3.1. Raw material composition
Table 2 shows the compositional analysis of the raw materials, as well as the polyphenolic and anthocyanin content, and the antioxidant activity. The results showed that the composition of annatto and açai are similar except for the hemicellulose content. However, the lignocellulosic composition was in agreement with other studies reported in the literature. Buratto et al. (2021) calculated an açai seeds content of, respectively, 8.5%, 48.1%, and 11.6 % for cellulose, heicellulose, and lignin. In contrast, 14.4% cellulose, 34.0% hemicellulose, and 10.8% lignin have been reported for annatto seeds (Kumar et al., 2007). The high lignocellulosic composition allows them to be a potential source of biofuel, with calorific values of 16.98 MJ kg− 1 for açai seeds (Alves et al., 2021) and 16.0 MJ kg− 1 for annatto seeds (Atienza et al., 2021). These values have been equal to or even higher than wood chips or pine and with a comparable açai energy density of 10.01 GJ m− 3 with wood pellets (11.1 GJ m− 3) (Alves et al., 2021). The high calorific values are also explained by the high extract content found in both fruits since extractives promote biomass ignition at the initial combustion stage. The extract content is greater in this work than another açai (Souza De Oliveira et al., 2020) and annatto (Okorie et al., 2020) studies. Concerning the ash composition, values were slightly higher for acai seed than those reported by Sato et al. (2019). Meanwhile, the values for annatto seed were lower than those reported in the literature (C. Alcázar-Alay et al., 2015). These results can be explained by species and crop factors, such as the ripening stage and harvest season.
Table 2
Physicochemical characterization of annatto seeds and açai fractions
Parameter | Mass composition (%) |
Annatto seed | Açai seed | Açai pulp |
Initial moisture | 40.01 (0.05) | 31.26 (0.02) | 89.63 (0.32) |
Total extractives* | 28.46 (1.91) | 22.31 (0.51) | - |
Fiber* | - | - | 11.78 (1.36) |
Total carbohydrates* | - | - | 29.91 (1.20) |
Cellulose* | 18.81 (0.73) | 13.05 (1.46) | - |
Hemicellulose* | 11.34 (1.20) | 42.67 (1.81) | - |
Lignin* | 13.92 (0.35) | 15.91 (6.71) | - |
Fats* | 2.76 (0.06) | 2.98 (0.10) | 51.86 (1.45) |
Pectin* | 16.00 (0.04) | - | - |
Protein* | 8.71 (0.39) | - | 4.21 (0.70) |
Ash* | 5.39 (0.07) | 7.54 (0.11) | 2.24 (0.30) |
Polyphenols content** | 5.45 (0.26) | - | 23.56 (0.72) |
Antioxidant activity IC50*** | 443.65 (5.37) | - | 285.84 (3.54) |
Anthocyanins content**** | - | - | 22.58 (1.41) |
Values in brackets refer to standard deviation. |
*Composition on a dry basis. |
**Results in mg of GA equivalents g− 1 of the sample. |
***Results in µmol L− 1. |
****Results in equivalent mg of cyanidin-3-glucoside equivalent 100mg− 1 of sample. |
Table 2 Physicochemical characterization of annatto seeds and açai fractions
The açai pulps are highly perishable at room temperature by the rapid action of its peroxidases and polyphenol oxidases. These enzymes cause browning, anthocyanin degradation, production of peroxide radicals, and lipid oxidation. Therefore, it is recommended a fast fruit processing maximum of 48 hours after harvest) and the application of methods such as pasteurization or novel technologies such as isostatic high-pressure processing, high-pressure processing pulsed light, ultrasound, and microwave (Dantas et al., 2021). Fats extraction from the açai pulp must be carried out to avoid deterioration. This oil is used as a supplement for animal feed, especially in lactation sheep, and for cosmetics (da S. dos Santos et al., 2019). A lipids content close to 50% (on a dry basis) allows the pulp to be an energy source for food products. The total dietary fiber content was low than other fruits, such as passion fruit (53.5%), citrus lemon (87.1%), and coconut (69.9%) (Garcia-Amezquita et al., 2018) since açai pulp was filtered and a certain fraction of the fiber was possibly discarded in this process. Meanwhile, the carbohydrate content is in agreement with the typical range of berries, as blueberries (Lucas et al., 2018) and açai (A. R. Oliveira et al., 2020).
The açai presented high values in polyphenols content than other fruits that are considered sources of these nutrients, such as European cranberry (161 mg GA Eq. 100g− 1), honeyberry (311 mg GA Eq. 100g− 1), black cowberry (565 mg GA Eq. 100g− 1) (N. L. Oliveira et al., 2021), and blueberries (378.2 mg GA Eq. 100g− 1) (Li et al., 2017). Some biocompounds of açai, such as anthocyanin and carotenoids, have shown therapeutic, anti-inflammatory, and anticancer properties (Romualdo et al., 2015). Some studies exhibited the anthocyanin as the main compound of polyphenols in açai, cyanidin-3-glucoside, and cyanidin-3-rutinoside as the predominant forms and are responsible for the purple color of the fruit (Yamaguchi et al., 2015). Regarding the phenolic content of annatto seeds, it showed better results when there are extracted with KOH (4.47 mg GA g− 1) (Raddatz-Mota et al., 2016) or methanol (1.5 mg GA g− 1) (Chisté et al., 2011).
3.2. Dye extraction
As the main results, mass yields of dye extraction of 15.2% and 58.4% were achieved for natural and ground seeds, respectively. Furthermore, exhausted seed yields of 80.3% for the natural seed and 42.1% for the ground seed were achieved. Therefore, annatto processing faces the challenge of waste treatment due to the high generation of exhausted seed. The bottleneck in the production of this dye is the high-water demand, both for the softening and rinsing stages of the fruit, achieving a total water usage of 13.5 L kg− 1 and 10.5 L kg− 1 for the natural and ground seed, respectively. The extraction of bixin and norbixin was quantified in each rinse (see Fig. 2), and it is possible to analyze different issues. (i) For the ground seed, three rinses were performed, while for the natural seed, there were four. This can be explained by the decrease in particle size increases the surface area, allowing greater contact between the seed and the friction media, increasing the extraction performance. (ii) Total depletion of the dyes was not achieved (null extraction) since the seed was rinsed until it was observed that the water did not turn reddish. (iii) A total yield (dye mass per seed mass) of bixin of 44.84 and 36.66 mg g− 1 was achieved for ground and natural seeds, respectively (productivity increase of 22.3% for ground seed). (iv) A total norbixin yield of 2.02 mg g− 1 for ground seed and 2.79 mg g− 1 for whole seed was achieved. No significant difference was observed in the extraction of this dye. (v) As bixin and norbixin were detected in the extraction of the dye paste, mechanical friction is not selective to only one dye. Nevertheless, the small amount of norbixin (compared to bixin) makes the separation process technically unfeasible. (vi) A potential for bixin production was found since it has been established that contents higher than 2.7% in seeds are suitable for commercialization in international markets (Giridhar & Parimalan, 2010). Based on these results, dye extraction was better for the ground seed due to its high extraction yield and high bixin and norbixin content.
Figure 2 Bixin and norbixin extraction yields of the dye throughout seed rinsing. Error bars represent the standard deviation
Although dye extraction through mechanical friction is a clean and chemical-free methodology, it is not widely studied in the literature. Therefore, the results will be compared with other methodologies reported in the literature. The present work results were in agreement with the data reported by several authors. Barrozo et al. (2013) studied the mechanical extraction of bixin powder from annatto seeds using a spouted bed. The authors concluded that the best result was 23 g kg− 1h− 1 of powder with a bixin content of 44% (bixin yield of 10.12 mg g− 1 seed). Shuhama et al. (2003) evaluated a new method for preparing annatto powders based on alkaline seed extraction and subsequent drying in a spouted bed with inert particle bodies, obtaining 3 mL min− 1 of an extract with a bixin concentration close to 13% (1.3 mg g− 1). Other studies have emphasized the extraction of bixin and norbixin through solvents or alkaline agents, showing lower extraction yields than the present work. Pigment extraction yields (g pigment per g seed) of 2.55–4.11% using water, 3.02–4.83% using ethanol, and 4.22–6.04% using KOH (2%) as solvents have been reported, with norbixin contents of 0.06–0.15 mg g− 1 and bixin contents of 6.5–31.5 mg g− 1 of seed (Raddatz-Mota et al., 2016). Taham et al. (2015) evaluated bixin extraction through a fixed-bed extractor using supercritical CO2, ethanol, and an ethanol-water mixture as solvents, finding that the best yields were, respectively, 0.9, 8.4, and 5.5 mg g− 1 of seed.
3.3. Integration rate definition
Table 3 shows the algorithm criteria evaluated for the base raw material and for three proposed integration ratios (1:1:1, 1:0.5:0.5, 1:2:2, EAS:AS:ASL). These integration rates are based on information about raw materials in Chocó. In this sense, for the case of the 1:2:2 EAS:AS:ASL integration (which is the highest), it would consider the projected growth of raw materials in Chocó. Besides, it is expected that the raw material processing will be more standardized to manage better the supply of residues and their application in the production of value-added products. Therefore, Table 3 is made by inquiring about the criteria that will determine the decision-making in the algorithm. At the same time, it is necessary to define a base case (EAS for this study), to subsequently evaluate whether or not the proposed integrations improve the analyzed criteria.
Table 3
Criteria information for the integration proposed. Exhausted annatto seed is the base raw material
Criteria | Base raw material (EAS) | 1:1:1 (EAS:AS:ASL) | 1:0.5:0.5 (EAS:AS:ASL) | 1:2:2 (EAS:AS:ASL) |
Information | Restrictions | Information | Restrictions | Information | Restrictions | Information | Restrictions |
Scale | Pilot plant scale | Artisanal process already established in the region | More than base scale | Açai: There is no standardized cultivation, so in this region it is considered a weed | Less than integration 1:1:1, but more than base scale | Açai: There is no standardized cultivation, so in this region it is considered a weed | More than integration 1:1:1 and base scale | Açai: There is no standardized cultivation, so in this region it is considered a weed |
Composition | The composition of EAS is rich in cellulose which makes it suitable for use | - | The mixing of these residues generates a considerable increase in cellulose and lignin content | Lignin content for anaerobic digestion process | The mixing generates a low increase in cellulose and lignin content | Lignin content for anaerobic digestion process | The mixing generates a high increase in cellulose and lignin content | Lignin content for anaerobic digestion process |
Phase and particle size | Solid-phase, reduction of the size required | 0.5-4 mm | Solid-phase, reduction of the size required for the raw materials (homogenizer) | 0.5-4 mm | Solid-phase, reduction of the size required for the raw materials (homogenizer) | 0.5-4 mm | Solid-phase, reduction of the size required for the raw materials (homogenizer) | 0.5-4 mm |
Pretreatment stage | Dryer and miller | Energy needs | Dryer and miller | More energy needs than the base case | Dryer and miller | Less energy needs than integration 1:1:1 | Dryer and miller | More energy needs than the base case and integration 1:1:1 |
Prices of raw materials and production of value-added products | Production of bioenergy products | More proportion in bioenergy products production than the base case, and more raw material cost | More proportion in bioenergy products production than a base case but less than integration 1:1:1, and more raw material cost | More proportion in bioenergy products production than the base case and integration 1:1:1, and more raw material cost |
Environmental impact | There is no use of other crop residues, but there is use of one of the processing residues (EAS) | Use of processing residues (EAS, AS, and ASL) | Use of processing residues (EAS, AS, and ASL) | Use of processing residues (EAS, AS, and ASL) |
Availability and fluctuation in price | There are no problems with the availability or accessibility of annatto. There are no seasons of significant price variations due to suitable production conditions | There are no problems of availability or accessibility of each raw material. There are no seasons of significant price variations due to suitable production conditions | Similar to integration 1:1:1. Less amount of açai generates less cost associated with its achievement | Similar to integration 1:1:1. More amount of açai generates an increase in cost associated with its achievement |
The first criterion refers to the scale. For both raw materials, the production correspond to low scale, even for the inegration of annatto (Ávila Ávila et al., 2017) and for açai (Isaza Aranguren et al., 2014). In the case of EAS, the restrictions to applying the process are related to the management of these residues since they come from an artisanal process of obtaining annatto dye. However, if this stage can be logistically and technically improved, the scale could be much more stable. Therefore, the proposed integrations are expected to improve the viability of the process and obtain value-added products. The restriction of the integration of açai residues is focused on the problems related to establishing crops (S. Y. Castro et al., 2015). This raw material in the study region has not been established as a producer. It is considered a weed, a native plant, and there are no specific delimitations for its crop.
The second criterion is related to composition. In this criterion, it is needed to know the composition of the raw materials individually. For this purpose, the results of the characterization are analyzed. This information shows whether the integration improves according to the products and platforms defined for the process. Finally, when the best integration ratio is selected, the composition of the mixture is experimentally confirmed.
The phase and particle size (third criterion) of the raw materials determine the pre-processing conditioning requirements. In this case, the raw materials are in a solid phase and are in a small particle size, which indicates that there is no need for considerable conditioning (Centro Nacional de Tecnología Agropecuaria y Forestal, 2010). However, homogenization at the time of blending must be adequately ensured. The fourth criterion for defining the best integration ratio is directly related to the previous one. If a pretreatment step is present, the energy requirements are increased, harming the process (Amin et al., 2017). However, in this case, a dryer and a mill are necessary to homogenize the integrations. Because the raw materials are intended to be integrated during processing, the pretreatment steps are not as significant since the raw materials are already in conditions that are close or at least easy to reach.
Table 3 Criteria information for the integration proposed. Exhausted annatto seed is the base raw material
The prices of raw materials and products (fifth criterion) are evaluated individually. Then it is shown whether integration improves or not, balancing with the value of the value-added products to be obtained. In this study, açai and annatto in Chocó have a price of 0.25 USD kg− 1 and 2.9 USD kg− 1, respectively. The integrations will inevitably increase this value concerning the base raw material. However, biogas as a biorefinery product provides additional income to the stand-alone annatto (or açai) process. In this sense, the information placed in Table 3 for this criterion corresponds to the comparison of bioenergy products between the proposed integrations. The environmental impact (sixth criterion) is related to analyzing whether the raw material within its agronomic or processing component mitigates negative effects on the environment. The residues are considered only in the processing stage (colorant and pulp) for this study. In this sense, residues and their impact are only reflected in this stage. The agronomic part (residues such as peels, leaves, and branches) was not considered raw materials for the integrations.
Finally, the last criterion corresponds to raw material price fluctuation and its availability. In this regard, the acquisition of the residues proposed for the integrations depends on the processing of raw materials. This criterion is related to the cultivation and harvesting of açai and annatto. In the case of açai, it has been reported that it is possible to obtain this fruit throughout the year, but the representative harvest is mainly carried out twice a year. On the other hand, in the case of annatto, there is no problem in obtaining it since in the Chocó region, it is grown practically all year round (except in February and March, when it is in short supply). Therefore, price fluctuations for both raw materials are not very high. This information was evaluated for each proposed integration.
Considering the above analysis and the score defined for each criterion in the three proposed integration ratios, the integration ratio to be worked at the experimental level will be the 1:1:1 EAS:AS:ASL ratio. However, the experimental results using this integration ratio should be analyzed to identify or make adjustments. If this happens, a new integration ratio will be defined to be used in the simulations.
3.4. Anaerobic digestion
In anaerobic digestions, VS and TS content are important variables for calculating substrate and sludge loading and estimating biogas productivity. Table 4 shows the substrate characterization in terms of solids content. A high VS content implies higher biogas productivity. However, the chemical structure and the variability of the organic composition in the samples unbalance the quantification. It should also be noted that according to the initial conditions of the sample for analysis, the results can be discrepant due to the moisture composition. For example, it can be noted that the açai seed has a higher VS content compared to the other samples. Therefore, analyzing only the VS is not completely accurate for estimating maximum biogas productivities. The biodegradability index (BI) is a more reliable parameter for substrate consumption in anaerobic digestions. This index corresponds to the ratio of volatile solids to total solids (VS/TS). Thus, all the samples have similar values that induce good performances in the biogas tests since there are no significant differences between them.
Table 4
Solid composition of the anaerobic digestion substrates
Sample | VS (% wt.) | TS (% wt.) | Biodegradability index (%) |
EAS-N | 24.3 (0.53) | 25.4 (0.37) | 95.7 |
EAS-G | 20.2 (0.25) | 20.6 (0.27) | 98.1 |
AS | 90.3 (0.11) | 94.5 (0.14) | 95.5 |
ASL | 29.1 (0.89) | 29.4 (0.82) | 98.9 |
EAS-G:AS:ASL | 65.7 (0.59) | 66.7 (0.65) | 98.5 |
EAS-N:AS:ASL | 63.9 (0.52) | 66.2 (0.63) | 96.5 |
EAS-N: natural annatto; AEAS-G: ground annatto; AS: açai seed; ASL: açai slurry; EAS-G:AS:ASL: mixture with ground annatto; EAS-N:AS:ASL: mixture with natural annatto. |
Values in brackets refer to standard deviation. |
Table 4 Solid composition of the anaerobic digestion substrates
Figure 3a shows the results of daily productivity in terms of biogas yields. It is possible to note biogas production from the first day, indicating no microorganism adaptation to the substrate (hydrolysis phase). It was also evidenced an increase in production rates for all samples during the first three days of digestion, being the annatto the most representative, with average values of 45.1 and 34.3 mL gVS− 1d− 1 for ground and natural seeds, respectively. However, after the third day, a decrease in the productivity rate was observed, which can be explained by the depletion of soluble and low molecular weight compounds (such as free sugars) that are easily assimilated by the microorganism. Moreover, from the fifth day onwards, the productivities are relatively constant (between 5–35 mL of biogas per day) throughout the digestion time for the açai and mixed residue samples. This may indicate a constant consumption of more complex molecules or biopolymers such as cellulose and hemicellulose. In contrast, an increase in productivity is shown from the ninth day for the annatto samples. This variation can be explained by consuming high molecular weight carbohydrates and other major compounds in the annatto seed, such as lipids, pectin, and protein.
Figure 3 Biogas productivity performance. (a) Biogas yield; (b) methane composition; and (c) H2S concentration. Error bars represent the standard deviation. The legend is the same for all Figures
As shown in Fig. 3a, there is variability in biogas production. Different factors can explain these differences. (i) No pretreatment of the raw material was performed to improve accessibility to biodegradation. Pretreatments decrease the crystallinity and recalcitrance and increase the surface area and porosity of the sample, leading to a higher biodegradability rate (Angelidaki & Ahring, 2000). The only treatment performed on some samples was particle size reduction. However, this treatment does not influence biogas production since annatto seeds have similar productivities (difference of 9.46%), as shown in Table 5. (ii) Partial inhibitions in the açai samples may prevent effective digestion performance. During the initial stage of anaerobic digestion, the accumulation of inhibitory volatile fatty acids (VFA), such as propionic, acetic, and butyric acids (produced during hydrolysis and acidogenesis), is promoted, leading to a decrease in the pH of the system and hindering the further growth of methanogenic bacteria (Wainaina et al., 2019). Simple and soluble sugars, hemicellulose oligosaccharides, and pectin are rapidly hydrolyzed and converted into methanogenic intermediates (mainly VFA) that partially inhibit biogas productivity (Chanakya et al., 1995). (iii) Ammonia can also affect the inhibition of anaerobic digestions if it exceeds a specific concentration of 0.1-2 g-N/L (Parawira et al., 2004). It has been reported that at concentrations above the threshold level of 1.7 g-N L− 1, ammonia nitrogen has a stronger effect on acetoclastic methanogenic bacteria than on hydrogenic methanogenic bacteria (Koster & Lettinga, 1984). During anaerobic digestion, the balance between the production of acetoclastic methanogenic bacteria and hydrogenic bacteria is crucial. The latter help to preserve a low hydrogen concentration to ensure a favorable thermodynamic conversion of propionic acid into hydrogen and acetic acid (methanogenic bacteria substrates) (Fujishima et al., 2000).
Table 5
Summary of anaerobic digestion results of annatto, açai, and the substrates integration
Sample | Biogas yield (mL gVS− 1) | Biomethane yield (mL gVS− 1) | Maximum production rate (mL d− 1) | Average concentration |
CH4 (% vol.) | H2S (ppm) |
EAS-N | 934.7 | 533.2 | 22.0 | 53.7 | 291.1 |
EAS-G | 838.8 | 466.3 | 24.7 | 51.5 | 187.9 |
AS | 219.3 | 129.8 | 8.0 | 59.7 | 44.9 |
ASL | 213.6 | 144.2 | 6.3 | 66.7 | 43.1 |
EAS-N:AS:ASL | 272.9 | 171.7 | 8.7 | 63.1 | 55.1 |
EAS-G:AS:ASL | 307.6 | 186.8 | 8.8 | 60.6 | 46.9 |
Table 5 Summary of anaerobic digestion results of annatto, açai, and the substrates integration
Table 5 shows the results of final cumulative yields and average concentrations of biogas. It was found that the exhausted annatto seeds show the highest production yields for both biogas and biomethane. Likewise, the annatto has the largest average H2S concentrations, decreasing its quality as a biofuel. H2S is a pollutant gas that harms pipes and processing equipment since it promotes fouling formation, reducing their diameter and finally clogging them after a certain operating period. Furthermore, in combustion processes, the formation of H2SO4 that corrodes accessories and components of the biogas internal combustion engine has been reported (Mamun & Torii, 2015). Nevertheless, all samples (Fig. 3c) have concentrations below the limit (< 1000 ppm) for thermochemical biogas application technologies such as Gas Heating Boilers and Combined Heat and Power (Choudhury et al., 2019). In contrast to the annatto, the ASL has the highest average CH4 concentration, reaching the maximum concentration of 76.5% (vol.) on day 19 (Fig. 3b). Regarding the AS sample, a cumulative biogas and biomethane yield of 219.3 and 129.8 mL gVS− 1, respectively, and a maximum CH4 concentration of 66.4% (day 26) were obtained. These results are in agreement with some studies reported in the literature. Sganzerla et al. (2021) evaluated the biogas production from açai seed (derived from a food industry) in a 6.8 L biodigester at mesophilic conditions. The authors obtained a final methane yield of 158.8 mL gVS− 1 at an average composition of 56.5% (vol.) during the first half of the digestion. In addition, Maciel-Silva et al. (2019) studied mesophilic biogas production from seeds and wastewater from açai processing following pretreatment with subcritical water. The authors obtained a biogas yield of 791.8 mL gVS− 1 when the pretreatment was performed at 200°C and 7.8 mL gVS− 1 in the absence of pretreatment (control assay) with a fed with 25% açai seed and 45% wastewater. It is noteworthy that the pretreatment with subcritical hydrolysis is efficient since it increases the yield by more than 100 times.
3.4.1. Substrate integration
The results of the proposed integrations showed a maximum production rate of 8.7 mL d− 1 for EAS-N:AS:ASL and 8.8 mL d− 1 for EAS-G:AS:AS:ASL. In this sense, both performances were lower than the exhausted annatto seed-only assays. It demonstrates that feedstock integration does not always guarantee improvements in biogas yields. It is explained by the chemical composition of the mixture, which is more complex for the metabolism of anaerobic microorganisms. Therefore, a pretreatment stage should be considered to facilitate access to platform molecules such as sugars. Another possible explanation for this decrease in productivity may be the variation of the C/N ratio. The indicator of the carbon and nitrogen content of the substrate can interact with the medium, which leads to different ammonia concentrations and inhibitory effects (Wang et al., 2014). It has been demonstrated that the mixing of substrates through co-digestion favors the C/N ratio (Shahbaz et al., 2020). However, fruit mixtures are disadvantaged due to the high protein content (Jesus et al., 2018), especially when dealing with açai slurry with considerable pulp, which finally alters the optimum C/N ratio (25–30). Analyzing these results and as mentioned in Section 3.2, adjusting the initial definition of the integration rate is necessary. In global terms, it is evident that the best performance in biogas production was annatto residues. Even though the biogas quality is the best for the evaluated cases. Therefore, it would be expected that the new integration ratio should have a majority mass representation of annatto compared to açai residues. Hence, the 1:0.5:0.5 EAS-N:AS:ASL is proposed as the new integration ratio used in simulation scenarios.
3.4.2. Kinetic model
Online Resource 3 shows the mathematical fit of the Gompertz model for cumulative methane productivity of annatto samples. it was possible to observe a model deviation for the first 15 days of digestion, even with adaptation time results, as shown in Table 6. On the other hand, differences between the experimental and predicted values of 4.8% and 3.4% were obtained for the EAS-N and EAS-G, respectively, for methane production potential (A). Moreover, a difference of less than 5% was obtained between the maximum production rates of the model and the experimental results for EAS-N (24.1 mL gVS− 1d− 1) and EAS-G (23.1 mL gVS− 1d-1). Concerning the açai residues (Online Resource 4), both samples showed productivity from the beginning of the digestion; however, the AS was the sample with the most moderate adjustment (R2 of 0.978). In addition, there was a difference (between experimental and model results) in the methane production potential of 7.9% for the AS and 0.2% for the ASL, respectively. For the maximum methane productivities, similarities were obtained for the AS substrate and less than 8% errors for the ASL. With these results, the model shows that there can be small variations regarding the experimental results, being the initial digestion stage the most relevant to variation.
Table 6
Parameter results of Gompertz model for anaerobic digestion
Parameter | Sample |
EAS-N | EAS-G | AS | ASL |
R2 | 0.988 | 0.989 | 0.978 | 0.997 |
A (mL gVS− 1) | 626.35 | 520.62 | 334.25 | 154.63 |
\({\mu }_{max}\) (mL gVS− 1d− 1) | 25.19 | 23.41 | 5.62 | 6.65 |
λ (day) | 4.00 | 3.80 | 8.09 | 1.43 |
Table 6 Parameter results of Gompertz model for anaerobic digestion
3.5. Simulations analysis
3.5.1. Techno-energetic results
The techno-energetic results were determined based on mass and energy balances. Table 7 shows the results of the indicators for the proposed scenarios. In terms of YP index, it is possible to evidence that the yields in Sc1, Sc2, Sc3, and Sc4 are maintained for annatto seed colorant and açai pulp under the same processing scale. However, if this index is analyzed globally, the values indicate that Sc5 presents the highest raw materials yield per kg. It means that with the integration of annatto and açai, more fractions of the raw materials are used to obtain value-added products. Sc5 also presented a higher value than the other scenarios for the PMI and MLI indicators since the product determines both flows obtained in the process. Finally, in terms of the RMI mass indicator, Sc1 presents the highest value for this indicator, while Sc5 presents the lowest value. It is explained by the amount of inputs required in the process. Sc1 requires only one input (water), while Sc5 requires three (water, NaClO, and sludge).
Table 7
Mass and energy indicators for scenarios proposed
Mass indicators |
Scenario | Product yield (YP) | Process mass intensity index (PMI) | Mass loss index (MLI) | Renewability material index (RMI) |
Sc1 | 43.48 kg dye 100kg− 1 annatto | 19.44 kg raw materials kg− 1 dye | 18.44 kg waste streams kg− 1 dye | 0.118 kg renewable feedstock kg− 1 raw materials |
Sc2 | 52.99 kg pulp 100kg− 1 açai | 5.86 kg raw materials kg− 1 açai | 4.86 kg waste streams kg− 1 pulp | 0.322 kg renewable feedstock kg− 1 raw materials |
Sc3 | 43.48 kg dye 100kg− 1 annatto | 57.20 kg raw materials kg− 1 products | 56.41 kg waste streams kg− 1 dye | 0.032 kg renewable feedstock kg− 1 raw materials |
11.61 kg biogas 100kg− 1 annatto | 56.99 kg waste streams kg− 1 biogas |
Sc4 | 52.99 kg pulp 100kg− 1 açai | 41.03 kg raw materials kg− 1 products | 40.34 kg waste streams kg− 1 pulp | 0.032 kg renewable feedstock kg− 1 raw materials |
22.97 kg biogas 100kg− 1 açai | 40.73 kg waste streams kg− 1 biogas |
Sc5 | 37.70 kg dye 100kg− 1 raw materials | 64.43 kg raw materials kg− 1 products | 63.82 kg waste streams kg− 1 dye | 0.026 kg renewable feedstock kg− 1 raw materials |
9.48 kg pulp 100kg− 1 raw materials | 64.27 kg waste streams kg− 1 pulp |
13.64 kg biogas 100kg− 1 raw materials | 64.20 kg waste streams kg− 1 biogas |
Energy indicators |
Scenario | Overall energy efficiency (η) | Specific energy consumption (SEC) | Resource energy efficiency (ηE) | Self-generation index (SGI) |
Sc1 | 0.36 | 1.11 MJ kg− 1 | 0.43 | 0.67 |
Sc2 | 0.46 | 0.95 MJ kg− 1 | 0.53 | 1.06 |
Sc3 | 0.73 | 1.69 MJ kg− 1 | 0.47 | 0.95 |
Sc4 | 0.69 | 6.78 MJ kg− 1 | 0.58 | 0.40 |
Sc5 | 0.60 | 3.82 MJ kg− 1 | 0.97 | 0.47 |
Table 7 Mass and energy indicators for scenarios proposed
On the other hand, energy indicators make it possible to evaluate the energy efficiency of the process and energy consumption and sufficiency. Sc3 presented the highest η indicator compared to the other scenarios. It indicates that it has a much higher overall efficiency, mainly due to the equipment used in the process. Compared to Sc1, this indicator also shows that adding a processing line (biogas production for Sc3) can energetically benefit the performance of the process. Regarding the SEC indicator, Sc4 shows 6.78 MJ kg− 1, the highest value among all the proposed scenarios. Furthermore, the integration of raw materials (Sc5) shows by employing the ηE indicator that the transformation of raw materials into products maintains 97% of the energy. Finally, the SGI indicator evaluates the capacity of the process to supply partially or totally the energy of the process. In the case of Sc2 (with a value greater than 1.0), the process energy is not only fully supplied, but there is a surplus that can be used in part of the value chain of the products. However, Sc4 and Sc5 supply less than 50% of the process energy.
3.5.2. Economic assessment
The economic analysis was performed considering parameters such as capital expenditure (CapEx), operational expenditure (OpEx), incomes, net present value (NPV), among others, as shown in Table 8. Concerning the CapEx, the raw material integration scenario (Sc5) has the highest cost, which was expected due to both processing units of açai and annatto. This capital investment involved the cost of equipment (144.2 k-USD), instrumentation (198.5 k-USD), installation civil work (38.5 k-USD), piping (22.9 k-USD), and electrical (5.3 k-USD). On the other hand, it can be observed that although the CapEx of the stand-alone pulp production (Sc2) is slightly higher than the annatto dye paste (Sc1), the addition of an anaerobic digestion stage leads to a higher CapEx for the dye production with biogas (Sc3) compared to the processing of açai with biogas (Sc4). This can be explained by the fact that the digester has a larger processing volume leading to an increase in the direct equipment, accessories, and installation cost. Therefore, from the CapEx comparison, Sc1 is the most economical process. Regarding the revenue indicator, the scenarios of annatto dye paste production (Sc1 and Sc3) are the most relevant due to the high selling price in the market (> 20 USD kg− 1). Indeed, it can be observed in Table 8 that the biogas sale does not influence the total revenue, contributing 148.4 k-USD year− 1 (equivalent to 16.9 USD h− 1). Likewise, higher gross income is observed for the annatto scenarios. Although the açai processing (Sc2 and Sc4) have the lowest gross income, they were the scenarios that best buffered the production costs (see Table 9), reducing revenues (comparison between revenues and gross incomes) by 14–17% compared to Sc1, Sc2, and Sc5, which were 33–39%.
Table 8
Economic results summary of the proposed scenarios
Parameter | Scenario |
Sc1 | Sc2 | Sc3 | Sc4 | Sc5 |
CapEx (k-USD) | 358.1 | 366.9 | 415.4 | 408.2 | 559.1 |
OpEx (M-USD year− 1) | 11.7 | 1.3 | 11.9 | 1.7 | 9.9 |
Raw material (M-USD year− 1) | 10.6 | 0.9 | 10.7 | 1.0 | 8.8 |
Utilities (M-USD year− 1) | 1.8 | 0.1 | 0.9 | 0.5 | 0.9 |
Depreciation (M-USD year− 1) | 45.8 | 46.9 | 53.1 | 52.2 | 71.5 |
Revenue (M-USD year− 1) | 32.2 | 10.3 | 32.4 | 10.6 | 26.4 |
Gross income (M-USD year− 1) | 19.6 | 8.9 | 20.4 | 8.8 | 17.7 |
NPV in 20 years (M-USD year− 1)* | 164.3 | 75.5 | 171.5 | 74.2 | 137.9 |
MPSEF* (kg d− 1)** | 73 | 148 | 84.2 | 161.9 | 88.8 |
*Net present value at the base flow rate of 10 ton d− 1. |
**Minimum processing scale for economic feasibility. |
Table 9
Production cost of dye paste, pulp, and biogas for the different scenarios
Scenario | Production cost (USD kg− 1) | Profit margin (%) |
Dye paste | Pulp | Biogas* |
Sc1 | 7.95 | - | - | 60.8 |
Sc2 | - | 0.68 | - | 87.3 |
Sc3 | 7.47 | - | 0.13 (0.16) | 63.2 |
Sc4 | - | 0.90 | 0.06 (0.07) | 83.2 |
Sc5 | 7.68 | 2.02 | 0.13 (0.17) | 62.1 |
*Values in brackets refer to the production cost in USD m− 3 |
Table 8 Economic results summary of the proposed scenarios
Table 9 Production cost of dye paste, pulp, and biogas for the different scenarios
Concerning the OpEx, Table 9 shows that the annatto processing scenarios are the most expensive, almost ten times more expensive than the processing of açai. This difference in variable costs is due to the high cost of raw materials (see Fig. 4), being 10.6, 10.7, and 8.8 M-USD year− 1 for Sc1, Sc3, and Sc5, respectively. For these scenarios, the annatto cost had the greatest influence on total raw material, representing more than 98%. The annatto seed cost was calculated based on the production cost per kg of seed in the agronomic crop stage in Chocó (Colombia), considering variables such as fertilizers, substrates, nursery construction, machinery & accessories for germination, land adaptation and harvesting, labor, transport, among others. This cost was in agreement with the annatto seeds sold by agronomists in the region. Furthermore, the raw material cost had the greatest impact on the OpEx in the açai processing scenarios, being 1.3 M-USD year− 1 for Sc2 and 1.7 M-USD year− 1 for Sc4. In terms of utilities, it was observed that they had a minor impact on the variable costs being within 7–10% of the OpEx for Sc1, Sc2, Sc3, and Sc5. In contrast, Sc4 utilities contributed 29.1%, where the low-pressure steam, cooling water, and electricity were, respectively, 60.8, 55.4, and 402.7 k-USD year− 1. The remaining OpEx (e.g., maintenance, administrative, plant overhead, laboratory charges, among others) had a low influence on total costs, ranging between 2% and 18%. Therefore, from an OpEx perspective, the açai processing scenarios are the least expensive.
Figure 4 Total distribution cost of (a) Sc1, (b) Sc2, (c) Sc3, (d) Sc4, and (e) Sc5. The legend is the same for all Figures
Table 9 shows that positive profits (> 60%) were obtained for all the proposed scenarios since the production cost is lower than the selling cost. Likewise, a positive cash flow balance was obtained over 20 years of economic analysis (see Table 8), showing that the accumulated net present value (NPV) was between USD 74 and USD 171 million per year. Therefore, economic viability is demonstrated for all the proposed scenarios. Based on the annatto processing perspective, the cumulative NPV for 20 years would be 193.7 and 500.9 M-USD year− 1 assuming the Chocó regional production (11.3 ton d− 1), and 202.9 and 524.5 M-USD year− 1 when working with the Colombian national production (11.8 ton d− 1) for Sc1 and Sc3, respectively. Meanwhile, working with 66.4-ton d− 1 of the national production of açai would provide a NPV of 514.1 M-USD year− 1 for Sc2 and 516.3 M-USD year− 1 for Sc4. Therefore, it was proposed to perform a sensitivity analysis based on the raw material scale to find the minimum point for economic viability, a term known as minimum processing scale for economic viability (MPSEF), as shown in Fig. 5. It was found that the annatto scenarios (Sc1 and Sc3) and integration (Sc5) demonstrate the lowest processing flows (see table). In contrast, obtaining açai pulp coupled with biogas production (Sc4) requires the largest input flow (161.9 kg d− 1). Nevertheless, all MPSEFs are below the regional and national production of both annatto and açai.
Figure 5 NPV at the minimum processing scale for economic feasibility