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Article

Production of High-Value Green Chemicals via Catalytic Fast Pyrolysis of Eucalyptus urograndis Forest Residues

by
Ricardo de C. Bittencourt
*,
Tiago Guimarães
,
Marcelo M. da Costa
,
Larissa S. Silva
,
Verônica O. de P. Barbosa
,
Stéphani Caroline de L. Arêdes
,
Krisnna S. Alves
and
Ana Márcia M. L. Carvalho
Department of Forestry Engineering, Federal University of Viçosa, Viçosa 36570-900, MG, Brazil
*
Author to whom correspondence should be addressed.
Sustainability 2024, 16(19), 8294; https://doi.org/10.3390/su16198294
Submission received: 23 April 2024 / Revised: 20 May 2024 / Accepted: 27 May 2024 / Published: 24 September 2024
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Abstract

:
Lately, pyrolysis has attracted significant attention due to its substantial potential for bio-oil production, with the ability to serve as a renewable energy source and/or facilitate the production of valuable chemical compounds. The chemical compounds generated and their amounts are completely influenced by the traits and chemical makeup of the initial biomass. In this work, the catalytic fast pyrolysis of Eucalyptus urograndis canopy was carried out using a pyrolyzer coupled to gas chromatography/mass spectrometry (Py-GC/MS) at different temperatures and in the presence and absence of catalysts. Elemental composition analysis was employed to characterize the chemical composition of the biomass. The results showed a biomass with a carbon percentage of 50.20%, oxygen of 43.21%, and hydrogen of 6.34%, as well as a lower calorific power of 17.51 MJ/kg. The Py-GC/MS analyses revealed the presence of several noteworthy compounds, including acetic acid (C2H4O2) and, in smaller quantities, hydrogen (H2), furfural (C5H4O2), and levoglucosan (C6H10O5). The technical-economic evaluation revealed that the production of acetic acid, furfural, hydrogen, and levoglucosan commands a high market price. Additionally, a single production cycle is anticipated to yield a favorable technical-economic balance, generating approximately USD 466.10 /ton of processed biomass. This outcome is achieved through the process of catalytic fast pyrolysis, where CuO has been identified as the most suitable catalyst.

Graphical Abstract

1. Introduction

Due to a potential shortage of fossil fuels [1], and especially with the environmental impact linked to their use and CO2 emission, there is a growing interest in the search for renewable, economical, sustainable, and efficient energy sources to meet the future needs of the world. Renewable energy sources, such as biomass, play a fundamental role in the energy, environmental, and socioeconomic scenario [2]. Biomass is obtained from organic materials that have the potential to be used as an energy source. Biomass is a renewable resource that encompasses various sources, such as forestry activities, livestock, agricultural crops, aquatic plants, food processing, and their waste. This raw material is mainly composed of carbon, hydrogen, oxygen, and nitrogen, although some types may also contain sulfur and ash in their composition [3].
Brazil is among the main producers of eucalyptus in the world, with 22% of global production. Most of this wood is used by the paper and pulp industries and the furniture industry. About 20% of the mass-produced wood is transformed into waste, and in forestry activities, 99.7% of the waste is left in the field [4]. The main thermochemical processes for energy recovery from biomass are gasification and pyrolysis [5]. In the pyrolysis process, organic macromolecules are thermally decomposed at high temperatures into low molecular weight products, in liquid, solid, and gaseous forms, changing the yield according to the process conditions, which can be used as fuel or energy source [6]. This process is known to be a viable solution that presents interesting advantages, including the rapid and complete decomposition of biomass [7].
The composition and yield of these products (liquids, solids, and gases) depend on the types of biomasses, the size of the particles, and the operating conditions of the pyrolysis [8]. Slow pyrolysis is carried out at moderate temperatures and long residence times, while fast pyrolysis is carried out at higher temperatures and shorter residence times [9]. Pyrolysis plays a crucial role both in the economic and biotechnological spheres, standing out as a versatile and promising technique [10]. Economically, pyrolysis enables the efficient conversion of biomass, agricultural residues, and plastics into a variety of valuable products such as biofuels, chemicals, and carbonaceous materials [11]. This approach not only reduces dependence on fossil resources but also contributes to mitigating greenhouse gas emissions [12].
Additionally, in the biotechnological realm, pyrolysis offers significant opportunities for the production of biofertilizers, biochar, and other value-added products, promoting agricultural sustainability and efficient organic waste management [13]. Thus, the application of pyrolysis plays a fundamental role in transitioning towards a more circular and sustainable economy, driving both technological innovation and environmental conservation [14]. There is also analytical pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC/MS), which is a technique that can infer the degree of thermal conversion of biomass and, consequently, of the products formed in situ [15].
In contrast to many other thermal stability techniques, Py-GC/MS is fast and does not require sample preparation, and therefore deserves further exploration [16]. This type of analytical pyrolysis is a fundamental technique for analyses of lignocellulosic biomass [17]. The main advantage is the use of small amounts of sample and high reproducibility [18]. Py-GC/MS is widely used to study the conversion of biomass into biofuels on a laboratory scale [19].
Currently, the production of high-value-added chemical products from forest biomass through catalytic fast pyrolysis is focused on improving the efficiency and selectivity of catalysts [20], as well as their stability under operational conditions [21]. Issues related to scalability for large-scale production and cost reduction are also being addressed, aiming at the commercial viability of the technology [22]. Furthermore, there is an ongoing effort to assess the total environmental impact of the process, considering not only the sustainability of the raw material but also issues such as the use of natural resources and greenhouse gas emissions throughout the entire process [23].
In the pyrolysis process, the catalytic fast pyrolysis of biomass can be adopted to selectively control the distribution of pyrolytic products, and the catalysts used can be applied to the pyrolysis vapors to eliminate or convert these undesirable compounds before condemnation into high-value-added compounds. Recently, several studies have been conducted to produce high-quality bio-oil via rapid catalytic pyrolysis of biomass, where the key issue for the process is to select the right catalysts for the desired type of reaction [24]. In this study, the novelty will be the use of the residue from the Eucalyptus urograndis canopy for the production of hydrogen and high-value-added chemical products, through catalytic fast pyrolysis, using catalysts such as copper oxide (CuO), titanium dioxide (TiO2), cobalt ferrite (CoFe2O4), and iron nanoparticles (nZVI).

2. Materials and Methods Experimental

2.1. Biomass Preparation

In this work, the biomass of forest residues obtained from the Eucalyptus urograndis canopy was used. The process of obtaining the sawdust was carried out according to the standard procedure Tappi T257 cm-85. For the preparation of the samples in the form of chips, a laboratory disc chipper with three knives was used. Then, the chips were transformed into sawdust in a Willey mill and subsequently classified in 40 and 60 mesh sieves.
The sawdust used in the analyses, retained in the 60 mesh sieve, was stored in a climate-controlled room, with constant relative humidity and temperature of 50% and 23 °C, respectively, and kept in hermetically sealed containers.

2.2. Biomass Characterization

The elemental analysis of carbon, hydrogen, and nitrogen (CHN) present in the canopy of the Eucalyptus urograndis trees was carried out using an elemental analyzer (Vario MACRO) equipped with a conductivity detector. The combustion tube was set up at 1150 °C and the reduction tube at 850 °C. Sulfanilamide was used as the CHN standard (C = 41.81%, N = 16.26%, H = 4.65%, S = 18.62%, % by mass).
The energy properties and the potential for energy recovery from the Eucalyptus urograndis canopy were evaluated through their lower calorific values, obtained by the (ABNT NBR 8633/84) standard [25]. The metals were analyzed by ICP-OES.

2.3. Preparation of Catalysts

Considering the cost of the catalyst and the potential for industrial applications, it is worth exploring approaches involving basic metal-based catalysts such as copper [26,27], titanium [28,29], cobalt [30], and iron [31,32]. From this qualification, the catalysts used in this work were zero-valence iron nanoparticles (nZVI), cobalt ferrite (CoFe2O4), copper oxide (CuO), and titanium dioxide (TiO2). Copper oxide (CuO) (CAS No. 1317-38-0) and titanium dioxide (TiO2) (CAS No. 13463-67-7) were obtained from SigmaAldrich (St. Louis, MO, USA).
The nZVI were synthesized according to the methodology adapted from Qian et al. (2019), in which 100.00 mL of NaBH4 (1.080 mol L−1) was added drop by drop to 50.00 mL of FeSO4⋅7H2O solution (0.470 mol L−1) at a rate of 0.100 mL s−1 under constant stirring at 500 rpm [33]. The nZVI were separated by vacuum filtration, followed by washing with water–alcohol (1:4, v/v), drying in a rotary evaporator, and storage under refrigeration (−20 °C).
The cobalt ferrite (CoFe2O4) was synthesized according to a method adapted from Alberton et al. (2020), in which cobalt ferrite is prepared by combustion reaction using iron nitrate (Fe(NO3)3.9H2O) and cobalt nitrate (Co(NO3)2.6H2O) as reagents and urea (CH4N2O) as fuel [34]. The reagents were mixed in a crucible to form a reducing mixture, where the oxidizing agent and the source of cations (Co2⁺ and Fe3⁺) were cobalt nitrate and iron nitrate.
To obtain 5.00 g of catalyst, 17.50 g of Fe(NO3)3.9H2O, 13.3 g of Co(NO3)2.6H2O, and 6.70 g of CH4 N2O were used. The substances were placed in a porcelain capsule, homogenized, and heated in a muffle at 480 °C for 20 min, producing CoFe2O4. To ensure thermal stability, after synthesis, the CoFe2O4 was calcined for 1 h at 500 °C in an air flow at a heating rate of 10 °C min−1.

2.4. Py-GC/MS Processes

The Py-GC/MS tests were conducted employing a pyrolysis micro-oven (manufactured by Frontier Laboratories Ltd., Fukushima, Japan) linked to a gas chromatograph equipped with a mass spectrometer detector (Shimadzu, Kyoto, Japan) QP2020 model, utilizing an Ultra-ALLOY® column (Shimadzu, Kyoto, Japan), (UA5, with dimensions of 30 m × 0.25 mm, and a film thickness of 0.25 μm).
The experiments were conducted at four different temperatures (350, 450, 550, and 650 °C) during the thermal degradation process, with a residence time of 0.1 min. The compounds released during this process were identified by comparing their mass spectra with the GC-MS spectral library (Willey and NIST) and referencing data from the literature [35,36]. The mass load ranged from 2 to 300, and the average of the 100 peaks with the largest area was reported.
Samples from the Eucalyptus urograndis canopy were weighed (0.100 ± 0.005 mg) and taken to Py-GC/MS. These samples were analyzed in the presence and absence of catalysts, adjusting the residence time and pyrolysis temperature. As the concentration of biomass and catalysts affect the results in the reaction, the mass used was standardized to 0.100 ± 0.005 mg with 1% (m/m) of catalyst in catalytic Py-GC/MS experiments. Throughout all the conducted experiments, the interface temperature was maintained at 300 °C. Helium served as the carrier gas, flowing consistently at a rate of 1 mL/min.
All experiments were carried out in triplicate.

3. Results and Discussion

3.1. Biomass Characterization

Through the characterization of the biomass, it was possible to obtain the results of the chemical composition of the Eucalyptus urograndis canopy, presented in Table 1.
The results of the elemental analysis and calorific power for the Eucalyptus urograndis canopy are in accordance with the results described in the literature, with the percentage of C close to 50%. Nakai et al. (2014) characterized the biomass of different species of eucalyptus and found C values of 47.74, 47.52, and 48.10% for the species Eucalyptus urophylla, Eucalyptus grandis, and Eucalyptus urograndis, respectively [37]. The LHV of 17.5 MJ/kg is also comparable to those found by Neiva (2018), who found, in their studies, values of 16.46 MJ/kg for the calorific value of eucalyptus chips [38].
The results found for the metals present in the Eucalyptus urograndis canopy are comparable to those described in the literature with more expressive results for K, Na, and Mg [39]. Félix et al. (2017) characterized samples from eucalyptus biomass for use in pyrolysis processes and encounters the presence of metals such as K, Ca, Mn, Mg, and Si [40]. The values of inorganic and insoluble in HCl (6M) are also within the expected, according to the literature [37].

3.2. Py-GC/MS of Eucalyptus urograndis Canopy

For comparison of the results obtained in the catalytic pyrolysis, control experiments were carried out using the Eucalyptus urograndis canopy. Figure S1 (Supplementary Materials) presents the typical chromatogram of non-catalytic pyrolysis (fast pyrolysis) of this control experiment. As shown in Figure S1, the rapid pyrolysis of the canopy of Eucalyptus urograndis produces a large amount of low molecular weight compounds [41].
The top 10 compounds produced from the non-catalytic fast pyrolysis of the of Eucalyptus urograndis canopy at 350 °C were listed and are arranged in Table S1 (Supplementary Materials), where it is observed that the majority product found was acetic acid (C2H4O2), with an area of approximately 18%. Other compounds of interest were also produced in smaller quantities, such as levoglucosan (3.21%), furfural (1.31%), and 5-hydroxymethylfurfural (HMF) (0.90%). The production of hydrogen, however, was very low, at around 0.80%.
The main parameter that influences the products generated in the pyrolysis process is related to the temperature of the process [42]. Thus, experiments were carried out at different pyrolysis temperatures in order to determine the best temperature for the production of hydrogen and levoglucosan from the residue of the canopy of Eucalyptus urograndis. The results for the main products obtained in the Py-GC/MS of the canopy of Eucalyptus urograndis at different temperatures are shown in Figure 1.
As can be observed in Figure 1, the proportion of products generated from the non-catalytic rapid pyrolysis of the Eucalyptus urograndis canopy varies with the pyrolysis temperature, but the best results, for the production of hydrogen, furfural, and levoglucosan, although low, are still found at the temperature of 350 °C. According to Sun et al. (2021), an option to increase the production of a compound of interest would be the use of a catalyst in the pyrolysis process [43]. In this context, the catalyst would act by influencing the decomposition of the Eucalyptus urograndis canopy, altering the distribution and content of chemical compounds, in addition to the yield of the products formed [44].
Therefore, experiments were carried out using different catalysts for the Py-GC/MS of the Eucalyptus urograndis canopy. The insertion of the catalyst into the pyrolysis system is one of the crucial elements in the catalytic fast pyrolysis of biomass, as it can seriously affect the decomposition and chemical composition of the products generated [45]. The summarized results with the main products obtained using nZVI as a catalyst at different temperatures are presented in Figure 2 and the ion chromatograms of the Py-GC/MS are provided in the Supplementary Materials (Figure S2).
As can be observed in Figure 2, the use of nZVI as a catalyst in the process increased the production of acetic acid (23.8%) and acetic acid-oxo (24.4%), but the production of levoglucosan significantly decreased (0.02%) at a temperature of 350 °C. Wang et al. (2022) used iron-based catalysts to evaluate the characteristics of the products produced via pyrolysis, and one of the highlights of the work was that these iron-based catalysts can be converted into activated metallic iron during the pyrolysis process, which, when reacting with a hydrogen molecule or radicals, would form iron oxides such as Fe3O4 and metallic Fe, which further facilitated the production of gasoline and diesel [31].
In the non-condensable pyrolytic gases, H2 is considered a clean renewable fuel because it has a much higher calorific power compared to fossil fuels, such as coal, gasoline, and methane, while the combustion of H2 gas generates few atmospheric pollutants [46]. As the objective of this work was the production of hydrogen and levoglucosan, the Eucalyptus urograndis canopy was subjected to catalytic fast pyrolysis using CoFe2O4 as a catalyst, and the summarized results with the main products obtained are presented in Figure 3, with the ion chromatograms of Py-GC/MS provided in the Supplementary Materials (Figure S3).
As can be observed in Figure 3, as the pyrolysis temperature increases, the production of levoglucosan and furfural is favored, but the formation of hydrogen decreases; therefore, the use of CoFe2O4 as a catalyst for the production of H2 is not viable. Titanium-based catalysts are described in the literature as highly capable of improving the production of some compounds of interest during the pyrolysis process [47]. Therefore, catalytic fast pyrolysis experiments of Eucalyptus urograndis canopy were carried out using TiO₂ as a catalyst, and the summarized results with the main products obtained are presented in Figure 4, with the ion chromatograms of Py-GC/MS provided in the Supplementary Materials (Figure S4).
When using TiO2 as a catalyst, the amount of levoglucosan produced remained stable at the different temperatures evaluated, but what stood out the most was the formation of hydroxy-acetaldehyde, which was favored at the pyrolysis temperature of 350 °C. The production of hydrogen also deserves mention, with the best temperature for its production being 550 °C; however, these values are still below expectations. Several works are described in the literature using CuO as a catalyst in different thermochemical processes for various purposes [48]. The use of such a catalyst is described by Xie et al. (2022), who, in their studies, used a copper catalyst, which proved to be efficient and stable for the selective oxidation of cyclohexane [27]. In this work, CuO was used as a catalyst for the production of hydrogen and levoglucosan from the Eucalyptus urograndis canopy, and the summarized results with the main products obtained for the catalytic pyrolysis are presented in Figure 5, with the ion chromatograms of Py-GC/MS provided in the Supplementary Materials (Figure S5).
The use of CuO as a catalyst most favored the production of hydrogen, with the optimal temperature being 550 °C, resulting in a production of approximately 7.5%. Other products of interest were also found in considerable amounts, with the top 10 presented in Table S2. As shown in Table S2, when the Eucalyptus urograndis canopy is subjected to catalytic thermal degradation using CuO as a catalyst, various low molecular weight organic compounds are formed, mainly acetic acid, hydrogen, and levoglucosan.
As the main objective of this work was the formation of green chemicals, a comparative study was conducted on the quantity of these compounds produced from the pyrolysis of the canopy of Eucalyptus urograndis, with and without the presence of different catalysts, at the various temperatures studied. The results are presented in Figure 6.
The results of this study indicate that the catalytic fast pyrolysis of canopy Eucalyptus urograndis has significant potential for the production of chemical products with high added value. As observed in Figure 6, the hydrogen production varies according to the catalyst used and the temperature of the pyrolysis process, and the CuO was identified as the most effective catalyst for the process, demonstrating the best results under operating conditions when compared to other catalysts, such as titanium dioxide (TiO2), cobalt ferrite (CoFe2O4), and iron nanoparticles (nZVI). The catalytic process studied in this work managed to produce about 30% (m/m) of acetic acid from the Eucalyptus urograndis canopy. Typically, without catalytic processing, the bio-oil produced by pyrolysis has an acetic acid content of less than 10% (m/m) [49].
Approximately 75% of the acetic acid currently produced comes from non-renewable sources, mainly through the carbonylation of methanol. There are also biological fermentation methods, but they are slow and inefficient in meeting market demands; they are currently very useful for meeting the needs of the food market in the production of vinegar [50]. Acetic acid has the advantage of being non-flammable, which makes its transport safer, in addition to being in the liquid phase, which facilitates the transport, storage, and handling of this product [51]. Other compounds produced during the catalytic fast pyrolysis of the Eucalyptus urograndis canopy using CuO as a catalyst, such as furfural and levoglucosan, also have a high market value [52,53], and therefore, a technical-economic assessment (TEA) was conducted for this reaction condition.

3.3. Technical-Economic Assessment (TEA)

According to the literature, on an industrial scale, the pyrolysis of lignocellulosic biomass yields a bio-oil with approximately 60% efficiency [54]. In addition, the yield of biochar is in the range of 30–35% [55,56]. Besides acetic acid (C2H4O2), other compounds of interest are formed during the pyrolysis of the Eucalyptus urograndis canopy using CuO as a catalyst.
These green chemical compounds, such as hydrogen (H2), furfural (C5H4O2), and levoglucosan (C6H10O5), contribute to the composition of the high-value-added product, albeit in smaller quantities. Upon evaluating the primary compounds formed, their combined mass constitutes approximately 50% of the bio-oil composition. Therefore, Figure 7 shows the techno-economic assessment for the catalytic fast pyrolysis of the Eucalyptus urograndis canopy using CuO as a catalyst.
It can be observed from Figure 7 that a single pyrolysis reaction of the Eucalyptus urograndis canopy using CuO as a catalyst will result in high profitability. The market price values provided were investigated based on the various applications of each product, as outlined in Table S3 (Supplementary Materials). Considering the contribution of these promising green chemicals, it is feasible to achieve a total balance of USD 466.10 per ton of Eucalyptus urograndis canopy processed via catalytic fast pyrolysis using CuO as the catalyst.

4. Conclusions

Based on the results obtained in this study on the catalytic fast pyrolysis of the Eucalyptus urograndis canopy, it can be concluded that this technique has high potential for the production of high-value-added chemicals from this biomass. The analysis of the chemical composition of the biomass revealed a significant content of carbon, oxygen, and hydrogen. During pyrolysis, various compounds of interest were formed, such as acetic acid, furfural, hydrogen, and levoglucosan.
The techno-economic assessment unveiled that the production of these compounds holds substantial market value, signifying potential profitability for catalytic fast pyrolysis. The study also highlighted CuO as the most suitable catalyst for the process, presenting the best results under the operational conditions used, and after admitting the contribution of each potential chemical product, the TEA balance showed a return of about USD 466.10 per ton of processed biomass.
Therefore, the results obtained in this work demonstrate that the catalytic fast pyrolysis of the Eucalyptus urograndis canopy can be a promising route for the production of bio-oil and high-value-added chemical compounds. Moreover, considering the positive techno-economic balance estimated, this technology can contribute to revenue generation from biomass processing, promoting sustainability and the use of renewable energy sources.
Studies are still necessary to separate and purify the chemical compounds produced. For hydrogen, methods such as membrane separation, absorption/desorption can be used, taking advantage of its permeability and condensability properties. Furfural can be purified by distillation, liquid-liquid extraction, and crystallization, while acetic acid can be separated by distillation, extraction, and crystallization. Levoglucosan, in turn, could be purified by chromatography, precipitation, and/or liquid-liquid extraction, aiming to achieve high levels of purity and yield of high-value-added chemicals.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/su16198294/s1, Figure S1: Representative pyrograms at 6″ and 350 °C from Eucalyptus urograndis treetop; Figure S2: Py-GC-MS chromatogram accomplished at pyrolysis time of 6″ for temperatures of 650, 550, 450, and 350 °C using nZVI as a catalyst from Eucalyptus urograndis forest residues; Figure S3: Py-GC-MS chromatogram accomplished at pyrolysis time of 6″ for temperatures of 650, 550, 450, and 350 °C using CoFe2O4 as a catalyst from Eucalyptus urograndis forest residues; Figure S4: Py-GC-MS chromatogram accomplished at pyrolysis time of 6″ for temperatures of 650, 550, 450, and 350 °C using TiO2 as a catalyst from Eucalyptus urograndis forest residues; Figure S5: Py-GC-MS chromatogram accomplished at pyrolysis time of 6″ for temperatures of 650, 550, 450, and 350 °C using CuO as a catalyst from Eucalyptus urograndis forest residues; Table S1: Main products produced by non-catalytic pyrolysis from Eucalyptus urograndis treetop; Table S2: Main products produced by catalytic pyrolysis from Eucalyptus urograndis treetop using CuO as a catalyst; Table S3: Market values of the main products obtained by catalytic pyrolysis from Eucalyptus urograndis treetop.

Author Contributions

Conceptualization, R.d.C.B., T.G., M.M.d.C. and A.M.M.L.C.; methodology, R.d.C.B., T.G., L.S.S., S.C.d.L.A., K.S.A. and V.O.d.P.B.; software, R.d.C.B. and T.G.; validation, R.d.C.B., T.G., M.M.d.C., L.S.S., S.C.d.L.A., K.S.A., V.O.d.P.B. and A.M.M.L.C.; formal analysis, R.d.C.B., T.G., L.S.S. and V.O.d.P.B.; investigation, R.d.C.B., T.G., M.M.d.C., L.S.S., S.C.d.L.A., K.S.A., V.O.d.P.B. and A.M.M.L.C.; resources, M.M.d.C. and A.M.M.L.C.; data curation, R.d.C.B., T.G., M.M.d.C., L.S.S., S.C.d.L.A., K.S.A., V.O.d.P.B. and A.M.M.L.C.; writing—original draft preparation, R.d.C.B., and T.G.; writing—review and editing, R.d.C.B., T.G., M.M.d.C., L.S.S., S.C.d.L.A., K.S.A., V.O.d.P.B. and A.M.M.L.C.; visualization, R.d.C.B., T.G., M.M.d.C., L.S.S., S.C.d.L.A., K.S.A., V.O.d.P.B. and A.M.M.L.C.; supervision, M.M.d.C. and A.M.M.L.C.; project administration, M.M.d.C. and A.M.M.L.C.; funding acquisition, M.M.d.C. and A.M.M.L.C. All authors have read and agreed to the published version of the manuscript.

Funding

The authors are thankful for the financial support provided by Fundação de Amparo à Pesquisa do Estado de Minas Gerais—Brazil (FAPEMIG), Conselho Nacional de Desenvolvimento Científico e Tecnológico—Brazil (CNPq/FAPEMIG agreement recorded in SICONV: 793988/2013 and INCT Midas) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil (CAPES—Finance Code 001). SAF is supported by research fellowships from CNPq.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are contained within the article and Supplementary Materials.

Acknowledgments

Laboratory Pulp and Paper (LCP-UFV).

Conflicts of Interest

The authors declare no conflicts of interest.

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Figure 1. Peak area percentage for the main products obtained from non-catalytic fast pyrolysis processes at different temperatures of the Eucalyptus urograndis canopy.
Figure 1. Peak area percentage for the main products obtained from non-catalytic fast pyrolysis processes at different temperatures of the Eucalyptus urograndis canopy.
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Figure 2. Peak area percentage for the main products obtained from catalytic fast pyrolysis processes using nZVI as a catalyst at different temperatures.
Figure 2. Peak area percentage for the main products obtained from catalytic fast pyrolysis processes using nZVI as a catalyst at different temperatures.
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Figure 3. Peak area percentage for the main products obtained from catalytic fast pyrolysis processes using CoFe₂O₄ as a catalyst at different temperatures.
Figure 3. Peak area percentage for the main products obtained from catalytic fast pyrolysis processes using CoFe₂O₄ as a catalyst at different temperatures.
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Figure 4. Peak area percentage for the main products obtained from catalytic fast pyrolysis processes using TiO₂ as a catalyst at different temperatures.
Figure 4. Peak area percentage for the main products obtained from catalytic fast pyrolysis processes using TiO₂ as a catalyst at different temperatures.
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Figure 5. Peak area percentage for the main products obtained in catalytic fast pyrolysis processes using CuO as a catalyst at different temperatures.
Figure 5. Peak area percentage for the main products obtained in catalytic fast pyrolysis processes using CuO as a catalyst at different temperatures.
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Figure 6. Peak areas of percentage formation of green chemicals obtained from catalytic fast pyrolysis processes using different catalysts and temperatures.
Figure 6. Peak areas of percentage formation of green chemicals obtained from catalytic fast pyrolysis processes using different catalysts and temperatures.
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Figure 7. Techno-economic assessment of green chemicals from the catalytic pyrolysis of the Eucalyptus urograndis canopy using CuO as a catalyst.
Figure 7. Techno-economic assessment of green chemicals from the catalytic pyrolysis of the Eucalyptus urograndis canopy using CuO as a catalyst.
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Table 1. Chemical characterization of the Eucalyptus urograndis canopy.
Table 1. Chemical characterization of the Eucalyptus urograndis canopy.
ParametersContent
Elemental analysis (%)Carbon50.2
Hydrogen6.34
Oxygen43.2
Nitrogen0.15
Sulfur0.11
Inorganics (%)0.78
HCl Insoluble (%)0.43
Metals (mg/kg)Ca1.90
Mg2.31
Fe0.51
Cu0.01
Mn1.36
Na4.61
K7.32
Lower heating value (LHV, MJ/kg)17.5
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Bittencourt, R.d.C.; Guimarães, T.; Costa, M.M.d.; Silva, L.S.; Barbosa, V.O.d.P.; Arêdes, S.C.d.L.; Alves, K.S.; Carvalho, A.M.M.L. Production of High-Value Green Chemicals via Catalytic Fast Pyrolysis of Eucalyptus urograndis Forest Residues. Sustainability 2024, 16, 8294. https://doi.org/10.3390/su16198294

AMA Style

Bittencourt RdC, Guimarães T, Costa MMd, Silva LS, Barbosa VOdP, Arêdes SCdL, Alves KS, Carvalho AMML. Production of High-Value Green Chemicals via Catalytic Fast Pyrolysis of Eucalyptus urograndis Forest Residues. Sustainability. 2024; 16(19):8294. https://doi.org/10.3390/su16198294

Chicago/Turabian Style

Bittencourt, Ricardo de C., Tiago Guimarães, Marcelo M. da Costa, Larissa S. Silva, Verônica O. de P. Barbosa, Stéphani Caroline de L. Arêdes, Krisnna S. Alves, and Ana Márcia M. L. Carvalho. 2024. "Production of High-Value Green Chemicals via Catalytic Fast Pyrolysis of Eucalyptus urograndis Forest Residues" Sustainability 16, no. 19: 8294. https://doi.org/10.3390/su16198294

APA Style

Bittencourt, R. d. C., Guimarães, T., Costa, M. M. d., Silva, L. S., Barbosa, V. O. d. P., Arêdes, S. C. d. L., Alves, K. S., & Carvalho, A. M. M. L. (2024). Production of High-Value Green Chemicals via Catalytic Fast Pyrolysis of Eucalyptus urograndis Forest Residues. Sustainability, 16(19), 8294. https://doi.org/10.3390/su16198294

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