewer runs (Hibbert, 2012; Dejaegher and Vander Heyden, 2009; Dejaegher et al., 2009; Montgomery, 2004). Various combinations of different levels of selected factors are generally included in these experimental designs by which the interactions among factors can be assumed. Such designs are more efcient in terms of dealing with large number of variables than one variable at a time (OVAT) design. The number of factors and the number of levels of each factor are used to classify factorial designs. For instance, a 2 2 factorial design means it has two factors each at two levels and a 2 3 factorial design means it has three factors and two levels for each factor. Usually in factorial design, the actual variable is converted to coded variable to give better uniformity. To determine the relative effects of a factor, the coded factor level analysis is recommended because the model coefcients are dimensionless

in a coded factor level analysis and thus directly comparable (Montgomery, 2004; Kuehl and Kuehl, 2000). Analysis of variance (ANOVA) or regression analysis can be the basis for analysis of a factorial design and for model-tting. Factorial designs are generally classied into two categories; one is full factorial design and another is factorial factorial design (Kennedy and Krouse, 1999).

2.1.1. Full factorial design A two level full factorial design might be useful for screening when few number of factors need to be studied (Vander Heyden et al., 2000; Dejaegher and Vander Heyden, 2009; Dejaegher et al., 2009). All possible combinations of all the input variables and their levels are included in a two level full factorial design (Dejaegher et al., 2009; Montgomery, 2004; Dejaegher and Vander, 2008; Lewis et al., 1999). Full factorial design can be denoted by 2n when n is the number of factors (Kennedy and Krouse, 1999). Each factor has two levels: high and low (Lundstedt et al., 1998; Deming and Morgan, 1993; Otto, 1999; Hanrahan et al., 2005) which are expressed as +1 and 1, respectively. Sometimes the effect of the studied factors on a particular response can be described by a polynomial model and if necessary, that response may be optimized by another design. The experimental trial numbers are increased geometrically with the increase of factors for a full factorial design. For example, 22 runs of experiment are required to examine the effects of two factors, and 23 runs of experiment are required for three factors. Caldera et al. (2012) optimized extraction parameters of SFE to extract antioxidant compounds (carnosol and carnosic acid) from rosemary (Rosmarinus ofcinalis L.). 23 full factorial design was used to select important variables before optimization of the selected factors by BoxBehnken design. Three factors (temperature, pressure and static extraction time) were studied in this experiment. Ramandi et al. (2011) applied a full factorial design for screening the extraction parameters of fatty acids from Borago ofcinalis L. owers by SFE technique before optimization using central composite design. Four factors: temperature, pressure, volume of modier and static extraction time were considered as independent variables for full factorial design. All these factors were studied at two levels. The bioactive compounds from Helianthus annuus L. (sunower) were extracted using SFE under various conditions (Casas et al., 2007). The impact of pre-treatment of the sample, temperature, pressure and modiers was investigated using a full factorial design in this study. Maio et al. (1997) investigated the inuence of different conditions of SFE on chlorinated benzenes and hexachlorocyclohexanes extraction from contaminated soil by full factorial design. Extraction time, temperature, pressure and modier concentration were considered as input variables. The highest important factors were temperature and time, and the less inuential factor was pressure. Llompart et al. (1996b) used two levels full factorial design for screening the most inuential variables for underivatized phenol and cresols extraction from soil using SFE. Flow-rate of CO2, uid density, extraction cell temperature, nozzle and trap temperatures, amount of

Table 2 Advantages and disadvantages of different screening designs. Design Two level full factorial Advantages The main effect and the interaction of factors can be identied Less number of experimental trails is needed compare to full factorial design for the equal number of factors Large number of variables can be examined with a very few experimental trails Disadvantages The increment of number of factors leads to geometric increment of trial number. So, the design is not feasible for screening more than sixteen factors The effect from factor interactions is very limited and may be misguided as there is no measurement of error in this design The design is only useful for identifying signicant main effect and do not consider any two factors interaction effect

Two level factorial factorial

PlackettBurman

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modier, static extraction time and the contact time between the added modier and sample prior to extraction were considered for screening test. Among these eight input variables two variables (temperature of extraction cell and density of uid) were found to show statistically signicant impacts for all studied analytes. 2.1.2. Factorial factorial design To evaluate the effects of a large number of factors, many experimental runs are necessary which is not economically and practically feasible. The effects of certain factors on a response can be studied with a factorial factorial design under an economical and practical manner (Luftig and Jordan, 1998). When relatively large number of experimental trials is needed for a full factorial design, a fraction of the full factorial design is often used to obtain the desired information. Factorial factorial design with two levels contains only a fraction of full factorial design and it can examine f factors at two levels by 2fv experiments (v = 1, 2, 3, . . ., n) (Dejaegher et al., 2009; Montgomery, 2004; Dejaegher and Vander, 2008; Lewis et al., 1999). A fractional factorial design is considered as a representative subset of a full factorial design. In the initial stage of any study, it seems to be a good alternative of a full factorial design (Otto, 1999; Hanrahan et al., 2005). In obtaining signicant parameters of SFE for the extraction of essential oil from Diplotaenia cachrydifolia, Khajeh (2012) applied factorial factorial design (252) before the employment of BoxBehnken design. The effects of ve parameters, namely pressure, temperature, volume of modier, dynamic extraction times and static extraction times on the extraction yield were inspected. Extraction (static and dynamic) times showed no effect on the essential oil extraction. Khajeh (2011) tried to nd out the effects of various parameters on supercritical uid extraction of essential oil from Satureja hortensis. Four parameters (temperature, pressure, percentage of modier and time of extraction) were included in this study to determine the most signicant input factors and their interactions by a two level factorial factorial design (241). Temperature, pressure and percentage of modier showed signicant effect but extraction time did not show signicant effect on the extraction yield. Jowkarderis and Raoe (2012) used factorial factorial experimental design to select the important variables from different inuential SFE variables for the recovery of 4-nitrotoluene and 3-nitrotoluene from soil sample. The central composite design was used after a factorial factorial design for optimization of selected variables. Temperature, pressure, volume of modier and dynamic extraction time were studied factors. The three parameters other than temperature were found to have statistically significant effects on the extraction. 2.2. PlackettBurman design PlackettBurman design is an extensively applied design to screen the signicant variables of a process (Kennedy and Krouse, 1999). It has been developed by Plackett and Burman and it is also a factorial factorial design with two-levels (Plackett and Burman, 1946). Maximum f = N 1 factors with N runs can be examined in an experiments by a PlackettBurman design, where N is a multiple of 4. If the examined factor numbers are lower than f = N 1, then a subset of PlackettBurman design for N runs may be applied (Wang and Wan, 2009). Experiments are sometimes replicated for determining the errors of experiment. Usually rst-order polynomial model is tted for the PlackettBurman design to estimate the effects of several factors. The signicant factors of the estimated model can be identied by ANOVA (Plackett and Burman, 1946). Reche et al. (2002) employed PlackettBurman design for the evaluation of the inuence of several parameters to determine Nnitrosamines from rubbers. Pressure, temperature, extraction time

(dynamic and static), temperature of restrictor and volume of modier with two levels were the considered variables for SFE. This design was carried out prior to central composite design and it required 12 experiments. PlackettBurman design was used for screening of SFE parameters before optimization of the estimated parameters by central composite design for the phenol extraction from soil sample (Llompart et al., 1996a). Nine variables namely ow rate of CO2, density of uid, temperature of extraction cell, nozzle and trap temperature, amount of derivatizing reagent, concentration of pyridine, static extraction time, the time of contact of the sample and derivatizing reagents prior to extraction were considered in this study. Folded Plackett-Burman design with 14 degrees of freedom was studied and it involved two centered points plus 24 randomized experimental runs which mean altogether there were 26 runs. The applications of full factorial design, factorial factorial design and PlackettBurman design for screening the most important variables of SFE are listed in Table 3. 3. Optimization design for SFE Optimization is another practice of experimental design that conrms the optimal conditions or settings of an experiment. The optimization approach usually starts with a screening design to select the important factors and it proceeds with an optimization design (Box et al., 2005; Bruns et al., 2006; Massart, 1997) such as Taguchi design, central composite design (CCD) or Box Behnken design (BBD). The use of optimization designs for Supercritical uid extraction is summarized in Table 4. 3.1. Taguchi design Three steps have been proposed by Taguchi to achieve a robust design which consists of concept design, parameter design and tolerance design (Taguchi, 1986, 1987). Parameter design is frequently used for more robust or optimized output of SFE. The stages of Taguchi design used in SFE are illustrated in Fig. 2. Taguchi approach uses orthogonal array for determining experimental runs. The degrees of freedom which are necessary to study the number of variables and their interactions determine the size of the orthogonal array. The control factors or interactions correspond with the columns of orthogonal array and the carried out experiments correspond with the rows. Orthogonal array can consider many factors at a time and in this design the run number increases with the factor numbers but much less than factorial design. For example, if we consider three factors with two levels then L4 orthogonal array with only 4 runs is needed and twelve factors with ve levels can be analyzed by L50 array, which consists 50 runs. ANOVA, range analysis and analysis of signal-to-noise ratio are the main analysis methods for Taguchi experimental design. Understanding of the process and main factors and their levels of optimal input can be analyzed by a single Taguchi method. But the appropriate result will mostly depend on the selection of the most inuential factors and their levels which are usually xed by the investigator. By applying Taguchi method Chen et al. (2011) determined the optimum conditions of SFE parameters to produce higher yield of oil from dry ginger. Dynamic extraction time, temperature, pressure and powder particle size were used at three levels as input variables for optimization. Nine experimental runs were performed as L9 (34) orthogonal array. The experimental data was calculated by signal-to-noise ratio (S/N ratio). Liu et al. (2009) used orthogonal array design to optimize the extraction parameters for seed oil extraction from Opuntia dillenii and to arrange the experimental trials. The effects of three parameters on the optimal extraction yield were evaluated and a L16 (45) orthogonal matrix

K.M. Sharif et al. / Journal of Food Engineering 124 (2014) 105116 Table 3 Application of screening experimental designs for SFE. Name of the experimental design Full factorial design Full factorial design Full factorial design Full factorial design Sample Venezuelan Rosemary leaves Borago ofcinalis L. ower Helianthus annuus L. Olive Leaves Extract Antioxidant compounds (carnosol and carnosic acid) Fatty acids Bioactive compounds Waxes, hydrocarbons, squalene, b-carotene, triglycerides, atocopherol, b-sitosterol, and alcohols Polar milk fat globule membrane (MFGM) lipids Lipid Essential oil Chlorinated benzenes and cyclohexane Phenol and cresols Remark Three factors (extraction pressure, extraction temperature and static extraction time) Four factors (pressure, temperature, volume of modier and static extraction time) Four factors (pre-treatment of the sample, temperature, pressure and modiers) Three factors (extraction pressure, extraction temperature and ethanol as modier) References Caldera et al. (2012)

109

Ramandi et al. (2011) Casas et al. (2007) Tabera et al. (2004)

Full factorial design Full factorial design Full factorial design Full factorial design Full factorial design

Buttermilk Eucalyptus globulus wood Savory (Satureja hortensis L.) Soil Soil

Two factors (buttermilk source and temperature) Three factors (temperature, pressure and methanol modier) Two factors (temperature and pressure) Four factors (pressure, temperature, extraction time and modier concentration) Eight factors (carbon dioxide ow-rate, uid density, extraction cell temperature, static extraction time, nozzle and trap temperatures, amount of methanol and the time of contact between the added modier and sample prior to extraction) Three factors (pressure, temperature, and extraction time) Two factors (temperature and pressure) Three factors (pressure, temperature and extraction time) Four factors (pressure, temperature, modier volume and dynamic and static extraction times) Four factors (pressure, temperature, percent of modier and extraction time) Four factors (pressure, temperature, modier volume, and dynamic extraction time) Three factors (Pressure, temperature and, static and dynamic extraction time) Six factors (pressure, temperature, static and dynamic time, restrictor temperature and volume of modier) Nine factors (carbon dioxide ow rate, uid density, extraction cell temperature, static extraction time, nozzle and trap temperatures, amount of derivatizing reagent, pyridine concentration, and time of contact between the derivatizing reagents and sample prior to extraction)

Astaire et al. (2003) Gonzlez-Vila et al. (2000) Esquvel et al. (1999) Maio et al. (1997) Llompart et al. (1996b)

Full factorial design Full factorial design Factorial factorial design Factorial factorial design Factorial factorial design Factorial factorial design Factorial factorial design Placket-Berman design

Liquidsolid extraction cartridge Avian feed Rapeseed cake Diplotaenia cachrydifolia Satureja hortensis Soil Hantzsch reaction Rubbers

Environmental pollutants Amine hydrochloride Oil and minor lipid Essential oil Essential oil 4-Nitrotoluene and 3nitrotoluene Formaldehyde N-nitrosamines

Ho and Tang (1992) Bicking (1992) Uquiche et al. (2012) Khajeh (2012) Khajeh (2011) Jowkarderis and Raoe (2012) Reche et al. (2000) Reche et al. (2002)

PlacketBerman design

Soil samples

Phenol

Llompart et al. (1996a)

was selected to arrange the experiments. Each of the three factors contained four levels. Taguchi design was also applied on essential oil extraction from clove buds (Guan et al., 2007). The effect of three parameters (temperature, pressure and particle size) was investigated using three levels orthogonal array design. Yasoubi et al. (2007) used Taguchi experimental design to optimize the different SFE experimental conditions in phenolic compounds extraction from Punica granatum L. Peel. Three levels orthogonal array design with a 34 matrix was used to optimize four factors namely temperature, pressure, extraction time and percentage of modier. Four parameters: pressure, temperature, dynamic extraction time with ethanol as a modier were used to optimize the SFE extraction yield of tea seed oil by Taguchi experimental design (Rajaei et al., 2005). Three levels orthogonal array (L9) was applied in this study. 3.2. Central composite design Box and Wilson developed Central Composite Design (CCD) (Box and Wilson, 1951). Both linear and quadric models are allowed to be determined by this design. CCD seems to be a good

alternative of a three level full factorial design as it provides comparable results with smaller number of experiments (Ferreira et al., 2007a; Tarley et al., 2009; Hibbert, 2012). CCD usually consists of a full factorial design or factorial factorial design with two levels, additional axial or star points and at least one central point of the experimental design (Box and Wilson, 1951; Montgomery, 1997; Box et al., 2005; Bruns et al., 2006). The axial design and the central design are almost the same for the two-level full factorial design except one factor that may take on levels either above the high level or below the low level (Kuehl and Kuehl, 2000). CCD requires experiment numbers according to N = k2 + 2k + cp, here cp is replicate numbers of center point and k is factor numbers. CCD has been applied extensively in the optimization process of an extraction step to determine the optimum conditions of different experimental parameters (Dron et al., 2002; Garrido-Lpez et al., 2006; Pizarro et al., 2006; Brachet et al., 2001; Conde et al., 2006; Gonalves et al., 2006; Pellati et al., 2005; Baranda et al., 2005; Garcia et al., 2004; Iriarte et al., 2006; Araujo and Fryland, 2006). Effects of three factors (pressure, temperature and time) on the yield of phenolic and tocopherol contents of roasted wheat

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Table 4 Application of optimization experimental designs for SFE. Name of the experimental design Taguchi design Sample Date seed Extract Phenolics Remark Four factors (extraction temperature, extraction pressure, extraction time, and number of extraction) Four factors (pressure, temperature, dynamic time, percentage of modier) Four factors (extraction time, temperature, pressure, Powder particle size) Three factors (temperature, pressure and modier concentration) Four factors (pressure, temperature, ethanol concentration and time) Three factors (extraction pressure, extraction temperature and time) Four factors (pressure, temperature, volume of ethanol, static time) Three factors (temperature, pressure, particle size) Four factors (pressure, temperature, dynamic time, modier volume) Four factors (Pressure, temperature, time and percentage of modier) Four factors (pressure, temperature, modier and sample particle size) Three factors (Pressure, temperature, dynamic time) Four factors (pressure, temperature, dynamic time, modier) Four factors (The extraction temperature, pressure, ethanol concentration and the ratio of solvent to material) Four factors (pressure, temperature, modier volume, dynamic time) Three factors (temperature, pressure, modier: water, ethanol, acetic acid and their interaction) Three factors (temperature, pressure and CO2 ow rate) Four factors (pressure, temperature, ow rate and soaking time) Three factors (volume of ethanol as a co-solvent, dynamic extraction time and pressure) Four factors (pressure, temperature, modier volume and dynamic extraction time) Four factors (temperature, pressure, extraction time, and CO2 ow rate) Three factors (temperature, pressure and extraction time) Four factors (pressure, temperature, modier volume, and dynamic extraction time) Four factors (pressure, temperature, volume of methanol as modier, static and dynamic extraction time) Three factors (pressure, temperature and ow rate of CO2) Two factors (temperature and pressure) Three factors (pressure, temperature and time) Three factors (temperature, pressure and modier concentration) Five factors (solvent/meal ratio, number of extractions, temperature, particle size, extraction time) Two factors (pressure, and supercial velocity of supercritical CO2 at 313 K) Three factors (extracting pressure, extracting temperature, and ow rate of carbon dioxide) Three factors (pressure, temperature, nature and percentage of the polar modier) Three factors (Pressure, temperature and time) References Liu et al. (2012) Majdi et al. (2012) Chen et al. (2011) Ghafoor et al. (2010) Sun et al. (2010) Liu et al. (2009) Tam et al. (2007) Guan et al. (2007) Xiao et al. (2007) Yasoubi et al. (2007) Peng et al. (2006) Kim et al. (2006) Rajaei et al. (2005) Guo-qing et al. (2005) Aghel et al. (2004) LopezSebastian et al. (1998) Akanda et al. (2012) Sarker et al. (2012) Ivanov et al. (2012) Ghasemi et al. (2011) Wang et al. (2012) Zahedi and Azarpour (2011) Jowkarderis and Raoe (2012) Ramandi et al. (2011) Nyam et al. (2010) Nik Norulaini et al. (2009a) Gelmez et al. (2009) Kassama et al. (2008) Kaur et al. (2008) Duarte et al. (2004) Ge et al. (2002) Brachet et al. (2000) Zhou et al. (2013)

Taguchi design Taguchi design Taguchi design Taguchi design Taguchi design Taguchi design Taguchi design Taguchi design Taguchi design Taguchi design

Tobacco Seed Ginger (Zingiber ofcinalis) Grape (Vitis labrusca B.) peel Bupleurum falcatum Opuntia dillenii Haw. Cyperus rotundus Clove (Eugenia caryophyllata Thunb.) Marchantia convoluta Punica granatum L. Peel Stellera chamaejasme L.

Seed Oil Ginger oil Bioactive compounds Saikosaponins Seed oil Main volatile constituents Clove bud essential oils and eugenol Essential oil Total phenolics Daphnoretin, 7-methoxydaphnoretin and 1,5-diphenyl-1pentanone Essential oil Seed oil Flavonoids

Taguchi design Taguchi design Taguchi design

Abies koreana Wilson Tea seed Humulus lupulus L.

Taguchi design Taguchi design

Mentha pulegium L. Rosemary extract

Essential oil De-aromatization

Central composite design Central composite design Central composite design Central composite design Central composite design Central composite design

Mango Seed Kernel Viscera of African Catsh (Clarias gariepinus) Linseed Myrtus communis L. leaves Cyperus rotundus Linn. Passiora seed

Cocoa butter analogy Fat Fish Oil Total oil Essential oils Essential oil Seed oil

Central composite design

Soil

4-nitrotoluene and 3-nitrotoluene

Central composite design

Flower of borage (Borago ofcinalisL.) Roselle seeds Anastatica hierochuntica Wheat germ Tomato skin Tomato paste

Fatty acids and essential oils

Central composite design Central composite design Central composite design Central composite design Central composite design

Phytosterol Non-polar compounds Antioxidants Lycopene Lycopene

Central composite design Central composite design Central composite design BoxBehnken design

Red pepper (Capsicum frutescens L.) Wheat germ Leaves of Erythroxylum coca var. coca Frankincense

Oleoresins Natural vitamin E Cocaine Volatile oil

K.M. Sharif et al. / Journal of Food Engineering 124 (2014) 105116 Table 4 (continued) Name of the experimental design BoxBehnken design Sample Mangosteen fruit pericarp (Garcinia mangostana L) Rapeseed Diplotaenia cachrydifolia Rosemary Leaves Maydis stigma Herba Moslae Zingiber zerumbet (L) Tomato skins Pueraria lobata Grapefruit (Citrus paradisi Macf.) seeds Spirulina platensis Castor oil Extract Xanthones Remark Three factors (pressure, temperature and time) References Zarena et al. (2012) Cvjetko et al. (2012) Khajeh (2012)

111

BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design BoxBehnken design

Oil Essential oil Antioxidant Compounds Flavonoids Essential Oil Non-polar compounds Lycopene Flavonoids Limonoids and naringin Antioxidants Fatty acid composition

Three factors (pressure, temperature and extraction time) Four factors (pressure, temperature, modier volume and, dynamic and static extraction times) Three factors (extraction pressure, extraction temperature and static extraction time) Three factors (temperature, pressure and co-solvent amount) Three factors (temperature, pressure and extraction time) Three factors (temperature, pressure and CO2 amount) Three factors (pressure, temperature and time) Three factors (pressure, temperature and co-solvent amount) Three factors (pressure, temperature and time or % co-solvent) Three factors (pressure, temperature and time) Four factors (pressure, temperature, methanol concentration and water concentration on the yield of methylated castor oil) Three factors (temperature pressure and time)

Caldera et al. (2012) Liu et al. (2011) Nie et al. (2010) Nik Norulaini et al. (2009b) Yi et al. (2009) Wang et al. (2008) Yu et al. (2007) Wang et al. (2007) Turner et al. (2004) Sonsuzer et al. (2004)

BoxBehnken design

Thymbra spicata

Aroma compounds

germ were determined during supercritical carbon dioxide extraction using CCD (Gelmez et al., 2009). The dependent variables were the yield of total phenolic compounds and the yield of total tocopherol compounds, and their antioxidant activities. Ghasemi et al. (2011) applied CCD to optimize the experimental parameters of SFE such as pressure, temperature, volume of modier, extraction time (static and dynamic) for essential oils extraction from Myrtus communis L. leaves. Three level CCD was used for optimization process after screening by a two-level fractional factorial design. Wang et al. (2012) isolated essential oil from the rhizomes

of Cyperus rotundus Linn using supercritical CO2. The four SFE factors (temperature, pressure, extraction time, and ow rate of CO2) were optimized by CCD for getting optimal yield of essential oils. A second-order polynomial model was used to calculate the oil yield. Ramandi et al. (2011) used SFE in different conditions for the extraction of fatty acids and essential oils from Borago ofcinalis L. owers. CCD was used to optimize the experimental parameters (temperature, pressure and volume of methanol as modier) after using a two levels full factorial design. Brachet et al. (2000) applied CCD as an optimization procedure for the extraction of cocaine

Fig. 2. Parameter design of Taguchi (adapted from Zhang et al. (2007)).

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Table 5 Comparison of run numbers and coefcient between BBD and CCD (adapted from Ferreira et al. (2007b)). Factors Number of coefcient Number of experiments BBD 2 3 4 5 6 7 8 6 10 15 21 28 36 45 13 25 41 61 85 113 CCD 9 15 25 43 77 143 273 Efciency BBD 0.77 0.60 0.61 0.46 0.42 0.40 CCD 0.67 0.67 0.60 0.49 0.36 0.25 0.16

from Erythroxylum coca var. coca leaves. After selection of signicant factors (pressure, temperature, nature of the polar modier and percentage of the polar modier), a CCD was used to optimize these factors to get higher extraction yield.

3.3. BoxBehnken design BoxBehnken design (BBD) was developed by Box and Behnken (Box and Behnken, 1960). This design consists of a factorial factorial design with three levels and an incomplete block design in such a way to present as a rotatable or nearly rotatable design and to avoid the extreme vertices. BBD requires experiment numbers based on N = 2k(k 1) + C0, here k is factor numbers and C0 is central point numbers. BBD is useful to avoid experiments which are in extreme conditions because the highest level and lowest level combinations for every factor cannot be included in BBD. Unsatisfactory results might be avoided in BBD. The signicant effects of BBD on the response can be examined by ANOVA and the optimal response can be determined by the regression model with calculating the derivatives of the model. CCD has more factor levels than BBD thus BBD can be used as an economical alternative of CCD (Otto, 1999; Hanrahan et al., 2005; Ferreira et al., 2007b). A comparison between BBD and CCD in term of experiment numbers and coefcient numbers are shown in Table 5. If an experiment has
Table 6 Application of some other experimental designs for SFE optimization. Name of experimental design D-optimal experimental design Sample Earthworms Extract Polycyclic aromatic hydrocarbons Oil and minor lipid Flavonoid compounds Flavonoid compounds Carotenoids

4 factors and 16 coefcients, it will require 25 runs for both BBD and CCD but by increasing the number of factors, the run number of BBD are slowly improved than CCD i.e. 273 runs are required for 8 factors experiments by CCD whereas BBD require only 113 (see Table 6). Among various applications, BBD are employed to determine the critical conditions for optimizing yield in extraction process (Turner et al., 2004; Gfrerer and Lankmayr, 2005). Nie et al. (2010) employed BBD to determine the optimal conditions of supercritical uid extraction of essential oil from Herba Moslae. Three factors (temperature, pressure and extraction time) with three levels of each factor were selected as input factors. The effects of these factors on the extracted essential oil yield were evaluated and total 15 runs were conducted in this study. The effects of three independent variables of SFE on the yield of lycopene extraction from tomato skins using BBD were investigated by Yi et al. (2009). Wang et al. (2008) employed SFE for the extraction of avonoids from Pueraria lobata. The optimal conditions were determined using BBD by evaluating the effects of three parameters (temperature, pressure and co-solvent amount) with three levels on the avonoid yield. Three variables (temperature, pressure and ow rate of CO2) were considered as independent variables and total 17 experimental runs were conducted in this study. BBD was used to optimize the effects of different extraction parameters on SFE of antioxidants extraction from Spirulina platensis (Wang et al., 2007). Three factors (pressure, temperature and time) were investigated at three levels in this study. Sonsuzer et al. (2004) optimized the parameters of SFE that were affecting extraction yield of aroma compounds from Thymbra spicata using BBD. Three independent variables at three levels were examined. The independent variables were temperature, pressure and time. 3.4. Other optimization designs for SFE Hoogerbrugge et al. (2003) extracted polycyclic aromatic hydrocarbons from earthworms and used D-optimal experimental design for optimization purpose of inuential SFE parameters. The yield of 15 polycyclic aromatic hydrocarbons (PAH) was optimized

Remarks 15 Polycyclic aromatic hydrocarbons (PAH) were extracted and the yield was optimized using ve factors (temperature, pressure, amount of trapping sorbent, ow, and dynamic extraction time) Three factors (pressure, temperature and extraction time) Three factors and three levels (pressure, temperature and dynamic extraction time) Three factors at three levels (extraction pressure, extraction temperature and dynamic extraction time) Two factors at ve levels (pressure and temperature)

Reference Hoogerbrugge et al. (2003)

Full factorial design Full factorial design Full factorial design Full factorial design

Rapeseed cake Spearmint (Mentha spicata L.) leaves Strobilanthes crispus (Pecah Kaca) leaves Scenedesmus almeriensis

Full factorial design

Spirulina Pacica algae

Carotenoids

Full factorial design

Genetic Algorithm (GA)

Spiked soil and marine sediment standard reference material Chamomile

Polynuclear aromatic hydrocarbons Chamomile extraction Nimbin

Four factor and three levels (temperature and pressure of the supercritical uid, dynamic extraction time and percentage of ethanol added as the modier) Four factors and ve levels (pressure, temperature, extraction uid volume and methanol modier concentration) The effect of particle diameter on extraction yield of Chamomile was investigated and the yield was optimized using two factors (temperature and pressure) GA optimization was compared with GS optimization technique and GA found to be a more efcient technique. Temperature, pressure, CO2 ow rate and particle diameter were the optimization factors MOS is highly efcient for studying a large number of variables and identifying optimal extraction conditions

Uquiche et al. (2012) Bimakr et al. (2011) Liza et al. (2010) MacasSnchez et al. (2010) Careri et al. (2001) Notar and Leskovs (1997) Rahimi et al. (2011) Zahedi et al. (2010)

Genetic Algorithm (GA) and traditional Gradient Search (GS) Multivariate optimization scheme (MOS)

Neem seeds

Soil samples

Pesticide residues

Zhou et al. (1997)

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using ve factors namely temperature, pressure, trapping sorbent amount, ow, and extraction time (dynamic). Liza et al. (2010) extracted bioactive avonoid from Strobilanthes crispus (Pecah Kaca) using supercritical carbon dioxide extraction. Three levels full factorial design was applied for optimization of input parameters for obtaining highest yield. Pressure, temperature and extraction time (dynamic) were considered as input parameters. Macas-Snchez et al. (2010) observed the inuence of temperature and pressure on the extraction of lutein and b-carotene from freeze-dried powder of Scenedesmus almeriensis. A three level full factorial design was used for the optimization of two input parameters. The effects of independent variables, temperature and pressure were optimized for Chamomile extraction with SFE using genetic algorithm optimization technique (Rahimi et al., 2011). Zhou et al. (1997) applied multivariate optimization scheme (MOS) to investigate the effects of SFE parameters for the extraction of pesticide residues from soil. Large number of factors can be examined and optimized using MOS. A list of these designs with their application on SFE is provided in Table 5. 4. Recommended Strategies of using experimental design in SFE 4.1. Stage 1: Appropriate experimental design selection In practice, there are two types of situations where the use of experimental design in SFE is benecial. The rst situation is trying to understand the main controlling factors on the SFE yield and the other is measuring the optimal value for the dominant factors. Fig. 3 illustrates the approach of the selection of experimental design. Before going for optimization, it is benecial to use screening design in a process which will both save time and labor. When the factor numbers are small, the two level full factorial design can be the choice for screening. But when the factor numbers increase (>5), Pluckett-Burman or factorial factorial become the option for screening purpose. Minimum experimental trials are needed in a Plackett-Burman design to screen the impacting factors. The variable range of the selected factors may contribute to the total yield in different ways. The best value for maximizing the yield is sometimes too theoretical to achieve, hence the term optimum has been applied. Optimization studies try to nd the most optimal levels of factors in SFE. For the optimization, choosing the levels to be inves-

tigated are crucially important. Taguchi, CCD or BBD can be used for optimization of small number of factors. BBD design allows much economical alternative than other optimization designs.

4.2. Stage 2: Experimental designing software and preparation of design matrix At this point, design matrix of an experimental study needs to be generated. Some specialized experimental design software exists commercially in market like DOE expert, Fusion Pro and Modde. Some general statistical software with experimental design compatibility can also be used for this purpose. Minitab, JMP and Matlab are well known package for experimental design purpose. A list is provided in Table 7 showing some experimental design software packages. Most of the software packages use different user interface to make this stage easy and convenient. Familiarity with software before data use is also recommended. Little effort is required to design and analyze data for routine analysis by specialized software that is user-friendly. For example, DOE expert has its rst page where investigators have to click on appropriate design and select number of factors and their levels. Based on the data this software is made to produce a design matrix for the experiment. At this point, investigator should do trials in real life and put their data on the previously prepared design matrix. After clicking the analysis button, investigators will nd a detail result of lack of t, coefcient, p-value and many other statistics, graphics to understand results. On the other hand, Matlab has more functionality on data analysis of designed experiment than specialized software. But for its complicated user interfaces, it is only recommended for complex data analysis. Matlab (Mathworks, Inc., USA) has some toolbox for specialized application of experimental design. Neural network toolbox, genetic algorithm toolbox etc. are mainly made for more application oriented research and can easily be incorporated for SFE optimization. In addition, Design-Expert and Minitab software have schemes like RSM by desirability function for multiple response optimization. These software packages are also useful to optimize a large number of factors simultaneously. Furthermore, neural network models based multiple-response optimization can also be carried out by genetic algorithm using the software package of Matlab.

Fig. 3. Design selection chart.

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Table 7 Software packages for experimental design and analysis (adapted from Hibbert (2012)). Specialized experimental design and analysis software Design-Expert Stat-Ease Inc., http://www.stateease.com/ Fusion Pro S-Matrix Corporation, http://www.smatrix.com/ Modde Umetrics, http://www.umetrics.com/moddde Unscrambler Camo AS, http://www.camo.com DOE++ ReliaSoft Corporation., http://www.doe.reliasoft.com/ DOE Wisdom Launsby Consulting. http://www.launsby.com/ DOEpack Productivity-Quality Systems, Inc. http://www.pqsystems.com/ General statistical software with experimental design compatibility JMP SAS Institute Inc., http://www.sas.com/ Minitab Minitab Inc., http://www.minitab.com STATISTICA StatSoft, http://www.statsoft.com Matlab The Mathworks Inc., http://www.mathworks.com. Origin Microcal Software, http://www.originlab.com/ Statgraphics Startpoint Technologies, http://www.startgraphics.com

Experimental Experimental Experimental Experimental Experimental Experimental Experimental Statistical Statistical Statistical Statistical Statistical Statistical

design design design design design design design

Software Software Software Software Software Software

4.3. Stage 3: Experimental trials SFE experimental trials are sometimes troublesome because of numerous external parameters involved. Reproducibility and precision must be checked before SFE experiments are being carried out in a particular setting. Most of the time, room temperature, water content, particle size and collection of analysts need to be constant for complete experimental trials. Day to day variability and reproducibility in a particular day should be considered before a run. Data collection process should be rigorously monitored, for example, stopwatch and traditional clock is used in collecting information about time. 4.4. Stage 4: Data analysis and interpretation The rst step of data analysis should be concentrated on tting the value of experimental data with mathematical model applied. It is primary steps to go for further analysis and interpretation. Sometimes investigators will nd that mathematical models are not sufcient to consider full experimental range under study. A higher order model can be a way to overcome this problem. Evaluation of model tting for experimental design in SFE study can be done by ANOVA. A statistical signicant regression and a non-signicant lack of t data represent that the experimental data are well tted with the model used. Another way is to look at residual value. If the large amount of variation can be described by residual values instead of regression equation, it can be interpreted as the variation observed due to pure error will also question the model quality (Pimentel and Barros, 1996; Cornell, 1990). A well tted model should show a normal distribution of residuals if a visual graph is created for easier inspection of model tting. The visualization of the predicted model equation can be obtained by the surface response plot. 5. Concluding remark Experimental design is very important for conducting modern research using SFE to obtain precise data. Designed experiment can give systematic investigation route and provide sequential steps for understanding linear, interaction and more complex types of interaction. But successful applications of experimental design in SFE rely on both understanding about SFE and knowledge on experimental design techniques. Some of commonly used experimental designs in SFE are demonstrated and the applications of different experimental designs to screen the SFE affecting factors and consequently to optimize of those selected factors are summarized. This review demonstrates the dimensionality of the experimental designs in SFE study.

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