Torrefaction as a Pretreatment Technology for Chlorine Elimination from Biomass: A Case Study Using Eucalyptus globulus Labill
Abstract
:1. Introduction
2. State-Of-The-Art
2.1. Biomass
2.2. Biomass Thermochemical Conversion
2.2.1. Torrefaction Process
- Initial heating: The temperature of the biomass starts to increase and moisture starts to evaporate in the end.
- Pre-drying: It occurs at approximately 100 °C and, during this stage, free water present in biomass evaporates at a constant rate.
- Post-drying and intermediate heating: The temperature of the biomass increases to 200 °C. At this stage, biomass releases water present in its chemical bonds, practically eliminating all the moisture. Due to the evaporation of light organic compounds, some mass loss can occur.
- Torrefaction: This is the stage where the biomass is torrefied. It happens during the time in which the temperature is superior to 200 °C, or 220 °C as previously mentioned, and consists of a heating period, a constant temperature period, and a cooling period. Mass loss starts during the first and stops after the latter. The maximum constant temperature reached is known as the torrefaction temperature (TTor).
- Solids cooling: The torrefied biomass cools further until it reaches room temperature.
2.2.2. Torrefaction Parameters
- Temperature and residence time: They are crucial to understand how the exposure of biomass to high temperatures affects its structure since it generally results in mass loss. The temperature attained and its duration influence the degree of thermal degradation. Regarding residence time, previous studies commented the importance of replacing this term with reaction time since the former mainly influences the degradation of hemicellulose, while the latter affects the cellulose mass loss [65,66]. As mentioned, the torrefaction process has several heating stages, even before torrefaction starts. Therefore, residence time does not represent biomass exposure to torrefaction. When comparing the effects of temperature and residence time on the characteristics of the final product, it is important to mention that both are connected and dependent on each other, even though temperature has a more significant influence since it defines the kinetics of the reaction.
- Heating rate: The heating rate (°C/min) chosen during torrefaction affects solid, liquid, and gaseous portions in the final product, since it influences secondary degradation reactions. The use of high heating rates reduces parallel reactions, which impacts the distribution of the products. A recent study suggested that the effects of heat and mass transfer in the particles decrease by increasing the heating rate [67].
- Atmosphere composition: The torrefaction process can be affected by the gas flow used during the process due to the secondary interactions between the gases. Carbon monoxide is the main gas released in the process, occurring through a secondary reaction as the temperature increases. Furthermore, the longer is the residence time, the lower is the CO2/CO ratio. There are no substantial changes in biomass reactivity or in the solid reaction products depending on the presence of O2 in the atmosphere.
- Reactor type: Besides being a relatively new technology, there are several reactors available in the market [68,69]. Reactor design is the main difference between the technologies, each one with its heat transfer method and mixing pattern, determining product quality. The most commonly used technologies are the rotatory drum kiln, which is indirectly heated (through the reactor wall) and the rotary drum reactor, which is directly heated [70].
2.2.3. Torrefied Biomass Properties
- Moisture content: Before torrefaction process, moisture content in raw biomass ranges from 10% to 50%, but, by the end, it reaches 1–3% due to the high temperatures obtained during the process. This reduction contributes to many improvements, such as a lower transportation cost since there is no unwanted water in the product, simplified storage, transportation given by its new hydrophobicity, and better performance during the subsequent conversion process due to a higher heating value.
- Energy and bulk density: The torrefaction process results in loss of mass in different states, which leads to an increase in biomass porosity. As a result, both volumetric and bulk densities decrease, even though several studies have shown a substantial increase of more than 50% in energy density [72].
- Grindability: Biomass is naturally fibrous and tenacious. During torrefaction, structural changes decrease the length of the fibers, making it weaker. This modification favors the utilization of biomass alongside coal in processes such as co-firing and co-gasification, since solid fuel is now easily ground. Apart from that, energy consumption during grinding decreases significantly, with some studies observing reductions of 70–90% [73].
- Heating value: The torrefaction process increases the carbon content, while the oxygen and hydrogen content of the biomass decrease with increasing temperature. The amount of carbon lost during the process is lower than the loss of other components, which leads to a higher heating value when compared to raw biomass. This increase results in better combustion characteristics and approaches properties of torrefied biomass to those of coal.
2.3. Soil and Nutrient Depletion
2.4. Forest Typology of Mainland Portugal
- Pine forests are the second largest forest formation, but had a more considerable reduction in the occupied area.
- Evergreen broadleaves are cork oak and holm oak and represent about 1/3 of the forest.
- Deciduous hardwoods composed of oaks, chestnut trees, and others are the least representative forest formation concerning the occupied area.
- Industrial broadleaf forests are composed by eucalyptus, which showed an increment in occupied area over the last 50 years, representing about 26% of the mainland forest.
2.5. Eucalyptus
3. Materials and Methods
3.1. Materials
3.2. Torrefaction Process
3.2.1. Sample Selection and Preparation
3.2.2. Torrefaction Procedure
3.2.3. Torrefaction Parameters
3.3. Laboratorial Characterization of the Samples
3.3.1. Initial Moisture Content
3.3.2. Chlorine Content
3.3.3. Major and Minor Elements Analysis
3.3.4. Elemental Analysis
3.3.5. Proximate Analysis
3.3.6. Heating Value
3.3.7. Energy Density and Mass and Energy Yield
4. Results and Discussion
4.1. Mass Distribution and Initial Moisture Content
4.2. Chlorine Content
4.3. Elemental Analysis
4.4. Proximate Analysis
4.5. Heating Value
4.6. Energy Density and Mass and Energy Yield
5. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Stages | Torrefaction Steps | Temperature (°C) | Residence Time (min) |
---|---|---|---|
1 | Initial heating/pre-drying | Troom–T1 | t1 |
2 | Post-drying and intermediate heating | T1–T2 | t2 |
3 | Torrefaction | T2 | t3 |
4 | Solids cooling | T2–50 °C | t4 |
Torrefaction | tR (min) | T1 (°C) | T2 (°C) |
---|---|---|---|
Tor 1 | 60 | 150 | 240 |
Tor 2 | 90 | ||
Tor 3 | 120 | ||
Tor 4 | 60 | 175 | 280 |
Tor 5 | 90 | ||
Tor 6 | 120 | ||
Tor 7 | 60 | 200 | 320 |
Tor 8 | 90 | ||
Tor 9 | 120 |
Tree | Trunk (%) | Bark (%) | Leaves (%) |
---|---|---|---|
1 | 54.71 | 63.75 | 47.30 |
2 | 54.71 | 63.75 | 47.30 |
3 | 41.74 | 55.27 | 41.10 |
4 | 45.51 | 52.01 | 40.88 |
5 | 50.08 | 63.23 | 49.63 |
6 | 53.32 | 62.50 | 51.52 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Raw biomass | 1 | 56.93 | 5.76 | 0.39 | 0.01 | 0.05 | 36.86 |
2 | 57.87 | 5.88 | 0.23 | 0.00 | 0.03 | 35.99 | |
3 | 57.75 | 5.85 | 0.19 | 0.01 | 0.04 | 36.17 | |
4 | 58.03 | 5.88 | 0.15 | 0.00 | 0.03 | 35.91 | |
5 | 56.62 | 5.78 | 0.22 | 0.00 | 0.03 | 37.35 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 1 | 1 | 65.08 | 5.18 | 0.26 | 0.00 | 0.00 | 29.48 |
2 | 62.49 | 5.23 | 0.16 | 0.00 | 0.00 | 32.12 | |
3 | 64.04 | 5.25 | 0.19 | 0.00 | 0.00 | 30.52 | |
4 | 62.73 | 5.28 | 0.15 | 0.00 | 0.00 | 31.84 | |
5 | 65.02 | 5.14 | 0.16 | 0.00 | 0.00 | 29.68 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 2 | 1 | 72.27 | 4.95 | 0.28 | 0.00 | 0.00 | 22.50 |
2 | 67.59 | 5.12 | 0.19 | 0.00 | 0.00 | 27.10 | |
3 | 69.56 | 5.06 | 0.20 | 0.00 | 0.00 | 25.18 | |
4 | 67.48 | 5.19 | 0.19 | 0.00 | 0.00 | 27.14 | |
5 | 68.92 | 5.03 | 0.20 | 0.00 | 0.00 | 25.85 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 3 | 1 | 72.30 | 5.02 | 0.34 | 0.00 | 0.00 | 22.34 |
2 | 68.31 | 5.32 | 0.20 | 0.00 | 0.00 | 26.17 | |
3 | 72.37 | 5.05 | 0.19 | 0.00 | 0.00 | 22.39 | |
4 | 69.35 | 5.25 | 0.16 | 0.00 | 0.00 | 25.24 | |
5 | 74.25 | 4.84 | 0.21 | 0.00 | 0.00 | 20.70 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 4 | 1 | 64.48 | 5.20 | 0.26 | 0.00 | 0.00 | 30.06 |
2 | 62.10 | 5.30 | 0.16 | 0.00 | 0.00 | 32.44 | |
3 | 64.41 | 5.16 | 0.17 | 0.00 | 0.00 | 30.26 | |
4 | 63.20 | 5.29 | 0.13 | 0.00 | 0.00 | 31.38 | |
5 | 64.18 | 5.22 | 0.15 | 0.00 | 0.00 | 30.45 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 5 | 1 | 72.97 | 4.99 | 0.30 | 0.00 | 0.00 | 21.74 |
2 | 64.06 | 5.48 | 0.14 | 0.00 | 0.00 | 30.32 | |
3 | 66.93 | 5.29 | 0.18 | 0.00 | 0.00 | 27.60 | |
4 | 66.12 | 5.43 | 0.16 | 0.00 | 0.00 | 28.29 | |
5 | 66.87 | 5.29 | 0.18 | 0.00 | 0.00 | 27.66 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 6 | 1 | 78.42 | 4.22 | 0.35 | 0.00 | 0.00 | 17.01 |
2 | 68.64 | 5.05 | 0.19 | 0.00 | 0.00 | 26.12 | |
3 | 72.04 | 4.95 | 0.19 | 0.00 | 0.00 | 22.82 | |
4 | 70.25 | 4.95 | 0.16 | 0.00 | 0.00 | 24.64 | |
5 | 70.62 | 5.01 | 0.20 | 0.00 | 0.00 | 24.17 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 7 | 1 | 92.76 | 2.72 | 0.39 | 0.00 | 0.00 | 4.13 |
2 | 89.95 | 2.75 | 0.29 | 0.00 | 0.00 | 7.01 | |
3 | 89.94 | 2.74 | 0.25 | 0.00 | 0.00 | 7.07 | |
4 | 90.19 | 3.00 | 0.24 | 0.00 | 0.00 | 6.57 | |
5 | 90.94 | 2.85 | 0.24 | 0.00 | 0.00 | 5.97 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 8 | 1 | 94.31 | 2.70 | 0.47 | 0.00 | 0.00 | 2.52 |
2 | 91.05 | 2.57 | 0.22 | 0.00 | 0.00 | 6.16 | |
3 | 93.07 | 2.74 | 0.23 | 0.00 | 0.00 | 3.96 | |
4 | 91.44 | 2.34 | 0.16 | 0.00 | 0.00 | 6.06 | |
5 | 92.40 | 2.56 | 0.24 | 0.00 | 0.00 | 4.80 |
Test | Sample | CHN (%) | S (%) | Cl (%) | O (%) | ||
---|---|---|---|---|---|---|---|
C | H | N | |||||
Torr 9 | 1 | 93.61 | 2.85 | 0.39 | 0.00 | 0.00 | 3.15 |
2 | 96.40 | 2.44 | 0.29 | 0.00 | 0.00 | 0.87 | |
3 | 92.59 | 2.96 | 0.33 | 0.00 | 0.00 | 4.12 | |
4 | 91.04 | 2.75 | 0.24 | 0.00 | 0.00 | 5.97 | |
5 | 91.58 | 2.52 | 0.24 | 0.00 | 0.00 | 5.66 |
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Sá, L.C.R.; Loureiro, L.M.E.F.; Nunes, L.J.R.; Mendes, A.M.M. Torrefaction as a Pretreatment Technology for Chlorine Elimination from Biomass: A Case Study Using Eucalyptus globulus Labill. Resources 2020, 9, 54. https://doi.org/10.3390/resources9050054
Sá LCR, Loureiro LMEF, Nunes LJR, Mendes AMM. Torrefaction as a Pretreatment Technology for Chlorine Elimination from Biomass: A Case Study Using Eucalyptus globulus Labill. Resources. 2020; 9(5):54. https://doi.org/10.3390/resources9050054
Chicago/Turabian StyleSá, Letícia C. R., Liliana M. E. F. Loureiro, Leonel J. R. Nunes, and Adélio M. M. Mendes. 2020. "Torrefaction as a Pretreatment Technology for Chlorine Elimination from Biomass: A Case Study Using Eucalyptus globulus Labill" Resources 9, no. 5: 54. https://doi.org/10.3390/resources9050054