Pyrolysis of algal biomass and coal in a rotary kiln reactor: Pyrolysis behaviour, product distribution and kinetic analysis
- Authors: Nyoni, Bothwell
- Date: 2023-12
- Subjects: Algal biofuels , Biomass energy , Coal -- South Africa
- Language: English
- Type: Doctorate theses , text
- Identifier: http://hdl.handle.net/10948/62550 , vital:72823
- Description: There are two primary reasons why the global economy is gradually reducing its dependence on coal as an energy source. Firstly, coal reserves are finite, and while some argue that current reserves will last for generations, the reality is that coal is a non-renewable resource. Secondly, the emissions associated with coal usage have adverse effects on both the environment and human health. While European countries have adopted seemingly aggressive strategies to replace coal and other fossil fuels, South Africa and other developing nations face economic constraints that limit such actions. Fortunately, there are more conservative approaches that can be employed, one of which involves a gradual introduction of renewable energy sources into the energy grid. Wind, solar, and biomass currently stand as the major renewable energy sources under consideration. However, it's worth noting that the intermittent nature of wind and solar energy production poses a significant challenge. Biomass holds the potential to replace coal in retrofitted coal-fired plants. However, the unchecked utilisation of biomass can lead to deforestation and have adverse effects on the human and animal food supply chain, as many essential food items are derived from plants. The debate over using biomass as a fuel source, especially when some types of biomasses can serve as food for humans and animals, has been a subject of ongoing discussion. Furthermore, biomass exhibits a lower energy density when compared to coal. Combustion stands as the primary technology for converting coal into energy and is widely used in most coal-based power plants. Gasification, on the other hand, has been employed for years in South Africa as a coal-to-liquids technology to supplement transportation fuel requirements and reduce reliance on crude oil imports. Pyrolysis, too, has found application as a key method for obtaining high-energy coal char, serving both as an energy source and a reducing agent in blast furnaces for the steelmaking industry. Pyrolysis technologies are gaining popularity in biomass-to-liquids processes due to their simplicity. Currently, there is growing research interest in simultaneous pyrolysis of coal and biomass. The study presented in this thesis focuses on investigating the pyrolysis of Scenedesmus algae biomass and low-grade coal in a small-scale rotary kiln, with particular emphasis on the synthesised liquid products. Algae represent a unique type of biomass that can be cultivated in photo-bioreactors with minimal use of agricultural land. This suggests significant potential for large-scale cultivation of algae, and ongoing efforts are exploring strategies for the mass production of algal biomass.Firstly, pyrolysis studies were carried out via thermogravimetric analysis instruments. It was revealed that because of algae’s considerably higher volatile content and lower carbon content when compared to coal, the pyrolysis process of algal biomass occurred at a faster rate. The highest pyrolytic reactivity of algae was 0.41 mg/min occurring at approximately 290 ᵒC in comparison with coal’s 0.06 mg/min occurring in the approximate temperature range of 550 – 600 ᵒC. The magnitude of the reactivity of the blends depended on the coal/algae ratios used. Furthermore, kinetics analysis revealed that the overall pyrolytic decomposition of coal followed 2nd order kinetics with an activation energy of 81.8 kJ/mol. The decomposition of algae and coal-algae blends occurred in two stages; the first stage decomposition followed 2nd order kinetics with activation energies in the range 130.3 – 145.5 kJ/mol. The second stage decomposition of algae followed 1st order kinetics with an activation energy of 27.3 kJ/mol, whilst coal-algae blends followed 2nd order decomposition with an activation energy range of 69.4 – 74.2 kJ/mol. Secondly, pyrolysis studies were carried out in a rotary kiln reactor wherefrom the char products were collected, and pyrolytic gases condensed to obtain pyroligneous liquid. It was found that the composition of oils synthesised from the pyrolysis of coal was rich in paraffins (52.6 % at 550 ᵒC), however the yield of oil from the pyrolysis of coal was low (6.9 %). Oils from algae and coal-algae blends were dominated by alcohols, fatty acids, fatty acid esters and poly-cyclic aromatic compounds. For example, the most abundant compounds in algae oil produced at 550 ᵒC were fatty acid esters (28.8 %), alcohols (17.6 %), fatty acids (10.8 %) and unsaturated aliphatics (10.7 %); the oil yield obtained from pyrolysis of algae was 40 %. The yields and composition of oils obtained from coal-algae blends were linked to individual contributions from coal and algae, especially at 550 ᵒC; however, the contributions were not proportional due to synergistic effects. This kind of study will contribute to the already existing but limited literature on coal-algae pyrolysis. Furthermore, this study demonstrates the potential of using low-grade coals (an abundant resource in Southern Africa) in conjunction with algal biomass (a renewable resource), in large-scale synthesis of liquid fuels and valuable chemicals via a simple pyrolysis process. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-12
- Authors: Nyoni, Bothwell
- Date: 2023-12
- Subjects: Algal biofuels , Biomass energy , Coal -- South Africa
- Language: English
- Type: Doctorate theses , text
- Identifier: http://hdl.handle.net/10948/62550 , vital:72823
- Description: There are two primary reasons why the global economy is gradually reducing its dependence on coal as an energy source. Firstly, coal reserves are finite, and while some argue that current reserves will last for generations, the reality is that coal is a non-renewable resource. Secondly, the emissions associated with coal usage have adverse effects on both the environment and human health. While European countries have adopted seemingly aggressive strategies to replace coal and other fossil fuels, South Africa and other developing nations face economic constraints that limit such actions. Fortunately, there are more conservative approaches that can be employed, one of which involves a gradual introduction of renewable energy sources into the energy grid. Wind, solar, and biomass currently stand as the major renewable energy sources under consideration. However, it's worth noting that the intermittent nature of wind and solar energy production poses a significant challenge. Biomass holds the potential to replace coal in retrofitted coal-fired plants. However, the unchecked utilisation of biomass can lead to deforestation and have adverse effects on the human and animal food supply chain, as many essential food items are derived from plants. The debate over using biomass as a fuel source, especially when some types of biomasses can serve as food for humans and animals, has been a subject of ongoing discussion. Furthermore, biomass exhibits a lower energy density when compared to coal. Combustion stands as the primary technology for converting coal into energy and is widely used in most coal-based power plants. Gasification, on the other hand, has been employed for years in South Africa as a coal-to-liquids technology to supplement transportation fuel requirements and reduce reliance on crude oil imports. Pyrolysis, too, has found application as a key method for obtaining high-energy coal char, serving both as an energy source and a reducing agent in blast furnaces for the steelmaking industry. Pyrolysis technologies are gaining popularity in biomass-to-liquids processes due to their simplicity. Currently, there is growing research interest in simultaneous pyrolysis of coal and biomass. The study presented in this thesis focuses on investigating the pyrolysis of Scenedesmus algae biomass and low-grade coal in a small-scale rotary kiln, with particular emphasis on the synthesised liquid products. Algae represent a unique type of biomass that can be cultivated in photo-bioreactors with minimal use of agricultural land. This suggests significant potential for large-scale cultivation of algae, and ongoing efforts are exploring strategies for the mass production of algal biomass.Firstly, pyrolysis studies were carried out via thermogravimetric analysis instruments. It was revealed that because of algae’s considerably higher volatile content and lower carbon content when compared to coal, the pyrolysis process of algal biomass occurred at a faster rate. The highest pyrolytic reactivity of algae was 0.41 mg/min occurring at approximately 290 ᵒC in comparison with coal’s 0.06 mg/min occurring in the approximate temperature range of 550 – 600 ᵒC. The magnitude of the reactivity of the blends depended on the coal/algae ratios used. Furthermore, kinetics analysis revealed that the overall pyrolytic decomposition of coal followed 2nd order kinetics with an activation energy of 81.8 kJ/mol. The decomposition of algae and coal-algae blends occurred in two stages; the first stage decomposition followed 2nd order kinetics with activation energies in the range 130.3 – 145.5 kJ/mol. The second stage decomposition of algae followed 1st order kinetics with an activation energy of 27.3 kJ/mol, whilst coal-algae blends followed 2nd order decomposition with an activation energy range of 69.4 – 74.2 kJ/mol. Secondly, pyrolysis studies were carried out in a rotary kiln reactor wherefrom the char products were collected, and pyrolytic gases condensed to obtain pyroligneous liquid. It was found that the composition of oils synthesised from the pyrolysis of coal was rich in paraffins (52.6 % at 550 ᵒC), however the yield of oil from the pyrolysis of coal was low (6.9 %). Oils from algae and coal-algae blends were dominated by alcohols, fatty acids, fatty acid esters and poly-cyclic aromatic compounds. For example, the most abundant compounds in algae oil produced at 550 ᵒC were fatty acid esters (28.8 %), alcohols (17.6 %), fatty acids (10.8 %) and unsaturated aliphatics (10.7 %); the oil yield obtained from pyrolysis of algae was 40 %. The yields and composition of oils obtained from coal-algae blends were linked to individual contributions from coal and algae, especially at 550 ᵒC; however, the contributions were not proportional due to synergistic effects. This kind of study will contribute to the already existing but limited literature on coal-algae pyrolysis. Furthermore, this study demonstrates the potential of using low-grade coals (an abundant resource in Southern Africa) in conjunction with algal biomass (a renewable resource), in large-scale synthesis of liquid fuels and valuable chemicals via a simple pyrolysis process. , Thesis (MSc) -- Faculty of Science, School of Biomolecular & Chemical Sciences, 2023
- Full Text:
- Date Issued: 2023-12
Investigation of the thermo-chemical behaviour of coal-algae agglomerates
- Authors: Baloyi, Hope
- Date: 2018
- Subjects: Biomass energy , Coal -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23913 , vital:30642
- Description: There is a growing research interest in the co-processing of biomass and coal, with the aim of addressing the negative attributes associated with the thermal processing of coal alone. Biomass feedstocks are regarded as a clean, renewable source, and the co-utilization of biomass feedstocks with coal is deemed to have a potential to reduce emission of pollutants (i.e. NOx and SOx) and volatile organic compounds (VOC’s). Moreover, biomass are thermally reactive and thus facilitate the conversion of coal during co-processing. Biomass material and coal are two autonomous fuel materials with different chemical characteristics and have a dissimilar thermal behaviour making it difficult to achieve chemical interaction between the two solid fuels to contribute to the formation of products. Coalgae® Technology developed at the Nelson Mandela University, involves the biological treatment of coal fines by adsorbing live microalgae biomass (in slurry form) onto waste coal fines to form coal-microalgae agglomerates. This new innovative approach seeks to integrate bio-based feedstock into coal thermal processing and to improve the utilization and thermal efficiency of coal fines as well as the interaction between the volatile components of biomass and coal during thermal processing (e.g. devolatilization), thereby overcoming some of the challenges that confront the co-processing of coal and biomass. Coal fines are low-ranked coals, generally characterized by high contents of sulphur, high ash yields, low calorific values and poor thermal reactivity, and these attributes limits the thermo-chemical processing of the coal fines. Therefore, this investigation was undertaken to assess the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorbing live microalgae slurry at varying ratios onto coal fines. For this purpose, the effects of adsorbing microalgae at varying ratios on the chemical characteristics and thermal behaviour of coal fines under pyrolytic conditions were investigated. The primary aim was to assess whether the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorption of live microalgae onto fine coal, is substantively modified compared to a simple additive model of the original coal and pre-dried microalgae biomass samples. Results obtained from the proximate analyses performed on an Eltra Thermo-gravimetric analyzer (TGA) thermostep, have shown that the adsorption of microalgae slurry onto coal fines does not possess greater influence in improving the yield of volatiles and ash in coal fines than can be expected from a simple additive model of the original raw materials. Based on the ultimate analyses results, it was found that the adsorption of microalgae slurry resulted in a systematic reduction in the sulphur content, a notable increase in the hydrogen and oxygen contents, however, no significant disparities were found between the measured ultimate properties of coal-microalgae agglomerates as compared to the theoretically-expected ultimate properties from a simple linear combination of parental coal and microalgae biomass. Assessment of the thermal behaviour of parental samples and coal-microalgae agglomerates involved the use non-isothermal (40-900ºC, 20 K/min) thermogravimetry under inert conditions. It was found that the adsorption of microalgae slurry onto coal fines resulted in an improved thermal reactivity of coal fines, although, did not affect the overall pyrolysis characteristics of the coal fines. Comparison of the thermal profiles (measured and calculated TG/DTG curves), revealed that the yield of volatile products during the pyrolysis of coal-microalgae blends do not exceed the expected volatile yields from a simple combination of coal and microalgae biomass. These results suggest that there was no positive or accelerative synergistic interaction between volatile components of adsorbed microalgae and coal fines during pyrolysis. Mild pyrolysis of raw coal and coal-microalgae performed in a fixed-bed reactor furnace (450ºC), resulted in improved yields of Fossil-Bio crude (FBC) oil (derived from coal-microalgae pyrolysis), at increased biomass ratio compared to coal tar. FBC Oil was found to contain relatively high contents of oxygen, hydrogen, and low sulphur content than coal tar. GC-MS analyses showed the presence of a heterocyclic compounds (i.e. Indole and 2, 6 dimethyl pyridine) in the FBC oil and these were not identified in the coal tar. Furthermore, high boiling compounds such as Flourene, pyrene and pentacosane were identified in the coal tar, however not identified in the FBC oil. Simulated distillation results showed notable differences between the FBC oil and coal tar in terms of the distribution of boiling point fractions particularly, high boing point components. Semi-devolatilized chars derived from coal-microalgae agglomerates showed substantial degree of decarboxylation and dehydrogenation compared to the coal chars.
- Full Text:
- Date Issued: 2018
- Authors: Baloyi, Hope
- Date: 2018
- Subjects: Biomass energy , Coal -- South Africa
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/23913 , vital:30642
- Description: There is a growing research interest in the co-processing of biomass and coal, with the aim of addressing the negative attributes associated with the thermal processing of coal alone. Biomass feedstocks are regarded as a clean, renewable source, and the co-utilization of biomass feedstocks with coal is deemed to have a potential to reduce emission of pollutants (i.e. NOx and SOx) and volatile organic compounds (VOC’s). Moreover, biomass are thermally reactive and thus facilitate the conversion of coal during co-processing. Biomass material and coal are two autonomous fuel materials with different chemical characteristics and have a dissimilar thermal behaviour making it difficult to achieve chemical interaction between the two solid fuels to contribute to the formation of products. Coalgae® Technology developed at the Nelson Mandela University, involves the biological treatment of coal fines by adsorbing live microalgae biomass (in slurry form) onto waste coal fines to form coal-microalgae agglomerates. This new innovative approach seeks to integrate bio-based feedstock into coal thermal processing and to improve the utilization and thermal efficiency of coal fines as well as the interaction between the volatile components of biomass and coal during thermal processing (e.g. devolatilization), thereby overcoming some of the challenges that confront the co-processing of coal and biomass. Coal fines are low-ranked coals, generally characterized by high contents of sulphur, high ash yields, low calorific values and poor thermal reactivity, and these attributes limits the thermo-chemical processing of the coal fines. Therefore, this investigation was undertaken to assess the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorbing live microalgae slurry at varying ratios onto coal fines. For this purpose, the effects of adsorbing microalgae at varying ratios on the chemical characteristics and thermal behaviour of coal fines under pyrolytic conditions were investigated. The primary aim was to assess whether the thermo-chemical behaviour of coal-microalgae agglomerates, formed by adsorption of live microalgae onto fine coal, is substantively modified compared to a simple additive model of the original coal and pre-dried microalgae biomass samples. Results obtained from the proximate analyses performed on an Eltra Thermo-gravimetric analyzer (TGA) thermostep, have shown that the adsorption of microalgae slurry onto coal fines does not possess greater influence in improving the yield of volatiles and ash in coal fines than can be expected from a simple additive model of the original raw materials. Based on the ultimate analyses results, it was found that the adsorption of microalgae slurry resulted in a systematic reduction in the sulphur content, a notable increase in the hydrogen and oxygen contents, however, no significant disparities were found between the measured ultimate properties of coal-microalgae agglomerates as compared to the theoretically-expected ultimate properties from a simple linear combination of parental coal and microalgae biomass. Assessment of the thermal behaviour of parental samples and coal-microalgae agglomerates involved the use non-isothermal (40-900ºC, 20 K/min) thermogravimetry under inert conditions. It was found that the adsorption of microalgae slurry onto coal fines resulted in an improved thermal reactivity of coal fines, although, did not affect the overall pyrolysis characteristics of the coal fines. Comparison of the thermal profiles (measured and calculated TG/DTG curves), revealed that the yield of volatile products during the pyrolysis of coal-microalgae blends do not exceed the expected volatile yields from a simple combination of coal and microalgae biomass. These results suggest that there was no positive or accelerative synergistic interaction between volatile components of adsorbed microalgae and coal fines during pyrolysis. Mild pyrolysis of raw coal and coal-microalgae performed in a fixed-bed reactor furnace (450ºC), resulted in improved yields of Fossil-Bio crude (FBC) oil (derived from coal-microalgae pyrolysis), at increased biomass ratio compared to coal tar. FBC Oil was found to contain relatively high contents of oxygen, hydrogen, and low sulphur content than coal tar. GC-MS analyses showed the presence of a heterocyclic compounds (i.e. Indole and 2, 6 dimethyl pyridine) in the FBC oil and these were not identified in the coal tar. Furthermore, high boiling compounds such as Flourene, pyrene and pentacosane were identified in the coal tar, however not identified in the FBC oil. Simulated distillation results showed notable differences between the FBC oil and coal tar in terms of the distribution of boiling point fractions particularly, high boing point components. Semi-devolatilized chars derived from coal-microalgae agglomerates showed substantial degree of decarboxylation and dehydrogenation compared to the coal chars.
- Full Text:
- Date Issued: 2018
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