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
The extraction, quantification and application of high-value biological compounds from olive oil processing waste
- Authors: Postma-Botha, Marthie
- Date: 2018
- Subjects: Organic compounds , Biochemistry , Biomass energy , Olive oil industry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34383 , vital:33371
- Description: Olive oil processing waste (pomace) as a by-product of the olive oil industry is regarded as a rich source of high-value biological compounds exhibiting antioxidant potential. The objective of the present work was to obtain a concentrated extract of high-value biological antioxidants from the pomace. The effect of extraction conditions on the concentration of the bioactive compounds in the extracts was investigated. The simultaneous recovery of both hydrophilic and lipophilic high-value biological compounds exhibiting antioxidant potential was achieved through a one-step extraction method under reduced pressure using a non-toxic solvent blend. A multilevel experimental design was implemented with the aim of optimising the recovery of selected compounds, namely, hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene from olive pomace by using solvent blends of n-heptane, d-limonene, ethanol and water. The factors considered were: extraction time, percentage composition of solvent blends and extraction temperature. The results suggested that a good recovery of the hydrophilic polyphenolic compounds, namely, hydroxytyrosol, tyrosol and oleuropein, as well as the lipophilic compounds, α-tocopherol and squalene may be achieved at a solvent temperature of 60°C at 400 mbar with a solvent blend of 30% n-heptane, 50% ethanol and 20% water and an extraction time of two hours. It was found that freeze-drying the pomace before extraction minimised production of artefacts, avoided degradation of biophenols, ensured long term stability of a reproducible sample and achieved better recovery of important hydrophilic and lipophilic bioactive compounds. Since the bioactive compounds are temperature sensitive, the extraction was performed under reduced pressure in order to reduce solvent reflux temperature and to improve extraction efficiency. The quantitative and qualitative determinations of the aforementioned high-value compounds were performed by high-performance liquid chromatography (HPLC), which revealed that the hydrophilic polyphenolic as well as the lipophilic α-tocopherol and squalene were present. In this study hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene were extracted from the pomace of two olive cultivars (Frantoio and Coratina). A comparison among the two cultivars showed quantitative differences between the two cultivars in all five high-value biological compounds and in the antioxidant capacity of the extracts evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2- picrylhydrazyl (DPPH) free radical. Coratina cultivar was found to have a significantly higher antioxidant capacity than Frantoio due to the much greater oleuropein content in the Coratina compared to the Frantoio although Frantoio had a significantly greater amount of hydroxytyrosol. The stability of olive waste extracts stored at four temperatures was also investigated and the results show that increased temperatures caused greater extent of degradation of both the hydrophilic polyphenolic and lipophilic compounds. The proposed optimum storage condition for the olive pomace extracts was found to be at 5°C in the absence of light. The extracts were incorporated into two cosmetic formulations and were found, from a stability study, to be stable at room temperature and optimally stable at 5°C in the absence of light.
- Full Text:
- Date Issued: 2018
- Authors: Postma-Botha, Marthie
- Date: 2018
- Subjects: Organic compounds , Biochemistry , Biomass energy , Olive oil industry
- Language: English
- Type: Thesis , Doctoral , DPhil
- Identifier: http://hdl.handle.net/10948/34383 , vital:33371
- Description: Olive oil processing waste (pomace) as a by-product of the olive oil industry is regarded as a rich source of high-value biological compounds exhibiting antioxidant potential. The objective of the present work was to obtain a concentrated extract of high-value biological antioxidants from the pomace. The effect of extraction conditions on the concentration of the bioactive compounds in the extracts was investigated. The simultaneous recovery of both hydrophilic and lipophilic high-value biological compounds exhibiting antioxidant potential was achieved through a one-step extraction method under reduced pressure using a non-toxic solvent blend. A multilevel experimental design was implemented with the aim of optimising the recovery of selected compounds, namely, hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene from olive pomace by using solvent blends of n-heptane, d-limonene, ethanol and water. The factors considered were: extraction time, percentage composition of solvent blends and extraction temperature. The results suggested that a good recovery of the hydrophilic polyphenolic compounds, namely, hydroxytyrosol, tyrosol and oleuropein, as well as the lipophilic compounds, α-tocopherol and squalene may be achieved at a solvent temperature of 60°C at 400 mbar with a solvent blend of 30% n-heptane, 50% ethanol and 20% water and an extraction time of two hours. It was found that freeze-drying the pomace before extraction minimised production of artefacts, avoided degradation of biophenols, ensured long term stability of a reproducible sample and achieved better recovery of important hydrophilic and lipophilic bioactive compounds. Since the bioactive compounds are temperature sensitive, the extraction was performed under reduced pressure in order to reduce solvent reflux temperature and to improve extraction efficiency. The quantitative and qualitative determinations of the aforementioned high-value compounds were performed by high-performance liquid chromatography (HPLC), which revealed that the hydrophilic polyphenolic as well as the lipophilic α-tocopherol and squalene were present. In this study hydroxytyrosol, tyrosol, oleuropein, α-tocopherol and squalene were extracted from the pomace of two olive cultivars (Frantoio and Coratina). A comparison among the two cultivars showed quantitative differences between the two cultivars in all five high-value biological compounds and in the antioxidant capacity of the extracts evaluated by measuring the radical scavenging effect on 1,1-diphenyl-2- picrylhydrazyl (DPPH) free radical. Coratina cultivar was found to have a significantly higher antioxidant capacity than Frantoio due to the much greater oleuropein content in the Coratina compared to the Frantoio although Frantoio had a significantly greater amount of hydroxytyrosol. The stability of olive waste extracts stored at four temperatures was also investigated and the results show that increased temperatures caused greater extent of degradation of both the hydrophilic polyphenolic and lipophilic compounds. The proposed optimum storage condition for the olive pomace extracts was found to be at 5°C in the absence of light. The extracts were incorporated into two cosmetic formulations and were found, from a stability study, to be stable at room temperature and optimally stable at 5°C in the absence of light.
- Full Text:
- Date Issued: 2018
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