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To cite this article: Siti Nuurul Huda Mohammad Azmin, Zainuddin Abdul Manan, Sharifah
Rafidah Wan Alwi, Lee Suan Chua, Azizul Azri Mustaffa & Nor Alafiza Yunus (2016):
Herbal Processing and Extraction Technologies, Separation & Purification Reviews, DOI:
10.1080/15422119.2016.1145395
Download by: [Universiti Teknologi Malaysia] Date: 26 January 2016, At: 00:34
Herbal Processing and Extraction Technologies
Siti Nuurul Huda Mohammad Azmin1,2, Zainuddin Abdul Manan1,2, Sharifah Rafidah Wan
Alwi1,2, Lee Suan Chua3, Azizul Azri Mustaffa1,2 and Nor Alafiza Yunus1,2.
1
Process Systems Engineering Centre (PROSPECT), Research Institute of Sustainable
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Environment (RISE),
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2
Faculty of Chemical Engineering,
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3
Institute of Bioproduct Development (IBD), Universiti Teknologi Malaysia, 81310 UTM, Johor
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Submitted Dec. 30, 2013; Revised Nov. 11, 2014 and Oct. 25, 2015; Accepted Jan. 14, 2016
Abstract:
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Herbs are widely utilized in food and health industries. Their beneficial effects to the human
body have been attributed to the presence of active phytochemical ingredients with some
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efficiency for disease treatment as well as for beauty and health enhancement. Public awareness
on the adverse effects of synthetic chemical products also increased the demand for herbal
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products. Highly efficient herbal processing and extraction technologies have been developed to
obtain the optimal amounts of active ingredients from herbs and cope with the rising demands
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for herbal products. This paper reviews the state-of-the-art development in herbal processing
and extraction methods from the year 1991 until 2015. The paper begins with a brief history of
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herbal usage, followed by descriptions of ten types of extraction processes and critical analysis
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methods are also presented. The paper concludes with a highlight of the current and future
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Keywords:
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1 INTRODUCTION
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Throughout human history, herbs have been used in food, cosmetics and fragrances [1]. In
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addition, they are a source of traditional medicines for the treatment of various illnesses and
diseases [2]. Traditional medicine has been defined by the World Health Organization (WHO)
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as “health practices, approaches, knowledge and beliefs incorporating plant, animal and mineral-
based medicines, spiritual therapies, manual techniques and exercises, applied singularly or in
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combination, to treat, diagnose and prevent illnesses or maintain well-being” [3]. Herbal
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recent WHO report [3] stated that 5.6 billion people, or approximately 80% of the world’s
population, use herbal products for their primary health care [3-5]. Herbal products are currently
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being used as dietary supplements, nutraceuticals, health products, and traditional medicines.
These products also are being prescribed by Chinese and Indian national pharmacopeias [5]. The
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botanical dietary supplement market in the U.S. has expanded rapidly from US$ 2.9 billion in
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1995 [6] to US$ 4.8 billion in 2008 [7]. Over 42% of the U.S population has claimed to have
used botanical dietary supplements either to widen their current diet or to treat or to prevent
health-related issues [5]. European dietary supplements have contributed to a steady 4% growth
rate of the market between 2004 and 2011. The total market in 2004 was valued at US$ 6.2
2
billions [8]. With Malaysians consuming over US$ 1.44 billion worth of herbal-related products
(with over 80% imported) [9], the opportunity to increase herbal product processing in Malaysia
has expanded. From 2000 to 2005, annual sales of traditional medicines increased from US$ 385
million (RM1 billion) to US$ 1.29 billion (RM45 billion), as reported by Malaysian National
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News Agency, BERNAMA [10]. The expected growth of the herbal medicine industry is
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With the increased demand for herbal products, Malaysia is well-positioned to be a key global
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player in this field because of its rich biological resources, cultural background, and trade links
[1]. In addition, Malaysia is ranked fourth in Asia and twelfth in the world as the most
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biodiverse nation, with 3,000 species of medicinal plants and 15,000 species of flowering plants
[12]. Among the 3,000 known medicinal plants [13], the top Malaysian traditional medicinal
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plants are Tongkat Ali (Eurycoma longifolia), Kacip Fatimah (Labisia pumila), Hempedu Bumi
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stamineus), and Pegaga (Centella asiatica). Among these known plants, less than 50 traditional
medicine species have been scientifically investigated, with the remainder not yet characterized
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[1]. Worldwide, more than 35,000 plant species have been reported to be employed for medical
purposes [14]. Even with this extensive number of available plant species, Rates [15] has
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reported that only 121 active compounds from herbs have been utilized, with approximately 25%
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Medicinal plants have often been applied for a broad range of acute and chronic conditions [16].
This provides ample opportunity to gain a vast wealth of knowledge through exploration of these
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plants. Phytochemical constituents in medicinal plants, such as flavonoids, phenolics, and
saponins [17], are believed to have numerous therapeutic abilities and are able to reduce the risk
of multiple diseases, including inflammatory conditions and cancer [18]. They contribute to the
protection of herbs from microbial and insect invasions [19]. Flavonoids have been utilized to
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improve human health via their multiple biological functions including anti-inflammatory [20],
antimicrobial [21], antioxidant [22], and anticancer activities [23] and the prevention of
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osteoporosis [24]. Tsao and Deng [25] have reported that phenolic acids from herbs have
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antioxidant activities that exceed the values exhibited by vitamins C and E. Polyphenols have
also been applied in the prevention of both cancer and heart disease [19]. Aqueous extracts of
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the Malaysian herb L. pumila, commonly known as Kacip Fatimah, have been demonstrated to
protect significantly human dermal fibroblasts from cell damage caused by ultraviolet irradiation
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[26], most likely as a result of the presence of flavonoids [27]. Ginseng, one of the most
commonly used herbs, contains saponins as active ingredients [28]. Ginseng exhibits a broad
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With the high demand for herbal products that promote health advantages, the identification of
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the most effective methods [30] for extracting the active ingredients from plants has become
increasingly important. Traditionally, herbal extracts are prepared by boiling the roots, leaves, or
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the entire plant in water using a method known as tisane or decoction. These types of extracts
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can be consumed orally, but these methods are time-consuming and may not be the most
effective method for extracting the active ingredients from the herbs. This article provides a
review of the state-of-the-art on herbal processing techniques and discusses the effectiveness of
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1.1 A History of the Uses of Herbs
Herbs have been used for many purposes, including as ingredients for medicinal products, beauty
enhancers, fragrances, and food. In the case of beauty enhancers, the natural components in herb
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products are easily absorbed by the human skin [19] and are both safe and compatible with
human body, as natural ingredients that have demonstrated no known toxicity. Natural products
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in skincare formulations have been shown to exhibit significant antioxidant [100], emollient
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[101], and UV–B protection [102] properties.
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In the early nineteenth century, the first chemical analyses performed by scientists were utilized
to determine the active ingredients from plant extracts, which subsequently led to the
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development of natural (traditional) medicines that had been passed historically through
generations by words of mouth [2]. Many of the herbs and spices used for food seasoning also
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yield useful medicinal compounds [31, 32]. Simple preparation methods for processing the plant
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herbs by boiling either the entire plant or selected parts of the plant have been employed by
Starting from the planting and harvesting stages, the steps practiced for processing the
natural products are very important. Every part of the plant matures at different times, which
suggests that the harvesting process should be optimized on the basis of the desired plant parts.
As shown in Table 1, the general guidelines for harvesting the three primary parts of the herbal
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plants (i.e., leaves, stems, and roots) are presented to enable selection of the harvesting time on
the basis of the part of the plant that provides the optimal results in the extraction process.
Karimi et al. [34] showed that the leaves of L. pumila exhibited higher antioxidant activities and
total saponin amounts [35] than the plant roots and stems. Ramlan [36] classified four different
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stages of herbal processing to produce the final herbal products.
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Before processing starts, the harvested herbal plants must be pre-processed. At this stage, the
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plants must be dried to remove moisture for preservation, preventing bacteria activity and
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restricting fungal growth [37]. To increase the surface area of the dried herb plant materials for
improved contact with the solvent during the subsequent extraction process, the dried plant must
first be ground.
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An increased surface area of the dried plant materials will improve the
performance of the extraction process. The particle size of the milled plants is one of the factors
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that can affect the extraction yield.
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In the extraction processes, the operating conditions can greatly affect the efficiency of a
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solvent system, the solvent-to-herbs ratio, the particle sizes of ground and dried herbs materials,
the temperature, the duration, and the agitation rate, as discussed by Sim et al. [37]. Preliminary
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studies are necessary to determine these operating conditions prior to starting the extraction
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experiments. Literature studies can provide very useful information for determining the optimal
operating conditions.
In some processes, solvents are mixed with herbal raw materials (normally in the dry
powder form) and then subjected to forces such as heat, pressure or microwave power to enable
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the phytochemicals to diffuse out of the herb cells into the solvent medium. The mixture of
solvent and extracted phytochemicals can exist in a miscible form, or can produce two liquid
layers (if essential oil is produced). The solvents are then removed from the mixture, typically
via evaporation in a rotary evaporator. Then, the crude extract is further processed into natural
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products.
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3.0 STATE OF THE ART IN HERBAL
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EXTRACTION METHODS
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With herbal processing, the type of extraction process can greatly affect the final natural
products obtained. Suitable extraction processes are needed to extract the desired active
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ingredients from herbs. Fig. 1 shows ten possible extraction methods that will be detailed
thereafter. In Table 2, the advantages and disadvantages of the available extraction methods are
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presented. The biggest advantage is when the extraction method can be used to extract plant
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compound in a short time with the minimum solvent consumption. Short extraction time is
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desirable due to the associated reduced electricity consumption and the ability to minimise any
Supercritical fluid extraction (SFE) is one of the extraction methods in herbal processing
due its ability to extract the valuable ingredients from herbs with high yield and good quality
[38]. Its favorable features include the ability to perform extractions at near-ambient
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temperatures, which prevents thermal degradation of the substance of interest [39]. SFE is also
being extensively studied as an alternative to conventional extraction methods [38]. Among the
possible SFE solvents, carbon dioxide (CO 2 ) is the most established and widely used solvent
[40]. CO 2 has unique properties, which include non-toxicity, non-flammability, lack of solvent
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residue in the final product, and lack of reactivity with extraction materials and equipment.
These behaviors make it commonly used in numerous extraction processes. In addition, this gas
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is less expensive than most common solvents, which reduces the cost of the extraction process.
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One of the most important benefits of CO 2 in the SFE processes is the reduction in the
environmental and health concerns that arise from the use of organic solvents [41, 42].
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In the SFE environment, only one fluid phase exists; the properties of this fluid resemble an
intermediate phase between gas and liquid. Carbon dioxide at the supercritical state has a critical
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temperature and pressure of 31.1 °C and 73.8 bar, respectively. Under these conditions, CO 2
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exhibits both gas-like characteristics, with high diffusion coefficients and low viscosities, and
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liquid-like characteristics, with high solvating power properties. These features make
supercritical CO 2 a good fluid solvent [43]. Both viscosity and diffusivity are factors that affect
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the penetration of solvent into the herbal materials. The decreased viscosity and increased
diffusivity of solvent facilitate the penetration of solvent into porous solid materials, resulting in
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increased mass transfer and reduced extraction times in SFE [63]. The solvation power, which
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changes with temperature and pressure, is another factor that can determine the effectiveness of
the SFE method. Modification of the solvent solvation power can be employed to achieve high
selectivity of the extraction product from herbs. In addition, modification of the solvent
solvation may be useful in the extraction of complex samples, such as plant materials [44, 45].
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One of the advantages of SFE is that the system operates at low temperatures, which is an ideal
technique for studying temperature-sensitive compounds [46-48] and may possibly lead to the
discovery of new natural compounds [49]. To minimize waste generation, the spent CO 2 can be
recycled and reused, even for large-scale system. SFE is very useful for removing pesticides
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from herbal medicines [50].
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Unmodified CO 2 may lead to a limited selectivity of this apolar solvent. Thus, a polar solvent
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modifier can be used to overcome this drawback. Significant losses of the desired compounds
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can occur if an inappropriate solvent modifier is applied. These losses can occur for desired
compounds that are removed with the solvent or via undesired reactions facilitated by the solvent
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itself [51]; such losses represent two of the major disadvantages of the SFE process. The most
commonly-used solvent modifiers are methanol, ethanol, acetonitrile, acetone, water, ethyl ether
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and dichloromethane. Methanol is a popular choice due to its effectiveness as a polar modifier
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(up to 20% miscible with CO 2 ). However, the use of methanol as a modifier could be
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disadvantageous when thermolabile compounds are involved because of the slightly higher
temperature required for methanol to reach its supercritical state. In addition, a major obstacle is
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water or alcohol, to extract the active ingredients from herbs. In MAE, the enhanced extraction
occurs as the result of changes in the vegetable cell structure caused by electromagnetic waves in
MAE [52]. On the other hand, in conventional extractions, the mass transfer of the
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phytochemicals occurs from inside (herbal particle) to the outside (solvent), although the heat
transfer occurs from the outside (heat source) to the inside (herbal particle) [53]. Generally,
microwaves are electromagnetic radiations with a frequency from 0.3 to 300 GHz [54]. The
microwave energy is delivered directly to the herbal particle through molecular interactions with
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the electromagnetic field via conversions of electromagnetic energy into thermal energy [55].
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Thus, MAE typically results in a short extraction time and high extraction yield. Besides, the
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combination of two transport phenomena; heat and mass gradients working in the same direction
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[53] also contribute to the high yield and short extraction time of MAE.
MAE has been applied to extract the ingredients from the leaves and roots of L. pumila [18].
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Abdul Qayoom et al. [56] used MAE to extract ingredients from the leaves and flowers of C.
angustifolia. The parameters that affect the extraction efficiency of this extraction method are
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the power and frequency of the microwaves, the duration of the microwave irradiation, the
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moisture content and particle sizes of the plant samples, the type and concentration of the
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solvent, the ratio of solid to liquid, the extraction temperature, the extraction pressure, and the
number of extraction cycles [57]. Among these factors, solvent selection is the most important
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parameter because the solvent affects the absorbance of the microwave energy, as determined by
the dissipation factor [58, 59]. The solvent must have an affinity for the target compound and an
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ability to absorb microwave energy [60]. Another critical factor in MAE is the ratio of the solid
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herbs to the amount of solvent. The bioactive ingredients in the herbs can effectively dissolve
when large amounts of solvent are used, thereby leading to improved extraction yields [60, 61].
Gao et al. [61] and Li et al. [62], who applied a high solvent ratio with MAE, reported consistent
results. However, their results differed from those of other studies by Guo et al. [63], Li et al.
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[64], and Spigno & Faveri [65], who found that when large quantities of solvent were utilized,
the extraction yield initially increased and then decreased as the solid-to-liquid ratio decreased.
When the amount of solvent was reduced (high-solid herbal materials), microwave energy may
have been absorbed and dispersed by the large amount of plant materials [61], thereby increasing
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the solid mass, and decreasing the surface area available for solvent to penetrate the plant
materials and solubilize the target molecules [66]. Agitation or shaking of the sample–solvent
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mixture may also have become inadequate when the microwaves were applied to the large-
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volume sample [67].
One of the advantages of MAE is the applicability of this process for both large-scale
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(industrial) and small-scale (laboratory) systems. This method is believed to be more efficient in
extracting active ingredients with less time compared to conventional methods. Oil that is
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extracted using MAE contains increased concentration of oxygenated compounds, and have been
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techniques for nonpolar target compounds or solvents and with highly viscous solvents [57, 71].
In addition, MAE is not appropriate for the extraction of temperature sensitive compounds [72].
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In this extraction method, conditions such as the time and the ratio of herbs to solvent share
similarities with the MAE processes, except the intensity of the ultrasonic equipment is replaced
instead with the microwave power to facilitate the extraction processes. Chua et al. [19] applied
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a sonication extraction technique to extract the dried leaves of L. pumila. The correct choice of
solvent coupled with appropriate agitation and/or heat characteristics are also the major factors in
optimizing this type of extraction process. The solvent extraction of herbal materials can be
improved through the use of ultrasonic power because of the mechanical effects resulted from
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the ultrasound process. This effect results in improved solvent penetration into the cellular
materials via improved mass transfer within the herbal cells. In addition, the mechanical effects
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disrupt the biological cell walls, thereby resulting in the release of the cell contents such as
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herbal oils [83].
among the molecules of the medium. In these regions of changing pressure, cavitation of formed
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gas bubbles occurs. During the rarefaction cycle, the surface area of these bubbles increases,
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which results in increased gas diffusion and an expansion of the bubble. In the compression
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cycle (i.e., when insufficient ultrasonic energy is provided), these vapor phases cannot remain in
an expanded state, which results in rapid condensation and the release of large amounts of energy
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[73-75]. The shock waves created with high temperatures (550°C) and pressures (50 MPa) [73,
75] are a consequence of the condensation process. Both high temperatures and pressures
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generate microjets directed toward solid surfaces (i.e., the herbs or the container wall) as the
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bubbles collapse onto those surfaces. These microjets are responsible for the degreasing effect
of ultrasound on metallic surfaces, and this technique is commonly used to clean materials [76].
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Sonication extraction is inexpensive, an efficient tool for large-scale commercial
particle-size reduction, and modification of viscosity [77, 78]. This extraction technique, which
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is easy to use, features numerous advantages, including reduced working time, increased yield,
improved solvent consumption, and possibly improved quality of the extract. Ultrasound has
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weak effects on both yield and kinetics for the extraction of oil such as wood seed [79]. The
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effects of ultrasound on the extraction yield and kinetics may be linked to the nature of the plant
matrix [57]. The presence of a dispersed phase contributes to the ultrasound wave attenuation
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whereby the active part of ultrasound inside the extractor is restricted to a zone located in the
vicinity of the ultrasonic emitter. The two factors mentioned must be considered carefully in the
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design of ultrasound-assisted extractors.
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Soxhlet extraction serves not only as a technique for extraction of phytochemicals, but also as a
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reference to compare the newer extraction techniques [80]. Soxhlet extraction involves the use
of a Soxhlet apparatus (as shown in Fig. 2) for the extraction of herbs. The sample is placed in a
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thimble holder that is gradually filled with fresh solvent from a distillation flask (see Fig. 2). As
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the liquid reaches the over-flow level, a siphon aspirates the solute from the thimble holder,
moving the aliquot back into the distillation flask and carrying the extracted analytes into the
bulk liquid. This process continues until the extraction process has been completed. The system
operates in a continuous mode as the solvent is recirculated through the sample. With this
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method, the extracts are isolated by being filtered and the solvent is removed at defined
temperatures under reduced pressure in a rotary evaporator [81]. This extraction technique can
maintain a high system temperature (at solvent boiling point) via a heat source applied directly to
the distillation flask. This method is also very simple and inexpensive [82].
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Soxhlet extractions are limited by the time required for the extraction process and by the large
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volumes of extractant (solvent) required. The solvents can be expensive to remove, and can
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cause environmental problems [83]. Note that in general, the compound boiling point is lower
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than that of the solvent. Due to the fact that the extraction process is usually performed at the
boiling point of the solvent for extended periods of time, thermal decomposition of the target
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compounds may also occur. In Soxhlet extraction, it is also necessary to choose the most
suitable solvent for extracting the targeted compounds because different solvent polarity will
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dissolve different compounds [84]. Hexane, which has a narrow boiling point (65°C) is the most
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widely applied solvent. However, this solvent is listed as an hazardous air pollutant by the US
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examples, instead of using hexane, d-limonene was used by Mamidipally and Liu [85], while
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water was applied by Hanmoungjai [86] to extract oil from the rice bran. The alternative
solvents, however, result in less recovery due to the lower molecular affinity between the
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alternative solvents and the solute. Sometimes, co-solvent is added to match the polarity of the
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Marinated extraction is an ancient extraction method conducted at room temperature. For this
technique, the parameters to be considered include the type of solvent, the ratio of dried herbs to
solvent, and the extraction time. This method requires a prolonged extraction time because it
does not use heat or other forces. The extraction products are commonly obtained by filtering
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the extracts first. The advantage of this method is that it requires neither special equipment nor a
special location such as a laboratory. The commonly cited disadvantage of this method is the
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long extraction time [87]. As an example, Laghari et al. [56] extracted flowers of Cassia
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angustifolia while Zhu [88] extracted Portulaca oleracea L. within 48 hours at room
distillation extraction is similar to that of the Soxhlet extraction process. Both methods are
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commonly used to isolate volatile and non-volatile polar components from aromatic plants [89],
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with small variations in the type of solvent applied and the equipment arrangement. In hydro-
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distillation extraction, the sample and water solvent are placed in a retort (Fig. 3). Heat is
applied to heat and vaporize the mixture. Water vapor causes small sacs in the raw plant
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material containing essential oil to burst. Extracted oil is then transported by steam in the vapor
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phase into the condenser where the condensate liquid mixture formed. The liquid mixture then
flows into a separator where water and the essential oil are separated by density difference. The
water-rich phase, which contains some plant essence is called ‘hydrosol’. As an example, when
roses are extracted using this method, the hydrosol is retained for use as a mild antiseptic and as
15
fragrance for floral aromatherapy. The experimental hydro-distillation extraction equipment
commonly used for herbal extraction is shown in Fig. 3. As a precaution, the temperature limit
inside the retort of a hydro-distillation extractor must be strictly observed in order to prevent
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temperatures between 373 to 391 K (100-118°C). Operation at temperatures higher than 391 K
will result in the extract containing more chemicals than the targeted aroma, causing the
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within a specified duration in order to ensure that the oil components are completely released.
One advantage of the hydro-distillation extraction method is that it does not require
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expensive organic solvent. Nonetheless, the method involves a separation step to separate the
liquid extract from water. This processing step may require a long period of time or the use of an
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additional solvent to facilitate separation [90].
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generation apparatus to supply steam to the mixture of solvent and plant raw material. Steam
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maybe supplied at a pressure and the corresponding saturation temperature that is sufficiently
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higher than the boiling point of the mixture in order to allow evaporation to take place at lower
temperatures. Next, the evaporated mixture of water and compound flows into a condenser
where it is condensed into a liquid mixture and later collected in a separator. The solvent is
finally evaporated and separated from the compound using a rotary evaporator. Note that, a
preliminary study is typically performed to select a suitable solvent to extract the phytochemicals
16
of interest [91]. A solvent with a polarity value that is close to that of the specific compound of
essential oils. As steam passes through the plant material, tiny pockets in the plant cell holding
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the essential oil will open and release the essential oil without damaging the oil structure. Thus,
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steam-distillation is a special extraction technique that can prevent the decomposition of organic
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compound due to high temperature as its temperature could be controlled. So that it could be
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operated below the decomposition temperature of the compounds.
pressure. The Ultra-high pressure extraction technique involves three steps: i) mixing herb with
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solvent, ii) extraction of the desired phytochemicals at high pressure, and iii) filtering of
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Jun [92] showed the experimental set up of this method. Raw herbs and solvent were placed
together in a polyethylene bag and sealed after removing bubbles. Then, the bag was placed in a
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pressure vessel that was equipped with a temperature controller (at the top and the bottom of the
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vessel) and pressure valve (to release the excess pressure). Fluid was used to apply pressure to
the vessel using an ultrahigh pressure booster pump. Extraction was carried out at high pressure
(100 MPa to 1,000 MPa) and at room temperature for a specified duration (5 to 15 minutes). As
17
in the case of other methods, after the extraction process, the mixture was filtered and
Under high pressure, the solubility of natural compounds in any solvent is enhanced [93]. This
leads to the faster diffusion time of compounds into the solvent medium. The pressure range
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used for the UHPE method, between 100 MPa to 1000 MPa, is the highest among the extraction
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methods. For example, the pressure used in supercritical fluid extraction is about 100 MPa,
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while in other extraction methods used atmospheric pressure. The ultra-high pressure applied in
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UHPE leads to the increase in the compound solubility and shorter extraction time. Xi [94]
compared the times needed for the extraction of green tea leaves using different extraction
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methods. In their investigation, high pressure extraction method gave the shortest time (1 min)
to extract 30% of polyphenols from green tea leaves in water. Other methods which involved
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extraction at room temperature, ultrasonic extraction and heat reflux extraction needed 20 hours,
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90 minutes and 45 minutes, respectively. The results prove that the high pressure extraction
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method can extract the needed compound within the shortest extraction time. Note that, even
though the UHPE method is operated at high pressure, it requires no electrical power supply
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during pressure holding. Power supply is only required when pressure has to be increased.
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Organic compounds in herbs are typically heat-sensitive [95]. Application of heat may cause the
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Compound decomposition can be avoided using UHPE that operates at room temperature [95].
The extract impurity is, however, a main issue and drawback of the UHPE method. As high
18
3.9 Accelerated Solvent Extraction (ASE)
and at pressures between 10 and 15 MPa maintaining the solvent in liquid form. These
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conditions tend to enhance the solvent diffusivity and accelerate the extraction process.
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Giergielewicz-Możajska [96] shows the ASE equipment used in experimental work. There is a
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pressurization system that creates and applies pressure to the pressure vessel. The temperature
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and pressure in this system are set to be constant. The sample, together with the solvent are
placed in the closed container inside the pressure vessel. The container is connected to a
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thermocouple to detect temperature change in the sample container. If temperature change
occurs, the heating and cooling jacket (surrounding the sample container) will operate in order to
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keep constant the temperature inside the sample container. The pressure, on the other hand, is
controlled by the pressure relief valve. When the pressure increases, the pressure relief valve
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will be opened to prevent pressure from building up. When the pressure decreases, the
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pressurization system will apply pressure to the vessel. Note that, pressure is only created when
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the pressure inside the vessel drops below the set pressure, thereby saving the pressurization
Note that the ASE method is normally applied for thermally-stable organic pollutants from
environmental matrices. The ASE is not suitable for thermally labile compounds because the
high temperature needed in the ASE method may lead to degradation of heat-sensitive
compounds. This is perhaps the reason why very few applications of ASE have been published
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The performance of ASE was proven effective by Kaufmann and Christen [97] who compared
the ASE method with the Soxhlet extraction for isolating steroids from the leaves of Lochroma
gesnerioides. In addition, the findings showed that both methods could produce the same results
in terms of recovery, repeatability and selectivity. The extraction time and solvent consumption
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may be reduced by using the ASE [57, 97].
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3.10 Hot Water Extraction
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Hot water extraction (HWE) belongs to the same category as the ASE process. The HWE
however uses hot water for extraction instead of an organic solvent. The use of water as a
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solvent results in lower operating cost for the in HWE method because water is a cheaper
solvent. As a solvent, water is also relatively easier to treat and recover, and poses relatively less
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environmental issue. Ayala and De Castro [98] proved that, the isolation of oregano essential oil
using HWE is quicker, cheaper and more effective than using hydro-distillation extraction
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method. Besides, Ozel [99] found that the HWE method can extract the most valuable
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antioxidants (carvacrol and thymol) from essential oils of Thymbra spicata at high concentration
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(~90%).
c
Carvacrol and thymol are valuable nutrients in the food industry. Eikani [100] also compared the
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efficiency of HWE, hydro-distillation and Soxhlet extraction in extracting essential oils from
coriander seeds (Coriandrum sativum L.). Their findings showed that hydro-distillation and
Soxhlet extraction showed higher extraction efficiencies than the HWE. However, the HWE
showed better results in the extraction of more concentrated and valuable oxygenated
components in essential oils (used in food industry). The extraction of essential oil from
20
marjoram leaves was done by Jimenez-Carmona [101]. The authors compared the performances
of HWE and hydro-distillation extraction processes and found that the volume of essential oil
extracted using HWE was 5.1 times the volume extracted using hydro-distillation. The authors
also reported that the extracted essential oil contained high amount of oxygenated components.
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Besides, the HWE is capable of extracting the same amount of essential oil within 15 minutes
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al. [101], Saim [102]]. Findings by the authors suggest that the HWE method is better for
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extracting essential oils.
4.0 COMPARISON OF
an THE EXTRACTION
PROCESSES
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Comparison of the extraction processes in the previous section reveals that SFE is a well-
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established technique for the extraction and separation [39] of both essential oils and its
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derivatives for the food, cosmetic, pharmaceutical, and other related industries. SFE processes
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also result in high-quality essential oils with commercially viable compositions, as compared to
the products obtained using conventional steam-distillation processes [103, 104]. In the SFE
c
method, the physicochemical properties of the extraction fluid, such as its density, diffusivity,
Ac
dielectric constant, and viscosity, can be easily controlled by varying the pressure or temperature
without crossing the phase boundaries [105]. Over the past four decades, supercritical CO2 has
been applied for the extraction and isolation of multiple valuable compounds from natural
products [106]. The use of CO 2 as a solvent in SFE has provided an excellent alternative to
21
chemical solvents to extract the bioactive components from herbs and other medicinal plants.
The use of supercritical CO 2 is also more environmentally friendly than most extraction
techniques that use organic and liquid solvents. For example, the MAE processes use organic
solvents, such as methanol and ethanol that are relatively less environmentally friendly than
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CO 2 . Hawthorne et al. [107] extracted essential oils from savory, peppermint, and dragonhead
using both SFE and steam-distillation processes. They determined that SFE and steam-
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distillation extracts had similar distributions of volatile components. The results of their study
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suggested that steam-distillation did not result in significant losses of the more volatile essential
oil components. In addition, SFE was determined to be a rapid and quantitative method for
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extracting essential oils from aromatic plants. Rezazadeh et al. [108] extracted lavender oil and
compared the efficiencies of both SFE and steam-distillation. They determined that the
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extraction yield of SFE was approximately six times higher than those obtained using the steam-
distillation process. The extraction time with SFE was considered suitable for the processing of
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high quality lavender oil, compared to the products obtained using steam-distillation processes.
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Abdul Qayoom et al. [56] studied the extraction of the leaves and flowers of Cassia
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angustifolia using four different extraction methods including microwave, sonication, marinated,
and Soxhlet extraction processes. Among these four extraction methods, the microwave
c
extraction method was found to be the best technique on the basis of its ease of use, robust
Ac
processing, and minimal time required to process the materials and to efficiently extract large
amounts of the desired phytochemicals. The extracts obtained by this method also exhibited an
increase in antioxidant activities. The other methods investigated were effective for extracting
phytochemicals, but exhibited low efficiencies. In addition, these other methods were found to
22
be very difficult to handle and needed longer periods of processing steps as compared to the time
A comparison between the sonication extraction and the MAE indicated that the
sonication extraction method was simpler even though both methods require the same amount of
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solvent. MAE, on the other hand, needed less extraction time as compared to the sonication
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extraction methods. In addition, the MAE apparatus and equipment are expensive and difficult
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Ayala and De Castro [98], Ozel et al. [99], Eikani et al. [100] and Jimenez-Carmona et al.
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[101] compared the performances of hydro-distillation and HWE techniques for the extraction of
essential oils from different plants. Compared to the hydro-distillation extraction process, they
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found that the HWE offers many more advantages, including the ability to perform separation
that is:
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• Quicker, (the HWE is capable of producing the same amount of extract within 15 minutes
• Cheaper (the HWE uses less electricity and power supply during the extraction process)
c
and,
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• More effective (the HWE is able to produce more concentrated and valuable oxygenated
components).
When comparing the conventional steam-distillation, Soxhlet, and MAE methods, Chen et al.
[67] suggested that MAE had distinct advantages of decreased extraction time, increased
23
extraction yields, improved selectivities and of producing superior quality targeted extract
materials. In addition, MAE was relatively cost-effective as compared to the accelerated Soxhlet
Xi et al. [94] compared three extraction methods which are sonication, marinated and ultra-high
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pressure to extract polyphenols from green tea leaves. Their investigation found that ultra-high
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pressure extraction method is suitable for fast extraction of polyphenols from green tea leaves as
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compared to other methods. Shouqin et al. [95] also compared the three methods for extracting
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compounds from Epimedium, green tea, propolis and Scutellaria herbs. They found that, ultra-
high pressure extraction is a very useful tool for the extraction of natural products. The shorter
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extraction time (5 to 10 minutes) is needed as the high pressure will quickly break the plant cell
and the solvent will permeate very fast through the broken solvent. This will increase the mass
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transfer rate of compound to the solvent area. Besides, ultra-high pressure extraction helps save
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a lot of energy because the energy is generated only when the pressure is lower than the set
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pressure.
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Kaufmann and Christen [97] extracted natural compound from nine different herbs using ASE
and MAE. They found that the MAE can reduce the extraction time and solvent volume needed
c
while ASE can increase the diffusivity of solvent which leads to increase in the extraction speed
Ac
and efficiency.
From the comparison of methods in extracting various phytochemicals, it can be seen that
researchers have been searching for the potential methods that could result in higher extraction
yield, better selectivity, less solvent and energy requirement, faster extraction time, as well as
24
environmentally friendly process. However, there have been works that have compared the ten
extraction methods together. The comparison provides useful guides for future researcher and
process design engineers who may be interested to know the relative advantages and
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5.0 CHALLENGES FOR THE HERBAL INDUSTRY
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Phytochemicals are very important constituents of herbal products because these active
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components can often determine the safety and effectiveness of herbal products. Data on
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phytochemical processing can be difficult to obtain, particularly the physical and chemical
properties [36], including solubility values, partition coefficients, and heat transfer coefficients,
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are not available. These critical data are required to develop an effective process model that can
be integrated into process design methods similar to those that have been established for the
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Determining the physical and chemical properties can be challenging because herbal materials
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contain multiple phytochemical components, and each component contributes to these properties.
Even with a full characterization of the phytochemical components, the components may have
c
Ac
isomers with different properties. For example, the components of L. pumila (Kacip Fatimah)
are still uncharacterized. In the herb extraction studies available in the literature, analysis using
that the components varied with the method and solvent applied during the extraction process.
This lack of standardization has limited the number of scientific studies reported for L. pumila,
25
with a dearth of published data on the chemical properties and pharmacological activities of the
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Scale-up of extraction equipment enables the commercial production of herbs at larger
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scale to meet customer demands. Before scaling up, the laboratory-scale method should be
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tested in order to make sure that the selected method can extract the optimum amount of
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phytochemicals. According to Santos [115] and Prado [116], the scale-up procedure assumed
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that the industrial-scale unit has the same performance as the laboratory-scale unit when the ratio
between the mass of solid and solvent, size of raw material plant and the operating conditions are
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kept constant. In validating scale-up criteria, it is necessary to assess their applicability to
different types of raw materials, as the mass transfer mechanisms may differ among species and
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parts of the plant used for extraction [117]. In a scale-up plant, there is typically a huge amount
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of waste either from solvent or solid waste. Thus, in scaling up the extraction method, reusing of
the waste can be very profitable [116]. As an example, grape seeds are considered a disposable
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waste material by the majority of wineries. The seeds are usually discarded, burned or used as
Santos et al. [115] compared the performances of Soxhlet and ultra-high pressure
extractions to extract phenolic compounds from jabuticaba skins at laboratory scale. They found
that the ultra-high pressure extraction was more efficient than the Soxhlet extraction method.
Then, the scale up was done for ultra-high pressure extraction. This scale-up method used
26
aqueous ethanol (a mixture of 70:30 v/v ethanol and water) as solvent. Other conditions were
0.045 g/cm3 of feed to solvent ratio, temperature of 353K, pressure of 5MPa and an extraction
time of only 9 minutes. Using these conditions, the extraction resulted in 13.3% of extraction
yield. The unit was designed to operate for 8,000 hours in a year, which corresponds to 330 days
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per year of continuous 24-h-per-day shift. Note that the actual operating hours of 330 instead of
365 days a year allowed for at least two days per month for the process and plant maintenance
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[119].
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Fiori [120] scaled up the SFE equipment for extracting grape seed. In this plant, CO 2
was used as solvent. The set operating conditions include pressure at 50 MPa, temperature at
an
373.15 K, ratio of solvent to feed at 4 kg CO 2 /kg grape seed and an extraction time at 2 hours.
The SFE unit includes three extraction vessels. The first vessel is for the extraction finishing,
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the second is to conclude the extraction semi-cycle, and the third is a backup vessel.
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Prado et al. [116] also performed a 17-fold scale-up for the Supercritical Fluid Extraction
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of grape seed. The scaled-up conditions include a temperature of 313K, pressure of 35 MPa,
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ratio of CO 2 solvent to feed of 8.21 kg CO 2 /kg grape seed and an extraction time of 300 minutes.
The plant was designed to operate for 24 hours with three daily shifts for 330 days, or a total of
c
7920 hours of operation per year (the rest hours was used for process and plant maintenance). In
Ac
their study, they found that higher solvent velocity tend to cause mechanical dragging
(entrainment of oil not solubilized in CO 2 ), ultimately resulting in a low yield for the scale-up
plant. In scaling-up SFE, increasing the solvent mass flow will increase the entrained solvent
27
condensed phase. In order to prevent this phenomenon, an optimal ratio of solvent to raw
The 15-fold scale-up of SFE for extracting clove and sugarcane was successfully done by
Prado [122]. In this design, carbon dioxide is utilized as a solvent. All of the conditions in the
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laboratory scale were set to be constant. For the extraction of clove, the temperature is set at
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313K, pressure at 15 MPa, the ratio of solvent to feed is 3.59 kg CO 2 /kg clove and the extraction
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time is 130 minutes. For sugarcane residue, the extraction conditions are at temperature of
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333K, pressure of 35 MPa, ratio of solvent to feed of 30 kg CO 2 /kg sugarcane residue and an
extraction time of 360 minutes. The scale-up yield was found to be slightly higher than that of
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the laboratory scale (i.e., 20% higher at 130 min for clove and 15% higher at 180 min for
sugarcane residue).
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Microwave-assisted extraction was scaled up by Filly [123] to extract essential oil from
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rosemary. At first, the laboratory scale extraction was performed for microwave-assisted and
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hydro-distillation extractions. The result showed that, the same extraction yield was obtained
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Both methods actually have their unique advantages in that, microwave gives a good yield while
c
without any added solvent or water. The objective of the study is to extract the essential oil from
rosemary on a laboratory scale and apply the same conditions to a pilot scale. The conditions
28
applied in the study included the use of 3 kg of dried rosemary, 30 W of microwave power and
30 minutes of extraction time without the use of any solvent. The microwave-assisted hydro-
distillation is a rapid technique that consumes less energy and no solvent. It is therefore
advantageous from an environmental point of view because no waste will be produced. The
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extraction schematic is shown in Fig. 5 [123].
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As per 2015, there are only SFE, microwave-assisted extraction and ultra-high pressure
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extraction methods in extracting plant/ herb that have been scaled up. Another method such as
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HWE was scaled up by Kilpelainen [124] to extract sawdust. The scale-up techniques require
many considerations on why the scale-up must be done. Only promising techniques, i.e. those
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that could yield a reasonably large amount of extracts within a short time will be chosen for
scale-up in order to make economic sense and to produce a good return on investment.
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7.0 CONCLUSIONS
d
te
The demand for herbal products has been increasing with the increased awareness of
ep
possible side effects of using products made from chemicals. The effectiveness of natural
products has been attributed to the presence of phytochemicals as the active compounds in herbs.
c
Extraction processes are required to obtain the active ingredients that will be used in the
Ac
Herbal/plant extraction techniques have been typically designed to achieve one or more
of the following goals – shortened extraction time, decreased solvent consumption, increased
29
extraction yield, and enhanced extract quality [57]. The most suitable method must therefore be
chosen to perform a particular extraction task. The extraction techniques described in this
review are suitable for the solid-liquid extraction of plant constituents. Among the common
methods to extract the essential oil are hydro-distillation, steam-distillation, Soxhlet and
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marinated extraction methods. These methods are effective, but can be time-consuming and
require high operating costs. For example, Soxhlet extraction, which uses a large amount of
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solvent not only requires a high operating cost but also causes additional environmental
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problems. Some other methods described in the review required longer time to extract the
needed compound from the herbs. For instance, the traditional method of boiling herbs to obtain
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phytochemicals requires longer extraction time. Thus, more advanced extraction methods such
as sonication-assisted extraction [125], microwave assisted extraction [97], SFE [126], ultra-high
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pressure extraction [94, 95], hot water extraction [98, 99] and ASE [97, 127] have been used as
alternatives for to perform faster extraction and obtain higher quality yield. These techniques
d
operate at higher temperatures and/or pressures and greatly decrease the extraction time.
te
However, these specialized extraction techniques have found application in limited occasions as
ep
they require higher capital investment for the complex equipment. ASE, for example, has been
performed at high temperatures for the extraction of organic compounds that are more stable at
c
high temperature relative to other compounds that tend to denature. Research is in progress to
Ac
better understand the various extraction mechanisms with the aim to improve their efficiencies
and cost-effectiveness, to remove their limitations and to perform scale up of these techniques
30
FUNDING
This work was supported by the Ministry of Education, Fundamental Research Grant Scheme
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Education, Malaysia MyPhD scholarship. This support is gratefully acknowledged.
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The authors have declared no conflict of interest.
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methods described in the
text.
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Soxhlet
apparatus
Figure 2:
extraction
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Figure 3: Hydro-distillation extraction equipment.
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Figure 5: Solvent-free microwave extraction: from laboratory to pilot scale.
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Table 1: General guidelines for harvesting various plant parts
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Full maturity. The maturity stage of the species must be first
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Roots or rhizomes
determined.
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Leaves Fully developed leaves.
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At the beginning of the rainy season. The maturity stage of the
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Stems or bark
species must first be determined.
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Table 2: Advantages and disadvantages of various extraction methods
Type of
Advantages Disadvantages
Extraction
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Solvent (CO 2 ) is inexpensive
Supercritical
Loss of desired compounds with
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extraction, all methods
Specialized equipment is required
SFE
Pure extraction yield can be attained
an Efficiency of microwaves is very poor
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for nonpolar target compounds or
Applicable for both industrial and
solvents or for extremely viscous
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Microwave
laboratory scales
solvents
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Assisted
Less time consuming than
extraction, Not appropriate for heat sensitive
ep
conventional methods
MAE compounds
c
investment
operate
Sonication Efficient tool for large-scale The active part of ultrasound is only
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extraction commercial applications the vicinity of the ultrasonic emitter
attenuation
t
Increased yield, reduced solvent
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consumption, and high extract quality Weak effect on the extraction of oil
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Requires excessive extraction times
Soxhlet
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Very simple and inexpensive method (solvent)
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Temperature in the extraction system No agitation that can accelerates the
extraction
can be maintained process
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sensitive compound
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extraction organic solvent is required No agitation to accelerate the process
Energy consuming
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Steam-
cr
Can extract water insoluble No agitation needed to accelerate the
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distillation
compound process
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extraction
Ultra-high
extraction
Reduce solvent consumption and
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extraction time
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Hot water Inexpensive method because no Not suitable for heat sensitive
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Extract essential oil with high
oxygenated components
investment cost
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c ep
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