Next Article in Journal
Enhanced Activity of Titanocene Complex for Electrocatalytic Nitrogen Reduction Reaction
Previous Article in Journal
Nanosheet-Like Ho2O3 and Sr-Ho2O3 Catalysts for Oxidative Coupling of Methane
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:

The Limonene Biorefinery: From Extractive Technologies to Its Catalytic Upgrading into p-Cymene

Dipartimento di Ingegneria Civile, dell’Energia, dell’Ambiente e dei Materiali (DICEAM), Università Mediterranea di Reggio Calabria, Via Graziella, loc. Feo di Vito, I-89124 Reggio Calabria, Italy
Dipartimento di Ingegneria, Università degli Studi di Messina, Contrada di dio, I-98158 Sant’ Agata di Militello, Messina, Italy
Dipartimento di Ingegneria Industriale (DIEF), Università degli Studi di Firenze, Via di S. Marta 3, I-50139 Firenze, Italy
Istituto per lo Studio dei Materiali Nanostrutturati, CNR, Via U. La Malfa 153, I-90146 Palermo, Italy
Authors to whom correspondence should be addressed.
Catalysts 2021, 11(3), 387;
Received: 15 February 2021 / Revised: 14 March 2021 / Accepted: 16 March 2021 / Published: 18 March 2021
(This article belongs to the Section Biomass Catalysis)


Limonene is a renewable cyclic monoterpene that is easily obtainable from citrus peel and it is commonly used as a nutraceutical ingredient, antibacterial, biopesticide and green extraction solvent as well as additive in healthcare, fragrance and food and beverage industries for its characteristic lemon-like smell. Indeed, the lack of toxicity makes limonene a promising bio-alternative for the development of a wide range of effective products in modern biorefineries. As a consequence, industrial demand largely exceeds supply by now. Limonene can be also used as starting substrate for the preparation of building block chemicals, including p-cymene that is an important intermediate in several industrial catalytic processes. In this contribution, after reviewing recent advances in the recovery of limonene from citrus peel and residues with particular attention to benign-by-design extractive processes, we focus on the latest results in its dehydrogenation to p-cymene via heterogeneous catalysis. Indeed, the latest reports evidence that the selective production of p-cymene still remains a scientific and technological challenge since, in order to drive the isomerization and dehydrogenation of limonene, an optimal balance between the catalyst nature/content and the reaction conditions is needed.

1. Introduction

The chemical conversion (upgrade) of lignocellulosic biomasses and wastes for the production of fuels and chemical building blocks, the so-called “biorefinery”, has been widely explored in the last two decades [1,2]. Modern biorefineries already use cellulose, hemicellulose and lignin (the three-key components of lignocellulose) as starting feedstocks for the preparation of furans, polyols, acids and aromatics [3,4,5]. However, other important platform chemicals can be easily extracted from biomass-derived wastes and residues and used as biobased building blocks for the preparation of value-added intermediates, products, renewable energy and biofuels, supporting and slowly replacing the well-assessed technologies that gave a great contribution to these fields [6,7,8,9,10].
In this context, limonene (1-methyl-4-(1-methyl phenyl) cyclohexene), the main constituent of citrus essential oil (around 68–98% w/w) is industrially derived from the citrus industry from orange processing waste [11]. An optically active cyclic monoterpene that exists in two enantiomeric forms, R-limonene (the predominant isomeric form in citrus varieties, also known as d-limonene) and S-limonene (the less common isomer found in mint oils) [12,13,14,15], limonene is generally adopted as a flavor and fragrance additive in the cosmetic and perfume industries due to its pleasant citrus smell, and in the food industry as a flavor and preservant, avoiding alterations of the organoleptic properties. Moreover, it is also extensively adopted as an ingredient in household cleaning products, as wetting and dispersing agent in manufacturing resins, in the production of varnishes, in germicide treatments for wastewaters [16] and as insect control. In this regard, limonene represents an efficient alternative to halogenated carbon hydrates or conventional degreasing agents. Likewise, due to its elevated apolar solvent properties, limonene is a versatile compound used as a green solvent for the extraction of natural products, replacing toxic oil-based solvents such as n-hexane [17,18,19]. For example, it was recently proven to have a unique ability to recover marine oils rich in omega-3 lipids, vitamin D and carotenoids from shrimp and anchovy leftovers [20,21,22]. These uses are particularly important in light of its anticancer, anti-tumoral and anti-diabetic properties [23,24]. The industrial demand of limonene largely exceeds its supply, limited by the yearly global production of orange crops. As a result, the price of orange essential oil (EO) has increased to such an extent that it is now a primary source of revenue for the orange juice industry [13,25].
Due to its versatile chemistry, when the supply of the terpene obtained via bacterial fermentation will replace limited supply from citrus processing waste, limonene will replace a number of aromatic intermediates currently produced from oil [13,26,27]. For example, 1,2-limonene oxide obtained via catalytic selective oxidation readily reacts with carbon dioxide to form biobased polycarbonates of exceptional optical and mechanical properties, with some important reviews published in recent years on this subject [28,29,30]. Likewise, limonene can be used as a substrate for the production of p-cymene, a fine chemical intermediate in several industrial chemical processes [31,32]. In fact, p-cymene is involved in the synthesis of fragrances, perfumes, flavors, fungicides, pesticides and pharmaceutical products [23]. At the same time, in the perfume industry, it is used as a raw material for the production of key intermediates including p-cresol that is used, for example, in the production of antioxidants such as butylated hydroxytoluene (BHT) [33,34,35]. Moreover, p-cymene can be added to inks, adhesives, paints and pigments and is widely used for the manufacture of some products that are normally obtained from petroleum-based compounds. Finally, p-cymene can be transformed into aromatic monomers, including terephthalic acid and dimethyl styrene, or used as starting substrate for the synthesis of non-nitrate mosses (i.e., tonalide).
The current industrial route to p-cymene using the Friedel-Crafts alkylation of benzene with methyl and isopropyl halides or of toluene with 2-propanol generates a large amount of byproducts. Moreover, the use of large quantities of hazardous acid catalysts gives rise to safety, corrosion, handling and waste disposal problems. In further detail, the FC alkylation is performed at high temperatures (200–450 °C) in the presence of AlCl3, BF3 or H2SO4 as catalysts, producing significant amounts of by-products (especially o- and m-cymene along with other multiple alkylation products) with an overall yield of p-cymene that usually does not exceed 50%. Finally, since the conventional p-cymene production occurs in a liquid phase, the separation of the reactants from the catalyst is an energy-intensive process [36,37,38]. Alternative methodologies for the production of p-cymene have been widely investigated, including the use of renewable limonene, also considering that a relatively low amount of p-cymene (4000 tonnes) is manufactured yearly [39,40,41,42,43].
In this account, we highlight recent advances in the extraction of limonene from citrus processing waste with particular attention to benign-by-design extractive processes, and its catalytic dehydrogenation for the production of p-cymene.

2. Extraction Methods for an Efficient Recovery of Limonene

Extraction techniques are the first step in any treatment of citrus fruits and medicinal plants. The extraction has a significant and crucial role in the final result and can be performed with different technologies [44]. Recently, eco-friendly unconventional extraction methods, such as microwave-assisted extraction (MAE), ultrasonic-assisted extraction (UAE), supercritical fluid extraction (SFE) and enzyme-assisted extraction (EAE) [45], which reduce time and the use of chemical solvents improving the yield and quality of the extracted essential oil, have been developed. At the same time, conventional extraction methods, such as hydrodistillation (HD), cold press (CP) [46] and solvent extraction, are still considered reference methods [44].
Table 1 summarizes the recovery of limonene from different species of citrus by means of conventional and novel extraction technologies. The amount of limonene recovered strongly depends on the extraction technique and on the type of citrus fruit used. Indeed, as shown in Table 1, the maximum yield of about 94–96% has been reached for the orange peel [47,48], while lower values were obtained for clementine and grapefruit. A lower extraction efficiency resulted also from the lemon, with a yield of limonene that did not exceed 70% [49].
The limonene recovery from citrus has been widely achieved by using conventional solvent extraction with different types of various solvents such as n-hexane, dichloromethane, diethyl ether and ethyl acetate. Among the several solvents used, n-hexane, due to its low boiling point, highly hydrophobic character and excellent solubilizing ability, was found to be the most efficient extracting agent [50,51]. Besides the type of the starting citrus fruit, the solvent extraction efficiency depends also on the operating parameters, such as extraction temperature, cycle number and substrate–solvent ratios. Battista et al. recently reported the recovery of limonene from the orange essential oil (OEO), extracted from orange peels (Ops) by means of a Soxhlet n-hexane extraction under optimized reaction parameters (85 °C; solvent/OPs ratio equal to 2:1) allowed higher OEO yields of 1.31% to be reached with a limonene content of about 90% [52]. At the same time, the high-pressure–high-temperature extraction (HPTE) process, using hexane, in an agitated reactor, has been successfully used by Lopresto et al. to recover d-limonene from lemon fruits, highlighting that the high temperature excites the analyte solubilisation by increasing both solubility and mass transfer rate, thus enhancing the extraction efficiency [53,54].
As shown in Figure 1, the non-conventional HTPE processes, carried out at 150 °C and 6 bar pressure with a matrix/solvent ratio equal to 1:4 during an extraction time of only 30 min, led to a yield in d-limonene three times higher (2.97% vs. 0.95%) compared to that of the classic Soxhlet extraction performed for 4 h at 68 °C and 1 bar pressure with a matrix/solvent ratio 1:25 [53].
However, due to its high toxicity, the use of hexane has been severely limited by various regulations, such as the REACH (EC 1907/2006) and the IPPC (96/61/EC), pushing the scientific research towards the use of green solvents, as an alternative to n-hexane, without compromising the yield of oil [55]. On this account, the use of green solvents obtained from the biomass (i.e., bio-based solvents) or nontoxic and biodegradable environmentally friendly petrochemical solvents could represent a valid alternative to replace hazardous volatile organic solvents, not only in terms of environmental and healthy impact, but also in terms of extraction efficiency. Ozturk et al., evaluated the performance of several bio-solvents, demonstrating how the use of cyclopentyl-methyl and 2-methyl-tetrahydrofuran, operating at T = 70 °C, t = 150 min and substrate/liquid ratio equal to 1:10, allows us to obtain a better performance of recovery and reuse in consecutive extraction cycles, and limonene extraction yields up to 80% and 40% respectively, in comparison with the conventional hexane extraction methodology [11].
The cold press, one of the ancient essential oil extraction methods and already integrated into most of the modern juice production systems, is based on the use of needles to tear the oil glands in the peels [23,56] and the use of a mechanical pressure to release the oils [49]. It has the major advantage of minimizing the degradation of the essential oil constituents [57], with the oil expeller pressed at low temperature and pressure. Additionally, the resulting oil is 100% pure and retains most of the volatile compounds and waxes, which are important for their aromatic properties [58]. Although the cold press extraction provides an inexpensive opportunity compared to conventional methods, as the equipment is very simple and does not requiring heat supply, usually it has the lowest yield of essential oil extraction compared most recent extraction techniques, such as hydro (HD) and steam (SD) distillation. Therefore, in recent years, the number of reports based on the cold press extraction of limonene was very limited.
Ferhat et al., in a comparative study of essential oil extraction from fresh citrus peels by conventional hydrodistillation (HD), cold pressing (CP) and innovative microwave-accelerated distillation (MAD), obtained via cold press extraction a yield of 73.75% from whole fresh lemon (Villa Franca, Citrus limon (L.) Burm cultivar), while, starting from whole fresh grapefruit (Marsh Seedless, Citrus deliciosa Ten C. tangerine cultivar) and whole fresh orange (Valencia cultivar Citrus sinensis (L.) Osbeck; Bouquetier de Nice (Citrus paradisi) cultivar), a yield of ca. 95–96% was reached. Such results further highlight the fundamental role played by the type of starting fruit on limonene yields, since a higher amount from oranges (around 95%) is obtained, while it is significantly less from lime and lemon fruit (around 70%). In any case, Ferhat et al., in the same study, showed that the innovative microwave process offers substantial advantages over conventional processes, in terms of both shorter distillation time (30 min vs. 3 h for hydrodistillation and 1 h for cold pressing), and improved yields (0.24% vs. 0.21% for hydrodistillation and 0.054% for cold pressing) [46].
As mentioned above, hydrodistillation (HD) is a classic method for the extraction of aroma-producing compounds that does not involve the use of organic solvents. It is performed before the dehydration of citrus materials, and it is generally widely used. Three main types of HD processes can be listed: (i) water distillation, (ii) steam distillation and (iii) water–steam distillation. HD requires long extraction times and cannot be widely used for thermolabile compounds extraction, such as terpenic compounds, due to the volatility of some components, possibly lost at high extraction temperatures [14,44,59]. The technique shows a simple apparatus based on the evaporation of a solution containing immiscible liquid compounds at a boiling temperature lower than the one of each component [59,60]. Starting from fresh orange peels, Ruiz et al. achieved a maximum extraction efficiency of limonene, above 44%, for the treatment at the higher steam flowrate (16 mL min−1) and the longest contact time (180 min) [61], according to the results previously obtained by Cannon et al. [62]. The extraction efficiency of limonene, obtained by Martin et al. by steam distillation at lab scale, with a distillation time ranging from 0 to 6 h, was above 70% [31], while, using the same technique, Uwida et al. reached limonene yields above 95% [15]. In any case, the limonene extraction efficiency obtained in the above studies cannot be directly compared owing to the different operating conditions.
Microwave-assisted extraction (MAE) is a green and versatile extraction technology usable starting from several raw materials and providing both faster extraction and lesser solvent consumption [63]. Recently, MAE has been largely used also for the extraction of pectin and betanin from the peel of red and green Opuntia ficus-indica fruits with high efficiency [64]. MAE shows many advantages, such as a less solvent volume, faster extraction, mass transfer intensification and protection of thermo-labile compounds from high temperatures. The temperature is the main control parameter. Moreover, MAE allows a better extraction efficiency of oxygenated compounds to be obtained compared to the classical hydrodistillation (HD), since the absence of solvent reduces the thermal and hydrolysis reactions, thus hindering the degradation of the oxygenated compounds [45]. In recent years, coupling MAE with other technologies, such as microwave-assisted hydro distillation (MADH) [23] and microwave Steam Distillation (MSD) [14], is of particular interest due to the reduced time of the extraction process and its allowing the recovery of essential oil without causing any change in the composition of the oil gas. On this account, Bustamante et al. studied the upscaling of the MAHD process for the extraction of the essential oil from citrus peel, developing a two-step process, where the microwave energy was supplied, with intermittent power, during the extraction time, obtaining a substantial saving in energy costs and a significant increase in the extraction efficiency. Indeed, as can be observed in Figure 2, the energy efficiency of the applied microwave energy decreases as the extraction time increases, confirming that short irradiation times are required to reach a significant extraction efficiency [48].
One of the most innovative approaches is solvent-free microwave extraction (SFME), a combination of microwave heating and dry distillation, performed at atmospheric pressure without using solvents or water. This technique affords similar yields as the traditional steam distillation with a considerably shorter extraction time and without the post-treatment steps [49,65]. The SFME extraction process was performed by Ciriminna et al. for the isolation of essential oils from different parts of the fruit: outer skin (exocarp), peel (exo- and mesocarp) and waste (exo-, meso- and endocarp), starting from three types of citrus fruits, orange, lemon and grapefruit, grown in Sicily. Numerous compounds have been identified in EOs with very high yields compared to other industrial methods (0.4% vs. 0.05–0.25%), with limonene as the main constituent (50–80%) in most cases [66].
Ultrasound (US) technology has been also applied for the recovery of essential oils [45]. The use of ultrasound has the advantage of being fast, simple and low cost [67] and is based on milder extraction operative conditions [23]. The control and optimization of process parameters (e.g., time, temperature, pressure, speed and power) make this method useful not only for the limonene extraction but also for the selective extraction of different compounds from citrus and plants [67]. According to Aliaño-González et al., the technique exploits the energy of ultrasounds for the extraction of different organically derived raw materials [68]. US was successfully used to intensify the extraction of d-limonene from the Citrus limetta (sweet lime) peel by Khandare et al. As evidenced in Figure 3, the ultrasound-assisted extraction (EAU) under optimized conditions allows yields to be achieved similar to those obtained by using Soxhlet, close to 100%, in very short extraction times, due to the physical and structural changes on the substrate surface and the consequent improvement of extraction efficiency [69].
On this account, Pingret et al. designed and developed the sono-Clevenger process, a new procedure employing the US technology for the extraction of essential oils from orange peels. Compared to the conventional Clevenger technique, this advantageous alternative provides a substantial reduction of the extraction time without interfering with the composition of target compounds [70].
González-Rivera et al. studied the solvent-free, microwave-assisted extraction (SMWAE) and the simultaneous ultrasonic and microwave irradiation hydrodistillation (US–MWHD). The cavitation effect of US favors the breakage of the internal cell membranes rushing the extraction of limonene and promoting the volatilization of compounds with higher boiling point, such as valencene. Indeed, the amount of limonene and myrcene, the two main compounds of the orange peel EOs, increases over time and reaches a limit value at the end of the process (Figure 4), resulting in a limonene content above 95% and a higher amount of valencene. Since the valencene amount in the orange EOs, due to its aromatic and flavoring characteristics, contributes to an increase in its quality and commercial value, it is evident that the US-MWHD cavity-less configuration can be considered not only a faster method, compared with the microwave coaxial hydrodistillation (MWHD) and conventional hydrodistillation (CH), but also the best way to obtain the highest quality of EO (Figure 4) [47].
The extraction by supercritical fluid (SFE) has been extensively studied and is generally considered a non-traditional eco-friendly extraction technique [71], using CO2 as green and renewable solvent. Although many other solvents can be used for plant extraction (such as propane), CO2 is considered an ideal solvent for SFE. The critical temperature of CO2 is slightly higher than room temperature, and the low critical pressure allows it to operate at moderate pressures, generally between 100 and 450 bar [44,45]. Therefore, limonene’s extraction by the traditional hydrodistillation technique may be replaced by the supercritical fluid extraction (15 MPa, 40 °C), which offers the possibility to save time and represents an eco-friendly alternative method [72]. Several researchers, by using supercritical CO2 to investigate the extraction of volatile components from the orange peel, showed that the concentrations of limonene and linalool depend significantly on the applied process parameters [73]. The optimization of process conditions for supercritical CO2 extraction plays a key role for the selectivity of the extracted components and their subsequent application in the food industry [55]. Finally, it is worth mentioning that, in recent years, the use of the supercritical CO2 (SC-CO2) as a solvent and hydrotropic extraction tool has been evaluated to extract limonoids from the citrus waste, allowing yields up to 13 times higher to be obtained than the traditional cold-pressing technique, recovering the 100% limonene yield. However, it is impossible to compare the efficiency of this technique with others, as the yield depends on the amount of CO2 used [49,74].
A recent study employed the enzymatic pre-treatment of cellulose for the extraction of essential oils from three different citrus peels [75]. Compared to conventional methods, the use of assisted enzymes allows an increase in essential oil yield by 2- and 6-fold for orange peel and grapefruit, respectively. The enzymatic treatment has the advantage of reducing the overall viscosity, which facilitates the breaking of an emulsion for the recovery of the oil from the aqueous phase [76]. The preliminary steps play an important role during the extraction of compounds from the biomass. Among these, drying and grinding are two factors that predominantly affect the final yield. Generally, dehydration involves the removal of the bound water from the peel by increasing the porosity of the cellular matrix, thereby facilitating diffusion rate and promoting the contact with enzymes, consequently enhancing the overall process [77]. Most important, the enzyme-assisted extraction can be coupled with other techniques (e.g., microwave-assisted, ultrasound-assisted, supercritical fluid and high-pressure) to increase the overall yield of the limonene.

3. Upgrading of Limonene into p-Cymene over Heterogeneous Catalysts

Limonene tends to turn into monocyclic terpenes (terpinenes and terpinolenes) that can dissociate into menthenes and cymenes as final products [42]. Indeed, in an alternative process, p-cymene can be produced via isomerization or hydrogenation, as well as by the direct dehydrogenation of limonene [78].
Reports on the transformation of limonene into p-cymene by homogeneous catalysts are quite limited since low yields and separation drawbacks generally occur, thus driving the interest towards heterogeneous systems (Table 2), able to ensure good performances and, at the same time, an easy separation from the post-reaction mixture [38,79].
In an interesting approach, Catrinescu et al. used several metal-modified bentonites as catalysts at 150 °C for 15 min in the presence of n-dodecane as solvent. The results show that the nickel-modified bentonites are the most active with respect to analogous Al- and Cr-based catalysts [80].
The catalytic conversion of limonene to p-cymene was also performed by Martin-Luengo et al., using sepiolite, a clay (hydrated magnesium silicate) of natural and economic origin, as a catalyst by microwave irradiation. High conversion of limonene to p-cymene, under solvent-free conditions, was achieved using a modified catalyst with Na, Ni, Fe or Mn oxides. Modification of the catalyst with nickel allows the complete conversion of limonene with a selectivity of 100% to p-cymene, after 20 min of reaction [31]. The same research group as before used mesoporous silica-alumina supports as catalysts with a SiO2 content ranging from 1% (SIRAL 1) to 40% (SIRAL 40) [26]. Both the limonene conversion and the p-cymene selectivity linearly increase with the silica content with SIRAL 20 and SIRAL 40 catalysts, leading to complete conversion of limonene into p-cymene.
In another approach, limonene was previously isomerized into α-terpinene, γ-terpinene and terpinolene and then converted into p-cymene over the H-FER (T) (ferrierite from Tosoh in which the Si/Al ratio amounts to 8.9) catalyst at 65 °C. At this temperature, after a reaction time of 60 min, a 38% limonene conversion was gained. Interestingly, limonene transformation was not observed over H-FER (Z) ferrierite catalysts characterized by Brønsted sites with higher acid strength [81].
The dehydrogenation of limonene to p-cymene was explored by Cui et al. using a Pd/HZSM-5 catalyst under both inert (N2) and reductive (H2) reaction conditions. Due to the endothermic nature of dehydroaromatization reactions, an increase in the reaction temperature is beneficial to the shift of the equilibrium toward p-cymene production both in the presence and in the absence of added hydrogen (Figure 5).
The addition of hydrogen leads to a lower selectivity to p-cymene, since it increases the hydrogenation rate on the double bonds, facilitating the isomerization reaction of limonene and preventing its reverse reaction [82]. Most important, it was proved that the first step in the conversion of limonene into p-cymene is the isomerization, followed by a sequential dehydrogenation process.
Retajczyk et al. carried out studies on the limonene isomerization process using Ti-SBA-15 and Ti-MCM-41 as catalysts, performing the limonene isomerization without any organic solvents [43]. The conversion of limonene increases by increasing both the reaction temperatures as well as the reaction time (Figure 6).
Results clearly show that, under the same processing conditions (temperature 160 °C, catalyst content 15% wt, for 23 h), the different mesoporous silica structures of MCM and SBA give rise to different yields of p-cymene (29% with a limonene conversion of 92% for Ti-MCM-41 and 56% with a limonene conversion of 99% for Ti-SBA-15).
A 2-step mechanism was proposed by Makarouni et al., starting from the limonene isomerization over activated natural mordenites and then its isomerization into p-cymene in a non-catalytic process, using atmospheric oxygen as a green oxidant (Figure 7).
The acid treatment with sulfuric acid aqueous solutions of natural mordenite causes the removal of sodium oxide from its micropores, which drastically increases the specific surface and acidity, making natural mordenite very active in the catalytic transformation of limonene into p-cymene and causing a significant enhancement in both the limonene conversion and in the amount of p-cymene obtained in the reaction mixture. A rather high p-cymene yield (63%) at 140 °C, with a limonene/catalyst ratio of 15 and a reaction time of 7 h, was obtained [35]. Another achievement of the same group was the use of aqueous solutions of various acids (CH3COOH, HCl, H2SO4, HNO3) to further improve the surface area and the acidity of natural mordenite with a significant increase in the conversion of limonene to p-cymene up to 65% [83].
It is generally accepted that the addition of a transition metal to supports like silica, alumina, silica–alumina mixed oxides, zeolites and natural clays generally improves the catalytic performance as a consequence of the dual functionality exhibited by metal-modified catalysts. In the case of the conversion of limonene into cymene, acid sites are responsible for the isomerization step, while metallic sites can promote the dehydrogenation reaction [37,84]. On this account, several Cr2O3, CuO, ZnO, ZrO2, MgO, La2O3, TiO2 and Pd supported on C catalytic systems have been successfully used for the dehydrogenation of terpenes [27], improving the p-cymene selectivity by up to 97% [78]. Kamitsou et al. recently reported an almost complete transformation of α-limonene into p-cymene (90% yield at 300 °C) over the TiO2 catalyst in a helium atmosphere. Titanium oxide is a very stable catalyst, and its high catalytic performance could be attributed to a good acidity/reducibility balance, allowing the Ti (IV)/Ti (III) transformation during reaction, thus positively promoting the limonene conversion. At the same time, by using CaO catalyst, the production of p-cymene takes place directly via limonene dehydrogenation, with a conversion rate of up to 98% and a selectivity of about 100% [37].
The transformation of limonene over different heterogeneous catalysts (Pt/Al2O3, Ni/Al2O3, and Pd/Al2O3) and in supercritical conditions of ethanol and 2-propanol was investigated by Yılmazoğlu et al. When the Pd/Al2O3 catalyst was used, the limonene was completely converted with an overall p-cymene yield of 80% [78].
In a very interesting approach, Zhang and Zhao proposed d-limonene as a hydrogen-donor molecule for the deoxygenation of fatty acids into alkanes and arenes (that can be used as bio-jet fuel) in the presence of the bimetallic Pd-Ni/HZSM-5 catalyst [85,86]. Palladium promotes the conversion of limonene into p-cymene and H2, which is the reducing agent also for the hydrodeoxygenation of stearic acid to alkanes over Ni and Pd-Ni sites (Figure 8). This kind of approach is of particular significance since catalytic transfer hydrogenation/hydrogenolysis reactions are getting increasing attention in the reductive upgrading of lignocellulosic biomasses and their relative macromolecules and derived molecules [87,88,89,90,91,92,93], thus opening new opportunities for the use of limonene as a green and renewable H-donor solvent.

4. Conclusions

Limonene is among the most promising renewable feedstocks for modern biorefineries. Citrus wastes are a good but intrinsically limited source of limonene. Among conventional recovery technologies, cold press extraction provides good yields and ease of applicability. Accordingly, it is the industrial state-of-the-art technology. Amid the new, solvent-free extraction technologies, the highly reproducible, versatile and simple microwave-assisted extraction is one of the more relevant alternatives. Other environmentally friendly methods include supercritical fluid and ultrasound extraction. All these methods are likely to find application when the microbial production of limonene by converting virtually unlimited raw materials such as sugars will be industrialized [94], in order to magnify its production and meet the so far largely unmet market demand for limonene.
At the same time, the development of new green pathways for p-cymene production from limonene is an excellent alternative to the traditional method of obtaining p-cymene via Friedel-Crafts alkylation of toluene with isopropene. The most recent investigations found that supercritical alcohols favoring the catalytic processes by enriching both the solubility and the diffusivity are the most interesting solvents. In almost all cases, p-cymene, γ-terpinene, α -terpinene and terpinolene are obtained. At the same time, the dehydrogenation process of limonene into p-cymene leads to hydrogen as a co-product that can be used for the reductive upgrading of other biobased molecules opening new perspectives in its use as renewable H-donor solvent.

Author Contributions

Conceptualization: C.E., R.C. and F.M.; writing—original draft preparation, A.S., C.E., E.P., P.S.C., M.P., R.C., F.M.; writing—review and editing: C.E., P.S.C., M.P. and F.M. All authors have read and agreed to the published version of the manuscript.


This research received no external funding.


Authors sincerely thank Emeritus Rosario Pietropaolo for the fruitful discussion.

Conflicts of Interest

The authors declare no conflict of interest.


  1. Zhou, C.H.; Xia, X.; Lin, C.X.; Tong, D.S.; Beltramini, J. Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. Chem. Soc. Rev. 2011, 40, 5588–5617. [Google Scholar] [CrossRef] [PubMed]
  2. De, S.; Saha, B.; Luque, R. Hydrodeoxygenation processes: Advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels. Bioresour. Technol. 2015, 178, 108–118. [Google Scholar] [CrossRef][Green Version]
  3. Ruppert, A.M.; Weinberg, K.; Palkovits, R. Hydrogenolysis goes bio: From carbohydrates and sugar alcohols to platform chemicals. Angew. Chem. Int. Ed. 2012, 51, 2564–2601. [Google Scholar] [CrossRef]
  4. Xu, C.; Paone, E.; Rodrìguez-Padrón, D.; Luque, R.; Mauriello, F. Reductive catalytic routes towards sustainable production of hydrogen, fuels and chemicals from biomass derived polyols. Renew. Sustain. Energy Rev. 2020, 127, 109852. [Google Scholar] [CrossRef]
  5. Xu, C.; Paone, E.; Rodríguez-Padrón, D.; Luque, R.; Mauriello, F. Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural. Chem. Soc. Rev. 2020, 49, 4273–4306. [Google Scholar] [CrossRef] [PubMed]
  6. Lin, C.S.K.; Pfaltzgraff, L.A.; Herrero-Davila, L.; Mubofu, E.B.; Abderrahim, S.; Clark, J.H.; Koutinas, A.A.; Kopsahelis, N.; Stamatelatou, K.; Dickson, F.; et al. Food waste as a valuable resource for the production of chemicals, materials and fuels. Current situation and global perspective. Energy Environ. Sci. 2013, 6, 426–464. [Google Scholar] [CrossRef]
  7. Sheldon, R.A. Green chemistry, catalysis and valorization of waste biomass. J. Mol. Catal. A Chem. 2016, 422, 3–12. [Google Scholar] [CrossRef]
  8. Frontera, P.; Macario, A.; Malara, A.; Antonucci, V.; Modafferi, V.; Antonucci, P.L. Simultaneous methanation of carbon oxides on nickel-iron catalysts supported on ceria-doped gadolinia. Catal. Today 2019, 257, 565–572. [Google Scholar] [CrossRef]
  9. Malara, A.; Paone, E.; Frontera, P.; Bonaccorsi, L.; Panzera, G.; Mauriello, F. Sustainable exploitation of coffee silverskin in water remediation. Sustainability 2018, 10, 3547. [Google Scholar] [CrossRef][Green Version]
  10. Frontera, P.; Macario, A.; Malara, A.; Santangelo, S.; Triolo, C.; Crea, F.; Antonucci, P.L. Trimetallic Ni-based catalysts over gadolinia-doped ceria for green fuel production. Catalysts 2018, 8, 435. [Google Scholar] [CrossRef][Green Version]
  11. Ozturk, B.; Winterburn, J.; Gonzalez-Miquel, M. Orange peel waste valorisation through limonene extraction using bio-based solvents. Biochem. Eng. J. 2019, 151, 107298. [Google Scholar] [CrossRef]
  12. Erasto, P.; Viljoen, A.M. Limonene—A Review: Biosynthetic, Ecological and Pharmacological Relevance. Nat. Prod. Commun. 2008, 3, 1193–1202. [Google Scholar] [CrossRef][Green Version]
  13. Ciriminna, R.; Lomeli-Rodriguez, M.; Demma Carà, P.; Lopez-Sanchez, J.A.; Pagliaro, M. Limonene: A versatile chemical of the bioeconomy. Chem. Commun. 2014, 50, 15288. [Google Scholar] [CrossRef] [PubMed]
  14. Mahato, N.; Sharma, K.; Koteswararao, R.; Sinha, M.; Baral, E.; Cho, M.H. Citrus essential oils: Extraction, authentication and application in food preservation. Cri. Rev. Food Sci. Nutr. 2017, 59, 611–625. [Google Scholar] [CrossRef] [PubMed]
  15. Uwidia, I.E.; Owolabi, B.J.; Okafor, R.C. Extraction, Derivatization, Characterization and Antifungal Investigation of Limonene from Citrus sinensis Peels. Tanz. J. Sci. 2020, 46, 419–429. [Google Scholar]
  16. Veillet, S.; Tomao, V.; Ruiz, K.; Chemat, F. Green procedure using limonene in the Dean–Stark apparatus for moisture determination in food products. Anal. Chim. Acta 2010, 674, 49–52. [Google Scholar] [CrossRef]
  17. Rubulotta, G.; Luska, K.L.; Urbina-Blanco, C.A.; Eifert, T.; Palkovits, R.; Quadrelli, E.A.; Thieuleux, C.; Leitner, W. Highly Selective Hydrogenation of R-(+)-Limonene to (+)-p-1-Menthene in Batch and Continuous Flow Reactors. ACS Sustain. Chem. Eng. 2017, 5, 3762–3767. [Google Scholar] [CrossRef]
  18. Aissou, M.; Chemat-Djenni, Z.; Yara-Varòn, E.; Fabiano-Tixier, A.-S.; Chemat, F. Limonene as an agro-chemical building block for the synthesis and extraction of bioactive compounds. Comptes Rendus Chim. 2017, 20, 346–358. [Google Scholar] [CrossRef]
  19. Lohrasbi, M.; Pourbafrani, M.; Niklasson, C.; Taherzadeh, M.J. Process design and economic analysis of a citrus waste biorefinery with biofuels and limonene as products. Bioresour. Technol. 2010, 101, 7382–7388. [Google Scholar] [CrossRef] [PubMed]
  20. Ciriminna, R.; Scurria, A.; Fabiano-Tixier, A.-S.; Lino, C.; Avellone, G.; Chemat, F.; Pagliaro, M. Omega 3 Extraction from Anchovy Fillet Leftovers with Limonene: Chemical, Economic, and Technical Aspects. ACS Omega 2019, 4, 15359–15363. [Google Scholar] [CrossRef][Green Version]
  21. Ciriminna, R.; Scurria, A.; Avellone, G.; Pagliaro, M. A Circular Economy Approach to Fish Oil Extraction. ChemistrySelect 2019, 4, 5106–5109. [Google Scholar] [CrossRef]
  22. Pagliaro, M.; Pizzone, D.M.; Scurria, A.; Lino, C.; Paone, E.; Mauriello, F.; Ciriminna, R. Sustainably Sourced Olive Polyphenols and Omega-3 Marine Lipids: A Synergy Fostering Public Health. ACS Food Sci. Technol 2021, in press. [Google Scholar] [CrossRef]
  23. Negro, V.; Mancini, G.; Ruggeri, B.; Fino, D. Citrus waste as feedstock for bio-based products recovery: Review on limonene case study and energy valorization. Bioresour. Technol. 2016, 214, 806–815. [Google Scholar] [CrossRef] [PubMed]
  24. Santiago, B.; Moreira, M.T.; Feijoo, G.; González-García, S. Identification of environmental aspects of citrus waste valorization into D-limonene from a biorefinery approach. Biomass Bioenergy 2020, 143, 105844. [Google Scholar] [CrossRef]
  25. 360 Market Updates. Global Limonene Market Size, Manufacturers, Supply Chain, Sales Channel and Clients, 2020–2026; 360 Market Updates: Maharashtra, India, 2020. [Google Scholar]
  26. Martin-Luengo, M.A.; Yates, M.; Martinez Domingo, M.J.; Casal, B.; Iglesias, M.; Esteban, M.; Ruiz-Hitzky, E. Synthesis of p-cymene from limonene, a renewable feedstock. Appl. Catal. B 2008, 81, 218–224. [Google Scholar] [CrossRef]
  27. Swift, K.A.D. Catalytic transformations of the major terpene feedstocks. Topics Catal. 2004, 27, 1–4. [Google Scholar] [CrossRef]
  28. Parrino, F.; Fidalgo, A.; Palmisano, L.; Ilharco, L.M.; Pagliaro, M.; Ciriminna, R. Polymers of Limonene Oxide and Carbon Dioxide: Polycarbonates of the Solar Economy. ACS Omega 2018, 3, 4884–4890. [Google Scholar] [CrossRef][Green Version]
  29. Ciriminna, R.; Parrino, F.; De Pasquale, C.; Palmisano, L.; Pagliaro, M. Photocatalytic partial oxidation of limonene to 1,2 limonene oxide. Chem. Commun. 2018, 54, 1008. [Google Scholar] [CrossRef] [PubMed]
  30. Cagnoli, M.V.; Casuscelli, S.G.; Alvarez, A.M.; Bengoa, J.F.; Gallegos, N.G.; Samaniego, N.M.; Crivello, M.E.; Ghione, G.E.; Pérez, C.F.; Herrero, E.R.; et al. “Clean” limonene epoxidation using Ti-MCM-41 catalyst. Appl. Catal. A Gen. 2005, 287, 227–235. [Google Scholar] [CrossRef]
  31. Martin-Luengo, M.A.; Yates, M.; Rojoa, S.E.; Arribas, D.H.; Aguilar, D.; Hitzkya, R.E. Sustainable p-cymene and hydrogen from limonene. Appl. Catal. A 2010, 387, 141–146. [Google Scholar] [CrossRef]
  32. Buhl, D.; Roberge, D.M.; Hölderich, W.F. Production of p-cymene froma-limonene over silica supported Pd catalysts. Appl. Catal. A Gen. 1999, 188, 287–299. [Google Scholar] [CrossRef]
  33. Sanches-Silva, A.; Cruz, J.M.; Sendón-Garcia, R.; Paseiro-Losada, P. Determination of butylated hydroxytoluene in food samples by high-performance liquid chromatography with ultraviolet detection and gas chromatography/mass spectrometry. J. AOAC Int. 2007, 90, 277–283. [Google Scholar] [CrossRef] [PubMed]
  34. Tavera Ruiz, C.P.; Gauthier-Maradei, P.; Capron, M.; Pirez, C.; Gardoll, O.; Katryniok, B.; Dumeignil, F. Transformation of DL Limonene into Aromatic Compounds Using Supported Heteropolyacid Catalysts. Catal. Lett. 2019, 149, 328–337. [Google Scholar] [CrossRef]
  35. Eggersdorfer, M. Terpenes. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH: Weinheim, Germany, 2012; Volume 36, pp. 29–45. [Google Scholar]
  36. Bueno, A.C.; Brandao, B.B.N.S.; Gusevskaya, E.V. Aromatization of para-menthenic terpenes by aerobic oxidative dehydrogenation catalyzed by p-benzoquinone. Appl. Catal. A Gen. 2008, 351, 226–230. [Google Scholar] [CrossRef]
  37. Kamitsou, M.; Panagiotou, G.D.; Triantafyllidis, K.S.; Bourikas, K.; Lycourghiotis, A.; Kordulis, C. Transformation of α-limonene into p-cymene over oxide catalysts: A green chemistry approach. Appl. Catal. A Gen. 2014, 474, 224–229. [Google Scholar] [CrossRef]
  38. Makarouni, D.; Lycourghiotis, S.; Kordouli, E.; Bourikas, K.; Kordulis, C.; Dourtoglou, V. Transformation of limonene into p-cymene over acid activated natural mordenite utilizing atmospheric oxygen as a green oxidant: A novel mechanism. Appl. Catal. B Environ. 2018, 224, 740–750. [Google Scholar] [CrossRef]
  39. Marchese, A.; Arciola, C.R.; Barbieri, R.; Silva, A.S.; Nabavi, S.F.; Tsetegho Sokeng, A.J.; Izadi, M.; Jafari, N.J.; Suntar, I.; Daglia, M.; et al. Update on Monoterpenes as Antimicrobial Agents: A Particular Focus on p-Cymene. Materials 2017, 10, 947. [Google Scholar] [CrossRef]
  40. Fiege, H. Cresols and xylenols. In Ullmann’s Encyclopedia of Industrial Chemistry; Wiley-VCH: Weinheim, Germany, 2012; Volume 10, pp. 419–460. [Google Scholar]
  41. Ghiaci, M.; Abbaspur, A.; Arshadi, M.; Aghabarari, B. Internal versus external surface active sites in ZSM-5 zeolite: Part 2: Toluene alkylation with methanol and 2-propanol catalyzed by modified and unmodified H3PO4/ZSM-5. Appl. Catal. A Gen. 2007, 316, 32–46. [Google Scholar] [CrossRef]
  42. Corma, A.; Iborra, S.; Velty, A. Chemical Routes for the Transformation of Biomass into Chemicals. Chem. Rev. 2007, 107, 2411–2502. [Google Scholar] [CrossRef]
  43. Retajczyk, M.; Agnieszka Wróblewska, A. Isomerization and Dehydroaromatization of R-(+)-Limonene Over the Ti-MCM-41 Catalyst: Effect of Temperature, Reaction Time and Catalyst Content on Product Yield. Catalysts 2019, 9, 508. [Google Scholar] [CrossRef][Green Version]
  44. Azmir, J.; Zaidul, I.S.M.; Rahman, M.M.; Sharif, K.M.; Mohamed, A.; Sahena, F.; Jahurul, M.H.A.; Ghafoor, K.; Norulaini, N.A.N.; Omar, A.K.M. Techniques for extraction of bioactive compounds from plant materials: A review. J. Food Eng. 2013, 117, 426–436. [Google Scholar] [CrossRef]
  45. Lefebvre, T.; Destandau, E.; Lesellier, E. Selective extraction of bioactive compounds from plants using recent extraction techniques: A review. J. Chromatogr. A 2021, 1635, 461770. [Google Scholar] [CrossRef]
  46. Ferhat, M.A.; Boukhatem, M.N.; Hazzit, M.; Meklati, B.Y.; Farid, C. Cold Pressing, Hydrodistillation and Microwave Dry Distillation of Citrus Essential Oil from Algeria: A Comparative Study. Electron. J. Biol. 2016, S1, 30–41. [Google Scholar]
  47. González-Rivera, J.; Spepi, A.; Ferrari, C.; Duce, C.; Longo, I.; Falconieri, D.; Piras, A.; Tinè, M.R. Novel configurations for a citrus waste based biorefinery: From solventless to simultaneous ultrasound and microwave assisted extraction. Green Chem. 2016, 18, 6399–6696. [Google Scholar] [CrossRef][Green Version]
  48. Bustamante, J.; Stempvoort, S.V.; García-Gallarreta, M.; Houghton, J.A.; Briers, H.K.; Budarin, V.L.; Matharu, A.S.; Clark, J.H. Microwave assisted hydro-distillation of essential oils from wet citrus peel waste. J. Clean. Prod. 2016, 137, 598–605. [Google Scholar] [CrossRef]
  49. Teigiserova, D.A.; Ligia Tiruta-Barna, L.; Ahmadi, A.; Hamelin, L.; Thomsen, M. A step closer to circular bioeconomy for citrus peel waste: A review of yields and technologies for sustainable management of essential oils. J. Environ. Manag. 2021, 280, 111832. [Google Scholar] [CrossRef]
  50. Nguyen, H. Biogas Production from Solvent Pretreated Orange Peel. Master’s Thesis, Department of Chemical and Biological Engineering, Chalmers University of Technology, Goteborg, Sweden, 2012. [Google Scholar]
  51. Liu, S.X.; Mamidipally, P.K. Quality comparison of rice bran oil extracted with d-limonene and hexane. Cereal Chem. 2005, 82, 209–215. [Google Scholar] [CrossRef]
  52. Battista, F.; Remelli, G.; Zanzoni, S.; Bolzonella, D. Valorization of Residual Orange Peels: Limonene Recovery, Volatile Fatty Acids, and Biogas Production. ACS Sustain. Chem. Eng. 2020, 8, 6834–6843. [Google Scholar] [CrossRef]
  53. Lopresto, C.G.; Petrillo, F.; Casazza, A.A.; Aliakbarian, B.; Perego, P.; Calbrò, V. A non-conventional method to extract D-limonene from waste lemon peels and comparison with traditional Soxhlet extraction. Sep. Purif. Methods 2014, 137, 13–20. [Google Scholar] [CrossRef]
  54. Paini, M.; Casazza, A.A.; Aliakbarian, B.; Perego, P.; Binello, A.; Cravotto, G. Influence of ethanol/water ratio in ultrasound and high-pressure/high-temperature phenolic compound extraction from agri-food waste. Int. J. Food Sci. Technol. 2016, 51, 349–358. [Google Scholar] [CrossRef]
  55. Kumar, S.P.J.; Prasad, S.R.; Banerjee, R.; Agarwal, D.K.; Kulkarni, K.S.; Ramesh, K.V. Green solvents and technologies for oil extraction from oilseeds. Chem. Cent. J. 2017, 11, 9. [Google Scholar] [CrossRef] [PubMed][Green Version]
  56. Mahato, N.; Sinha, M.; Sharma, K.; Rakoti Koteswararao, R.; Cho, M.H. Modern Extraction and Purification Techniques for Obtaining High Purity Food-Grade Bioactive Compounds and Value-Added Co-Products from Citrus Wastes. Foods 2019, 8, 523. [Google Scholar] [CrossRef][Green Version]
  57. Karaman, S.; Karasu, S.; Tornuk, F.; Toker, O.S.; Geçgel, Ü.; Sagdic, O.; Ozcan, N.; Gül, O. Recovery potential of cold press byproducts obtained from the edible oil industry: Physicochemical, bioactive, and antimicrobial properties. J. Agric. Food Chem. 2015, 63, 2305–2313. [Google Scholar] [CrossRef] [PubMed]
  58. Rassem, H.H.A.; Nour, A.H.; Yunus, R.M. Techniques for Extraction of Essential Oils from Plants: A Review. Aust. J. Basic Appl. Sci. 2016, 10, 117–127. [Google Scholar]
  59. Zema, D.A.; Calabrò, P.S.; Folino, A.; Tamburino, V.; Zappia, G.; Zimbone, S.M. Valorisation of citrus processing waste: A review. Waste Manag. 2018, 80, 252–273. [Google Scholar] [CrossRef]
  60. Ferhat, M.A.; Meklati, B.Y.; Chemat, F. Comparison of different isolation methods of essential oil from Citrus fruits: Cold pressing, hydrodistillation and microwave ‘dry’ distillation. Flavour Fragr. J. 2007, 22, 494–504. [Google Scholar] [CrossRef]
  61. Ruiz, B.; de Benito, A.; Rivera, J.D.; Flotats, X. Assessment of different pre-treatment methods for the removal of limonene in citrus waste and their effect on methane potential and methane production rate. Waste Manag. Res. 2016, 34, 1249–1257. [Google Scholar] [CrossRef][Green Version]
  62. Cannon, J.B.; Cantrell, C.L.; Astatkie, T.; Zheljazkov, V.D. Modification of yield and composition of essential oils by distillation time. Ind. Crop. Prod. 2013, 41, 214–220. [Google Scholar] [CrossRef]
  63. Lee, C.S.; Binner, E.; Winkworth-Smith, C.; John, R.; Gomes, R.; Robinson, J. Enhancing natural product extraction and mass transfer using selective microwave heating. Chem. Eng. Sci. 2016, 149, 97–103. [Google Scholar] [CrossRef]
  64. Ciriminna, R.; Fidalgo, A.; Avellone, G.; Danzì, C.; Timpanaro, G.; Locatelli, M.; Carnaroglio, D.; Meneguzzo, F.; Ilharco, L.M.; Pagliaro, M. Integral extraction of Opuntia ficus-indica peel bioproducts via microwave-assisted hydrodiffusion and hydrodistillation. ACS Sustain. Chem. Eng. 2019, 7, 7884–7891. [Google Scholar] [CrossRef]
  65. Boukroufa, M.; Boutekedjiret, C.; Chemat, F. Development of a green procedure of citrus fruits waste processing to recover carotenoids. Resour. Effic. Technol. 2017, 3, 252–262. [Google Scholar] [CrossRef]
  66. Ciriminna, R.; Fidalgo, A.; Delisi, R.; Carnaroglio, D.; Grillo, G.; Cravotto, G.; Tamburino, A.; Ilharco, L.M.; Pagliaro, M. High-quality essential oils extracted by an eco-friendly process from different citrus fruits and fruit regions. ACS Sustain. Chem. Eng. 2017, 5, 5578–5587. [Google Scholar] [CrossRef]
  67. Alves Filho, E.G.; Sousa, V.M.; Rodrigues, S.; de Brito, E.S.; Fernandes, F.A.N. Green ultrasound-assisted extraction of chlorogenic acids from sweet potato peels and sonochemical hydrolysis of caffeoylquinic acids derivatives. Ultrason. Sonochem. 2020, 63, 104911. [Google Scholar] [CrossRef]
  68. Aliaño-González, M.J.; Jarillo, J.A.; Carrera, C.; Ferreiro-González, M.; Ángel Álvarez, J.; Palma, M.; Ayuso, J.; Barbero, G.F.; Espada-Bellido, E. Optimization of a Novel Method Based on Ultrasound-Assisted Extraction for the Quantification of Anthocyanins and Total Phenolic Compounds in Blueberry Samples (Vaccinium corymbosum L.). Foods 2020, 9, 1763. [Google Scholar] [CrossRef]
  69. Khandare, R.D.; Tomke, P.D.; Rathod, V.K. Kinetic modeling and process intensification of ultrasound-assisted extraction of d-limonene using citrus industry waste. Chem. Eng. Process. 2021, 159, 108181. [Google Scholar] [CrossRef]
  70. Pingret, D.; Fabiano-Tixier, A.-S.; Chemat, F. An improved ultrasound Clevenger for extraction of essential oils. Food Anal. Methods 2014, 7, 9–12. [Google Scholar] [CrossRef]
  71. Khaw, K.-Y.; Parat, M.-O.; Shaw, P.N.; Falconer, J.R. Solvent Supercritical Fluid Technologies to Extract Bioactive Compounds from Natural Sources: A Review. Molecules 2017, 22, 1186. [Google Scholar] [CrossRef]
  72. Lopresto, C.G.; Meluso, A.; Di Sanzo, G.; Chakraborty, S.; Calabrò, V. Process-intensified waste valorization and environmentally friendly d-limonene extraction. EuroMediterr. J. Environ. Integr. 2019, 4, 31. [Google Scholar] [CrossRef]
  73. Jokić, S.; Molnar, M.; Cikoš, A.M.; Jakovljević, M.; Šafranko, S.; Jerković, I. Separation of selected bioactive compounds from orange peel using the sequence of supercritical CO2 extraction and ultrasound solvent extraction: Optimization of limonene and hesperidin content. Separ. Sci. Tech. 2020, 55, 2799–2811. [Google Scholar] [CrossRef]
  74. Mira, B.; Blasco, M.; Berna, A.; Subirats, S. Supercritical CO2 extraction of essential oil from orange peel. Effect of operation conditions on the extract composition. J. Supercrit. Fluids 1999, 14, 95–104. [Google Scholar] [CrossRef]
  75. Chávez-González, M.L.; López-López, L.I.; Rodríguez-Herrera, R.; Contreras-Esquivel, J.C.; Aguilar, C.N. Enzyme-assisted extraction of citrus essential oil. Chem. Pap. 2016, 70, 412–417. [Google Scholar] [CrossRef]
  76. Putnik, P.; Bursac Kovecevic, D.; Režek Jambrak, A.; Barba, F.J.; Cravotto, G.; Binello, A.; Lorenzo, J.M.; Shpigelman, A. Innovative “Green” and Novel Strategies for the Extraction of Bioactive Added Value Compounds from Citrus Wastes-A Review. Molecules 2017, 22, 680. [Google Scholar] [CrossRef] [PubMed][Green Version]
  77. Nadar, S.S.; Rao, P.; Rathod, V.K. Enzyme assisted extraction of biomolecules as an approach to novel extraction technology: A review. Food Res. Int. 2018, 108, 309–330. [Google Scholar] [CrossRef] [PubMed]
  78. Yılmazoğlu, E.; Akgün, M. p-Cymene production from orange peel oil using some metal catalyst in supercritical alcohols. J. Supercrit Fluids 2018, 131, 37–46. [Google Scholar] [CrossRef]
  79. Shokouhimehr, M. Magnetically separable and sustainable nanostructured catalysts for heterogeneous reduction of nitroaromatics. Catalysts 2015, 5, 534–560. [Google Scholar] [CrossRef]
  80. Catrinescu, C.; Fernandes, C.; Castilho, P.; Breen, C. Influence of exchange cations on the catalytic conversion of limonene over Serra de Dentro (SD) and SAz-1 clays Correlations between acidity and catalytic activity/selectivity. Appl. Catal. A 2006, 311, 172–184. [Google Scholar] [CrossRef]
  81. Rachwalik, R.; Hunger, M.; Sulikowski, B. Transformations of monoterpene hydrocarbons on ferrierite type zeolites. Appl. Catal. A 2012, 427–428, 98–105. [Google Scholar] [CrossRef]
  82. Cui, H.; Zhang, J.; Luo, Z.; Zhao, C. Mechanisms into dehydroaromatization of bioderived limonene to p-cymene over Pd/HZSM-5 in the presence and absence of H2. RSC Adv. 2016, 6, 66695–66704. [Google Scholar] [CrossRef]
  83. Lycourghiotis, S.; Makarouni, D.; Kordouli, E.; Bourikas, K.; Kordulis, C.; Dourtoglou, V. Activation of natural mordenite by various acids: Characterization and evaluation in the transformation of limonene into p-cymene. Mol. Catal. 2018, 450, 95–103. [Google Scholar] [CrossRef]
  84. Roberge, D.M.; Buhl, D.; Niederer, J.P.M.; Hölderich, W.F. Catalytic aspects in the transformation of pinenes to p-cymene. Appl. Catal. A Gen. 2001, 215, 111–124. [Google Scholar] [CrossRef]
  85. Zhang, J.; Zhao, C. A new approach for bio-jet fuel generation from palm oil and limonene in the absence of hydrogen. Chem. Commun. 2015, 51, 17249–17252. [Google Scholar] [CrossRef]
  86. Zhang, J.; Zhao, C. Development of a Bimetallic Pd-Ni/HZSM-5 Catalyst for the Tandem Limonene Dehydrogenation and Fatty Acid Deoxygenation to Alkanes and Arenes for Use as Biojet Fuel. ACS Catal. 2016, 6, 4512–4525. [Google Scholar] [CrossRef]
  87. Tabanelli, T.; Paone, E.; Blair Vásquez, P.; Pietropaolo, R.; Cavani, F.; Mauriello, F. Transfer Hydrogenation of Methyl and Ethyl Levulinate Promoted by a ZrO2 Catalyst: Comparison of Batch vs Continuous Gas-Flow Conditions. ACS Sustain. Chem. Eng. 2019, 7, 9937–9947. [Google Scholar] [CrossRef]
  88. Mauriello, F.; Paone, E.; Pietropaolo, R.; Balu, A.M.; Luque, R. Catalytic transfer hydrogenolysis of lignin-derived aromatic ethers promoted by bimetallic Pd/Ni systems. ACS Sustain. Chem. Eng. 2018, 6, 9269–9276. [Google Scholar] [CrossRef]
  89. Paone, E.; Tabanelli, T.; Mauriello, F. The rise of lignin biorefinery. Curr. Opin. Green Sustain. Chem. 2020, 24, 1–6. [Google Scholar] [CrossRef]
  90. Paone, E.; Beneduci, A.; Corrente, G.A.; Malara, A.; Mauriello, F. Hydrogenolysis of aromatic ethers under lignin-first conditions. Mol. Catal. 2020, 497, 111228. [Google Scholar] [CrossRef]
  91. Paone, E.; Espro, C.; Pietropaolo, R.; Mauriello, F. Selective arene production from transfer hydrogenolysis of benzyl phenyl ether promoted by a co-precipitated Pd/Fe3O4 catalyst. Catal. Sci. Technol. 2016, 6, 7937–7941. [Google Scholar] [CrossRef]
  92. Malara, A.; Paone, E.; Bonaccorsi, L.; Mauriello, F.; Macario, A.; Frontera, P. Pd/Fe3O4 Nanofibers for the catalytic conversion of lignin-derived benzyl phenyl ether under transfer hydrogenolysis conditions. Catalysts 2020, 10, 20. [Google Scholar] [CrossRef][Green Version]
  93. Gumina, B.; Mauriello, F.; Pietropaolo, R.; Galvagno, S.; Espro, C. Hydrogenolysis of sorbitol into valuable C3-C2 alcohols at low H2 pressure promoted by the heterogeneous Pd/Fe3O4 catalyst. Mol. Catal. 2018, 446, 152–160. [Google Scholar] [CrossRef]
  94. Ren, Y.; Liu, S.; Jin, G.; Yang, X.; Zhou, Y.J. Microbial production of limonene and its derivatives: Achievements and perspectives. Biotechnol. Adv. 2020, 44, 107628. [Google Scholar] [CrossRef]
Figure 1. Comparison between non-conventional high-pressure–high-temperature extraction (HPTE) and conventional Soxhlet extraction. Adapted with permission from Lopresto et al. [53]. Copyright (2014) Elsevier Ltd.
Figure 1. Comparison between non-conventional high-pressure–high-temperature extraction (HPTE) and conventional Soxhlet extraction. Adapted with permission from Lopresto et al. [53]. Copyright (2014) Elsevier Ltd.
Catalysts 11 00387 g001
Figure 2. MAHD energy efficiency (%) at different extraction times. Adapted with permission from Bustamente et al. [48]. Copyright (2016) Elsevier Ltd.
Figure 2. MAHD energy efficiency (%) at different extraction times. Adapted with permission from Bustamente et al. [48]. Copyright (2016) Elsevier Ltd.
Catalysts 11 00387 g002
Figure 3. Comparison of ultrasonic-assisted extraction (UAE) with conventional extraction methods. Adapted with permission from Khandare et al. [69]. Copyright (2021) Elsevier Ltd.
Figure 3. Comparison of ultrasonic-assisted extraction (UAE) with conventional extraction methods. Adapted with permission from Khandare et al. [69]. Copyright (2021) Elsevier Ltd.
Catalysts 11 00387 g003
Figure 4. Chemical composition of the orange peel essential oils (Eos) obtained by conventional hydrodistillation (CH), solvent-free, microwave-assisted extraction (SMWAE), ultrasonic and microwave irradiation hydrodistillation (US–MWHD) and MWHD at different extraction times with a composition higher than 2%. Adapted with permission from González-Rivera et al. [47]. Copyright (2016) Royal Society of Chemistry.
Figure 4. Chemical composition of the orange peel essential oils (Eos) obtained by conventional hydrodistillation (CH), solvent-free, microwave-assisted extraction (SMWAE), ultrasonic and microwave irradiation hydrodistillation (US–MWHD) and MWHD at different extraction times with a composition higher than 2%. Adapted with permission from González-Rivera et al. [47]. Copyright (2016) Royal Society of Chemistry.
Catalysts 11 00387 g004
Figure 5. Conversion of limonene into p-cymene over the Pd/HZSM-5 catalyst as a function of time at 240, 260, 280, 300 °C (a) in absence of added hydrogen and (b) under inert atmosphere. Reproduced with permission from Cui et al. [82]. Copyright (2016) Royal Chemical Society.
Figure 5. Conversion of limonene into p-cymene over the Pd/HZSM-5 catalyst as a function of time at 240, 260, 280, 300 °C (a) in absence of added hydrogen and (b) under inert atmosphere. Reproduced with permission from Cui et al. [82]. Copyright (2016) Royal Chemical Society.
Catalysts 11 00387 g005
Figure 6. Temperature effect on the isomerization of R-limonene. Adapted with permission from Retajczyk et al. [43]. Copyright (2019) MDPI.
Figure 6. Temperature effect on the isomerization of R-limonene. Adapted with permission from Retajczyk et al. [43]. Copyright (2019) MDPI.
Catalysts 11 00387 g006
Figure 7. The reaction mechanism of the two-step conversion of limonene into p-cymene. Reproduced with permission from Makarouni et al. [38]. Copyright (2018) Elsevier Ltd.
Figure 7. The reaction mechanism of the two-step conversion of limonene into p-cymene. Reproduced with permission from Makarouni et al. [38]. Copyright (2018) Elsevier Ltd.
Catalysts 11 00387 g007
Figure 8. Brief description of individual steps for stearic acid and limonene coactivation using the bimetallic Pd-Ni/HZSM-5 catalyst. Reproduced with permission from Zhang et al. [86]. Copyright (2016) American Chemical Society.
Figure 8. Brief description of individual steps for stearic acid and limonene coactivation using the bimetallic Pd-Ni/HZSM-5 catalyst. Reproduced with permission from Zhang et al. [86]. Copyright (2016) American Chemical Society.
Catalysts 11 00387 g008
Table 1. Comparison of different extraction methods for the recovery of limonene.
Table 1. Comparison of different extraction methods for the recovery of limonene.
Citrus Peel WasteExtractive MethodLimonene
(% in EO)
Extraction ConditionsRef.
Orange peel freshSFME94.6Solvent-free, 30 min[46]
MAHD80.0Water, 60 min, 100 °C[66]
Orange peel fresh (after juicing)HD96.8Water, 240 min, 100 °C[48]
MAHD97.4Water, 240 min, 100 °C[48]
MAHD80.0Water, 80 min, 100 °C[66]
Orange peel thawedHD94.4Water, 155 min[47]
MAHD94.7Water, 76 min[47]
SFME95.2Solvent-free, 5 min[47]
US-MWHD95.0Water, 60 min[47]
Orange flavedo peel freshHD95.5Water, 180 min[46]
MAHD55.0Water, 75 min, 100 °C[66]
Orange whole freshCP96.0Water, 90 min[46]
Lemon peel freshSFME74.0Solvent-free, 30 min[46]
MAHD50.0Water, 80 min, 100 °C[66]
Lemon peel fresh (after juicing)MAHD68.4Water, 240 min, 100 °C[48]
MAHD65.0Water, 70 min, 100 °C[66]
Lemon flavedo peel freshHD72.9Water, 180 min[60]
HD93.0Water, 180 min[46]
MAHD30.0Water, 60 min, 100 °C[66]
Lemon whole freshCP73.8Water, 90 min[46]
Grapefruit peel freshSFME91.6Solvent-free, 30 min[46]
MAHD45.0Water, 70 min, 100 °C[66]
Grapefruit peel fresh (after juicing)MAHD89.2Water, 240 min, 100 °C[48]
Grapefruit flavedo peel freshHD92.6Water, 180 min[46]
Grapefruit whole freshCP94.5Water, 90 min[46]
Table 2. Conversion of Limonene into p-cymene promoted by heterogeneous catalysts.
Table 2. Conversion of Limonene into p-cymene promoted by heterogeneous catalysts.
CatalystLimonenep-CymeneReaction ConditionsRef.
Conversion (%)Yield (%)
Ni-SD9617Batch, n-dodecane, 150 °C, 15 min[80]
H-FER (T)38n.d.Batch, 65 °C, 60 min[81]
SIRAL 20100100Batch, microwave, 175 °C, 10 min[26]
SepNi100100Batch, microwave, 210 °C, 20 min[31]
Pd/HZSM-5 (258)10082Batch, n-dodecane, 260 °C, 2 h, 8 bar N2[82]
Ti-SBA-159956Batch, 160 °C, 23 h[43]
TECHNOSA-H29865Batch, tetraethylene glycol dimethyl ether, 140 °C, 7 h, N2[83]
TiO210090Continuous flow, 300 °C, 6 h, H2[37]
Pd/Al2O310080Continuous flow, SC-ethanol, 300 °C, 30 s, 6.5 MPa[78]
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Satira, A.; Espro, C.; Paone, E.; Calabrò, P.S.; Pagliaro, M.; Ciriminna, R.; Mauriello, F. The Limonene Biorefinery: From Extractive Technologies to Its Catalytic Upgrading into p-Cymene. Catalysts 2021, 11, 387.

AMA Style

Satira A, Espro C, Paone E, Calabrò PS, Pagliaro M, Ciriminna R, Mauriello F. The Limonene Biorefinery: From Extractive Technologies to Its Catalytic Upgrading into p-Cymene. Catalysts. 2021; 11(3):387.

Chicago/Turabian Style

Satira, Antonella, Claudia Espro, Emilia Paone, Paolo Salvatore Calabrò, Mario Pagliaro, Rosaria Ciriminna, and Francesco Mauriello. 2021. "The Limonene Biorefinery: From Extractive Technologies to Its Catalytic Upgrading into p-Cymene" Catalysts 11, no. 3: 387.

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop