3.1. S. terebinthifolius Extract from CO2 Supercritical Extraction
At an operating pressure of 90 bar, the extraction yield was 0.152% at 40 °C, while it increased to 0.999% at 60 °C. Although the increase in temperature leads to a reduction in the density of CO
2, there is an increase in the vapor pressure of the solutes, which can lead to greater extraction. As can be seen in the work by authors such as Rosa et al. [
24] and Pereira and Meireles [
25], the effect of the temperature on the supercritical CO
2 density is more complex; one can claim that under constant pressure, an increase in temperature leads to a decrease in supercritical solvent density. Changes in temperature, in addition to influencing the solvent density, also influence the vapor pressure and kinetic energy of solute molecules. At temperatures close to the critical point, the effect of a decrease in supercritical solvent density is more pronounced.
Table 3 shows the area% data for the main compounds identified in the extracts from fruits of
S. terebinthifolius in different experimental conditions.
The chromatographic analysis of the examined extracts revealed that the application of a condition of 90 bar at 40 °C favors the extraction of monoterpenes (21.67%) and sesquiterpenes (58.39%). However, the utilization of 90 bar at 60 °C leads to a significant decrease in the extraction of monoterpenes (1.61%).
According to Murari et al. [
26], the extraction of compounds at high temperatures can lead to the degradation of monoterpenes or induce a molecular rearrangement, originating other compounds of a sesquiterpenoid nature. Furthermore, it is known from the literature [
27] that monoterpenes are more volatile than sesquiterpenes, which may have influenced the results obtained.
This outcome aligns with the findings previously elucidated by Piras et al. [
28], whose studies reported that the fruit and leaf components of the
S. terebinthifolius species from Brazil are notable for exhibiting substantial proportions of sesquiterpene and monoterpene hydrocarbons. The complexity of these phytochemical profiles is significantly influenced by geographic factors of origin, coupled with the harvesting seasonality, underlying growth conditions, and methodologies employed for compound extraction.
These natural components present in the
S. terebinthifolius extract, with their antioxidant and antimicrobial properties, demonstrate significant potential for food preservation; thus, they have gained relevance in the field of food science [
4]. This article aimed to determine the MIC values in μg.mL
−1 of extracts obtained under different conditions from two strains,
Staphylococcus aureus (ATCC 6338) and
Escherichia coli (ATCC 8739), as shown in
Table 4.
When interpreting the results provided, it is evident that the SFE conditions of 90 bar at 40 °C exhibited significant antimicrobial potential against both Staphylococcus aureus (ATCC 6338) and Escherichia coli (ATCC 8739), with inhibition values of 800 and 400, respectively. Additionally, the SFE conditions of 90 bar at 60 °C displayed even more potent antimicrobial effects against Staphylococcus aureus (ATCC 6338), with an inhibition value of 1600, while the impact on Escherichia coli (ATCC 8739) was lower, as evidenced by the inhibition value of 0.718. These findings underline the influence of the extraction conditions on the antimicrobial activity of the samples against the specific bacterial strains tested.
The essential oil derived from
S. terebinthifolius has exhibited the capacity to hinder the in vitro proliferation of bacteria belonging to the
L. monocytogenes and
E. coli groups. Both groups hold significant importance due to their association with potential product contamination within the food industry [
2]. This inhibitory effect was reinforced by the investigation conducted by Dannenberg et al. [
29], wherein a marked decrease in the growth of
S. aureus,
L. monocytogenes,
E. coli, and
S. typhimurium was observed upon assessing the integration of
S. terebinthifolius essential oil into active cellulose acetate films at concentrations of 2%, 4%, and 6% (
v/
v).
As elucidated by Dannenberg et al. [
30], the essential oil extracted from
S. terebinthifolius has demonstrated a remarkable capacity to completely impede the growth of microorganisms, particularly
S. aureus and
L. monocytogenes. This effect is evident when the oil is employed at a concentration of 2.72 mg.mL
−1 across a range of culture mediums. Such findings underscore the substantial potential of
S. terebinthifolius essential oil as a natural antimicrobial agent.
The studies by Gilbert and Favoreto [
31] and El-Massry et al. [
32], which meticulously evaluated the antimicrobial efficacy of both a
S. terebinthifolius extract and essential oil against Gram-positive bacteria, consistently underscore the noteworthy effectiveness of these compounds against such bacterial strains. It is important to note that the minimum inhibitory concentration of these compounds was consistently observed to be below >1000 μg/mL.
3.2. SFE Process—Simulation
As previously stated, two simulations were executed using the Aspen Plus v.13 software. The first simulation was related to the supercritical extraction experiment conducted in the laboratory, while the second simulation was aimed at scaling up the process to an industrial level.
Figure 3a,b illustrate the flow diagrams of the Aspen Plus simulations.
In the first simulation (
Figure 3a), an adiabatic compressor with a power of 3.314 W (72% efficiency) was required to compress the CO
2 feed stream (30 °C and 60 bar) and generate an output stream of CO
2 at 90 bar and 65.2 °C. To lower the temperature of this stream. a shell-and-tube heat exchanger with a thermal exchange area of 10.7 cm
2 was employed, which was fed with a cold utility flow (water at 25 °C) of 0.6 kg/h. Additionally, the outputs of the mathematical separator were based on the laboratory experiment, following the extraction efficiency of 0.152% (extract mass/biomass mass).
In the second simulation (
Figure 3b), the plant processing capacity was scaled up to 15 kg/h of biomass, leading to a proportional increase in the CO
2 feed rate. Consequently, the pressurization and cooling of a stream of approximately 3500 kg/h CO
2 were required. As a result, the compressor power was estimated to be approximately 19.89 kW. Furthermore, instead of one heat exchanger, three were simulated, with a thermal exchange area of 2 m
2 and a cold utility flow rate of 3600 kg/h, connected in series.
Table 5 provides a summary of the specifications for both flowsheets, which will be used in
Section 3.3 for the economic evaluation of the simulated process.
3.3. Economic Evaluation Analysis
Considering a plant that handles 15 kg of
S. terebinthifolius per batch and an operational time of 8000 h in one year, it was estimated that the total biomass required is 30 tons of biomass from
S. terebinthifolius. Moreover, based on experimental data and simulation, the total equipment necessary is summarized in
Table 6.
The operation costs are composed of the total costs of cooling water, the CO2 for the supercritical extractor, and the amount of biomass as the raw material for extraction (
Table 7). The prices are referenced from supplier’s information and a market analysis. The energy required for compression was disregarded due the low cost participation rate in the cost evaluation, since the size of the equipment is small. For one year of operation, the following results were achieved.
Regarding the impacts of these two parameters (CAPEX and OPEX),
Figure 4 illustrates the cost distribution of the equipment and utilities, where HE is the heat exchanger and the numbers 1, 2, and 3 are the tags for each equipment.
As can be observed, the supercritical separator and compressor account for 43% and 47%, respectively, in the CAPEX distribution of the total cost of the equipment, while the heat exchangers show a similar percentage. These results indicate that in order to reduce the cost of the process, the supercritical separator and compressor should be the focus, either during project development or supplier negotiation.
Utilities represent the main raw costs required for process operation; other costs such as employee payments are associated with the working capital using Peters and Timmerhaus’ methodology of economic evaluation. According to
Figure 5, water cooling accounts for the main costs of the OPEX distribution. The potential for optimization comes from better water use in the process. For this, energy integration or the use of methodologies to reduce water consumption should have a significant impact on the process.
The results from the software for the EACP economic analysis are organized in
Table 8 with the inputs and outputs. The data are based on the simulation and scale-up process for one year of operation.
From the analysis, it is possible to note the feasibility of the process. The NPV, which is positive within the lifetime of the plant, and the payback time of two years are great performance indicators for the process. Once the product of the plant has a high aggregate value, high economic revenue can be expected on a large scale. The break-even point represents the minimal production capacity of the plant that is necessary for the process to exceed its own cost of production. A value of less than 25% capacity was achieved in this work.
Other studies that also used the supercritical extraction technique and performed an economic evaluation such as those by Pereira et al. [
33] and Sánchez et al. [
34] have shown the feasibility of the supercritical-extractor-based processes. However, these characteristics are achieved when a high-value product is involved, once the operational costs represent a disadvantage of the process due to the utilities and raw materials required. Moreover, Sánchez et al. [
34] also indicate the representative cost participation in the CAPEX distribution of the extractor, which suggests a focus point for the economic assessment and project development.