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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
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  • Date Issued: 2023-12

Investigation of brewery waste grains and microbial fuel cells as value-additive technologies improving solvent production yields in Clostridium acetobutylicum (ATCC 824) fermentation

  • Authors: Du Toit, Ryan Guillaume
  • Date: 2023-10-13
  • Subjects: Biomass energy , Butanol , Fermentation , Microbial fuel cells , Brewery waste , Clostridium acetobutylicum
  • Language: English
  • Type: Academic theses , Master's theses , text
  • Identifier: http://hdl.handle.net/10962/424643 , vital:72171
  • Description: The production of the solvent compounds acetone, ethanol and butanol through fermentation of organic feedstocks using Clostridia species could be a promising route for biofuel production. However, the cost of raw materials, low yields and the complexity of anaerobic fermentation continue to hinder this means of generating these compounds. The research presented in this Thesis investigated low-cost interventions that could decrease the costs of production and to direct the synthesis of fuel compounds using microbial fuel cells. Low-cost anaerobic chambers were designed and constructed for the propagation and manipulation of Clostridium acetobutylicum, selected as a low-risk microbial catalyst. Fermentation was monitored using in situ pH measurements and a combination of turbidity measurements, nutrient assays (especially total carbohydrates) and HPLC-RI detection as a means of monitoring the consumption of nutrients (glucose), production of precursor compounds (butyric acid) and the formation of solvent molecules (acetone/ethanol and butanol) during fermentation by this organism. Brewer’s spent grains were tested as a sustainable and low-cost feedstock for solvent production, comparing the effects of sterilising before fermentation, or allowing resident microflora to remain during Clostridium-catalysed solvent production. Sterilised spent grains significantly improved the production of solvent molecules (e.g. 12.97 ± 0.38 g/L of butanol yielded, compared to 0.40 ± 0.33 g/L for defined media sampled during the solventogenic phase); compared to these, the use of non-sterilised brewer’s grain decreased both the reproducibility and yields of fermentation (8.66 ± 1.6 g/L of butanol). Microbial fuel cells were studied as a possible means of altering electron transfer to/from electrode-attached Clostridia to control the metabolic shift in bacteria from acidogenesis to solventogenesis. The base line MFC (11.00 ± 4.69 g/L) fermentation experiment did produce higher acetone/ethanol than the baseline batch experiment MB (5.47 ± 4.48 g/L), indicating an improvement to solvent production in C. acetobutylicum (ATCC 824) in a MFC fermentation. In this study, MFC-1 demonstrated remarkable superiority over MB in terms of butyric acid production, yielding significantly higher concentrations while also improving acetone and ethanol production. However, the enhanced butyric acid production did not correspond to significantly increased butanol yields when compared to batch fermentation of chemically defined media. These findings highlight the potential of MFC-1 as an efficient approach for enhancing the fermentative production of valuable compounds, with a particular focus on butyric acid and acetone/ethanol. , Thesis (MSc) -- Faculty of Science, Biotechnology Innovation Centre, 2023
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  • Date Issued: 2023-10-13

The quantification of Pinus patula recovery and productivity of manually orientated biomass collection in post mechanised full tree and semi mechanised tree length harvesting operations

  • Authors: Ncongwane, Thandekile Hazel
  • Date: 2023-04
  • Subjects: Pinus patula – south Africa , Forest ecology , Biomass energy
  • Language: English
  • Type: Master's theses , text
  • Identifier: http://hdl.handle.net/10948/61511 , vital:70692
  • Description: The use of biomass as an alternate source of energy has grown in popularity. Different types of biomass are obtained from a variety of sources including natural forests, forestry plantations and agriculture residues. However, forestry residues have been identified as the most promising source, due to the wide variety of plant products including leaves, twigs, branches, merchantable stem, stumps and roots. The main sources of plantation forest biomass are residues from thinning, clearfell and conventional products such as pulpwood and sawn timber operations. These residues can accumulate between 4.3 to 9.4 billion tonnes annually around the world. The biomass availability in plantation forests has led to the development of different harvesting systems to help collect the products from infield to sawmill. Biomass harvesting has mainly been achieved through mechanised systems because of their high yields. However, the use of manual systems has been neglected due to technical limitations and financial viability. Thus, in South Africa, there is no scientific research looking at manual systems of collecting biomass from plantations. Because of this, different forestry stakeholders, including small growers and contractors using manual systems for biomass harvesting have limited knowledge regarding what to expect in terms of recoverable amounts, productivity and cost. This research examines the productivity of the manual biomass collection and the quantification of recovered and unrecovered residues after mechanised full tree (FT) and semi mechanised tree length (TL) harvesting operations in Pinus patula compartments. A total number of 8 plots with +/-200 standing trees were marked in each system. The diameter and height of all marked trees were measured to determine tree volume. Moreover, the quantification of recoverable woody biomass was determined, where after, a residues assessment method using plots and line transects was used to determine the amount of unrecovered residues. , Thesis (MSc) -- Faculty of Science, School of Environmental Sciences, 2023
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  • Date Issued: 2023-04

Nutrient removal and biofuel potential of MaB-floc biomass from an integrated algal pond system treating domestic sewage

  • Authors: Sibelo, Linda
  • Date: 2020
  • Subjects: Biomass energy , Waste products as fuel , Algal biofuels , Sewage -- Purification -- Nutrient removal
  • Language: English
  • Type: text , Thesis , Masters , MSc
  • Identifier: http://hdl.handle.net/10962/144955 , vital:38395
  • Description: Integrated algal pond systems (IAPS) are a passive water treatment technology derived from the Oswald designed advanced integrated wastewater pond systems (AIWPS®) and effect wastewater treatment based on biological activity of microorganisms within the system, solar energy and gravity. The technology consists of an advanced facultative pond (AFP), a series of interconnected high rate algal oxidation ponds (HRAOP) and algal settling ponds. The symbiotic relationship between microalgae and bacteria facilitated by paddlewheel mixing of HRAOP results in the formation of biomass aggregates known as MaB-flocs. MaB-floc formation enhances nutrient abstraction, gravitational sedimentation and separation from water hence forming two product streams; recyclable water and biomass, both with valorisation potential. This work aimed to determine the suitability of MaB-floc biomass generated in the HRAOP of an IAPS treating domestic sewage as feedstock for biofuel production based on the content of carbohydrate and lipid. Nutrient removal efficiency, biomass productivity and bulk lipid and carbohydrate concentration were monitored for two consecutive three-month periods in the winter and summer seasons of 2018/19. Maximum removal efficiencies of nitrogen and phosphorus were determined as 71% and 75% respectively, demonstrating the efficiency of IAPS as a wastewater treatment technology. MaB-floc biomass productivity in winter and summer was 9.4 g/m2/d and 16.5 g/m2/d respectively indicating the heavy influence of seasonal temperature, possibly day length, and solar irradiation on biomass productivity in the HRAOP. Summer productivity was lower than the maximum theoretical productivity of 25 g/m2/d possibly due to photoinhibition of photosynthesis as well as grazing pressures caused by the proliferation of rotifers mainly of the Brachionus genus. MaB-floc biomass consistently contained higher amounts of carbohydrate than lipid despite the changes in species dominance from Scenedesmus sp. and Desmodesmus sp. in winter to Pediastrum sp. in summer. Variations in MaB-floc biomass carbohydrate content were linked to changes in nitrogen concentration, mainly in the form of nitrates. Lower nitrogen concentration significantly increased the carbohydrate content of MaB-floc biomass from 17.5 ± 0.15% to 33.5 ± 0.3 % recorded in summer. In winter, biomass carbohydrate increased from 18.3 ± 1.2% to 35.8 ± 0.3%.To induce accumulation of carbohydrates through nitrogen starvation, isolated microalgal species native to the HRAOPs of the IAPS at Institute for Environmental Biotechnology Rhodes University(EBRU) were used. The outcome from the laboratory studies showed that carbon partitioning within isolated strains could be altered from carbohydrate to lipid which is more energy-rich. Hence, exploring the biodiesel production option using HRAOP MaB-floc biomass, which had a lipid content ranging between 12.1 ± 0.64 % and 13.9 ± 0.5 %, would require a preconditioning step in the form of nitrogen starvation to enhance its lipid content. Overall, the outcome of outdoor monitoring studies on biomass biochemical composition indicated that HRAOPs operating under natural environmental conditions preferentially generated a biomass rich in carbohydrate. Therefore, anaerobic digestion may be a more viable option for HRAOP MaB-floc biomass because of the high carbohydrate levels ranging between 24.9 ± 0.6 % and 25.6 ± 1.3 % of the dry MaB-floc biomass weight. Despite the low biomass C/N ratio (7.1 to 7.8), the MaB-floc biomass can be anaerobically co-digested with a higher C/N ratio (24) substrate such as in-pond digester sludge, to improve methane yields calculated to be between 0.31 m3 CH4/ kg MaB-floc biomass and 0.33 m3 CH4/ kg MaB-floc biomass. Anaerobic digestion of biomass also produces CO2 which can be recovered and added to HRAOPs to enhance MaB-floc biomass productivity while lowering greenhouse gas emissions from a wastewater treatment plant. The digestate from the anaerobic process, which is rich in nitrogen and phosphorus can be used as a biofertiliser. Thus, a potential MaB-floc biomass biorefinery consisting of biogas and bio-fertiliser pathways can be established using IAPS treating sewage as the platform technology. IAPS is a system designed to operate in a way that is passive and without substantial environmental impact but technological innovations and a reduction in the size of the system are required to make the technology more acceptable.
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  • Date Issued: 2020

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.
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  • 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.
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  • Date Issued: 2018

Evaluation of cellulase and xylanase production by two actinobacteria species belonging to the Micrococcus genus isolated from decaying lignocellulosic biomass

  • Authors: Mmango-Kaseke, Ziyanda https://orcid.org/0000-0002-8936-1149
  • Date: 2016-05
  • Subjects: Lignocellulose , Biomass energy
  • Language: English
  • Type: Master's theses , text
  • Identifier: http://hdl.handle.net/10353/24197 , vital:62442
  • Description: Bacteria were isolated from sawdust and screened for cellulase and xylanase production on carboxyl methyl cellulose (CMC) and birchwood xylan agar. The bacteria showing halo forms around the colony were selected for further analyses and those isolates with the highest cumulative halozone size (isolate PLY1 and MLY10) were chosen for detailed studies. Evaluation of cellulase and xylanase production by saw dust actinobacterial species whose 16S rDNA nucleotide sequences were deposited in GenBank as Micrococcus luteus strain SAMRC-UFH3 with accession number KU171371 and Micrococcus yunnanensis strain SAMRC-UFH4 with accession number KU171372. Optimum culture conditions for the production of cellulase for respective axenic culture include incubation period (96 h), incubation temperature (25oC), agitation speed (50 rpm), and pH 5. For xylanase production, the optimum culture conditions in the presence of 1percent (w/v) birchwood xylan include incubation period (84 h), incubation temperature (25oC), agitation speed (200 rpm), and pH 10. For Micrococcus yunnanensis strain SAMRC-UFH4 cellulase production was optimal under such conditions as, incubation temperature (30oC), agitation speed (0 rpm), and pH 5, while xylanase production was optimal at, incubation temperature (30oC), agitation speed (150 rpm), and pH 10. The high cellulase and xylanase activity obtained from these isolates suggest suitability of the organisms as important candidates for commercial application. , Thesis (MSc) -- Faculty of Science and Agriculture, 2016
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  • Date Issued: 2016-05

An investigation into the synergistic action of cellulose-degrading enzymes on complex substrates

Hydrothermal co-liquefaction of microalgae biomass and coal

  • Authors: Charlie, David
  • Date: 2015
  • Subjects: Microalgae -- Biotechnology Biomass chemicals , Biomass energy
  • Language: English
  • Type: Thesis , Masters , MTech
  • Identifier: http://hdl.handle.net/10948/50087 , vital:42035
  • Description: In this research, the objective was to investigate under the chosen liquefaction conditions whether co-liquefaction of coal and microalgae biomass as agglomerates does possess a distinct advantage over the individual liquefaction of microalgae and coal. This was initially done by preparing dry micro algal biomass, followed by the preparation of coal fines and finally coal-algae as agglomerates. The agglomerates were prepared by continuously adsorbing wet concentrated microalgae slurry/solution onto the dry coal fines in order to prepare different ratios of coal-algae agglomerate(s). Ultimate analysis of the starting material (coal fines and the microalgae) as well the agglomerates then followed. According to research, wet microalgae biomass has the potential of acting as a hydrogen donor. By preparing the agglomerates, the rationale was to promote hydrogen supply from the micro algal biomass that has high hydrogen content to the coal with lower hydrogen content. The resulting product was then expected to have fairly higher hydrogen content. However, this was not observed or evident from the elemental analysis results. The results (elemental composition) showed no difference between the agglomerates and the coal. Based on the observed ultimate analysis results, liquefaction experiments were conducted to determine whether hydrogen transfer and the expected synergistic effect between micro algal biomass and coal would occur. The crude oil product was recovered and simulated distillation technique was used for the characterization of the crude oil product. The results we in agreement that higher yields can be achieved during co-liquefaction as compared to the individual liquefaction. A possible synergistic effect that was investigated in this research existed. Liquefaction results provided evidence of higher yields recovery from the agglomerates compared to those of coal fines and microalgae biomass. Although there was higher recovery on the agglomerates, there appears to be a downward trend (decrease) in product recovery with higher loadings of micro algal biomass on to the coal. This means that higher loading of micro algal biomass tend to suppress liquefaction of coal, thus resulting in lower product recovery. While lower loadings tend to effectively facilitate the liquefaction of coal, thus proving that the proposed synergistic effect between the two does exist. Overall product recovery (yields) of the agglomerates is higher compared to the individual recovery of coal fines and microalgae biomass. This was followed by mass balancing to determine the overall conversion. Higher conversions were achieved on the agglomerates compared to coal. This could mean that microalgae have the potential to facilitate the liquefaction of coal and improve its conversion. The observed trend results in improved conversion as well as higher oil yields (simulated distillation results). Overall, the mass balancing provided insightful information regarding the coal-microalgae interaction based on the conversion, and this further corresponds or supports the simulated distillation results. This research paper provides evidence of the synergistic effect that exists between micro algal biomass and coal.
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  • Date Issued: 2015

The effect of GH family affiliations of mannanolytic enzymes on their synergistic associations during the hydrolysis of mannan-containing substrates

A lignocellulolytic enzyme system for fruit waste degradation : commercial enzyme mixture synergy and bioreactor design

  • Authors: Gama, Repson
  • Date: 2014
  • Subjects: Enzymes -- Biotechnology , Enzymes -- Industrial applications , Lignocellulose -- Biodegradation , Biomass energy , Biomass conversion , Biochemical engineering , Agricultural wastes as fuel
  • Language: English
  • Type: Thesis , Doctoral , PhD
  • Identifier: vital:4114 , http://hdl.handle.net/10962/d1013073
  • Description: Studies into sources of alternative liquid transport fuel energy have identified agro-industrial wastes, which are lignocellulosic in nature, as a potential feedstock for biofuel production against the background of depleting nonrenewable fossil fuels. In South Africa, large quantities of apple and other fruit wastes, called pomace, are generated from fruit and juice industries. Apple pomace is a rich source of cellulose, pectin and hemicellulose, making it a potential target for utilisation as a lignocellulosic feedstock for biofuel and biorefinery chemical production. Lignocellulosic biomass is recalcitrant in nature and therefore its degradation requires the synergistic action of a number of enzymes such as cellulases, hemicellulases, pectinases and ligninases. Commercial enzyme cocktails, containing some of these enzymes, are available and can be used for apple pomace degradation. In this study, the degradation of apple pomace using commercial enzyme cocktails was investigated. The main focus was the optimisation of the release of sugar monomers that could potentially be used for biofuel and biorefinery chemical production. There is no or little information reported in literature on the enzymatic degradation of fruit waste using commercial enzyme mixtures. This study first focused on the characterisation of the substrate (apple pomace) and the commercial enzyme cocktails. Apple pomace was found to contain mainly glucose, galacturonic acid, arabinose, galactose, lignin and low amounts of xylose and fructose. Three commercial enzyme cocktails were initially selected: Biocip Membrane, Viscozyme L (from Aspergillus aculeatus) and Celluclast 1.5L (a Trichoderma reesei ATCC 26921 cellulase preparation). The selection of the enzymes was based on activities declared by the manufacturers, cost and local availability. The enzymes were screened based on their synergistic cooperation in the degradation of apple pomace and the main enzymes present in each cocktail. Viscozyme L and Celluclast 1.5L, in a 50:50 ratio, resulted in the best degree of synergy (1.6) compared to any other combination. The enzyme ratios were determined on Viscozyme L and Celluclast 1.5L based on the protein ratio. Enzyme activity was determined as glucose equivalents using the dinitrosalicylic acid (DNS) method. Sugar monomers were determined using Megazyme assay kits. There is limited information available on the enzymes present in the commercial enzyme cocktails. Therefore, the main enzymes present in Viscozyme L and Celluclast 1.5L were identified using different substrates, each targeted for a specific enzyme and activity. Characterisation of the enzyme mixtures revealed a large number of enzymes required for apple pomace degradation and these included cellulases, pectinases, xylanases, arabinases and mannanases in different proportions. Viscozyme L contained mainly pectinases and hemicellulases, while Celluclast 1.5L displayed largely cellulase and xylanase activity, hence the high degree of synergy reported. The temperature optimum was 50ºC for both enzyme mixtures and pH optima were observed at pH 5.0 and pH 3.0 for Viscozyme L and Celluclast 1.5L, respectively. At 37ºC and pH 5.0, the enzymes retained more that 90% activity after 15 days of incubation, allowing the enzymes to be used together with less energy input. The enzymes were further characterised by determining the effect of various compounds, such as alcohols, sugars, phenolic compounds and metal ions at various concentrations on the activity of the enzymes during apple pomace hydrolysis. Apart from lignin, which had almost no effect on enzyme activity, all the compounds caused inhibition of the enzymes to varying degrees. The most inhibitory compounds were some organic acids and metal ions, as well as cellobiose and xylobiose. Using the best ratio for Viscozyme L and Celluclast 1.5L (50:50) for the hydrolysis of apple pomace, it was observed that synergy was highest at the initial stages of hydrolysis and decreased over time, though the sugar concentration increased. The type of synergy for optimal apple pomace hydrolysis was found to be simultaneous. There was no synergy observed between Viscozyme L and Celluclast 1.5L with ligninases - laccase, lignin peroxidase and manganese peroxidase. Hydrolysing apple pomace with ligninases prior to addition of Viscozyme L and Celluclast 1.5L did not improve degradation of the substrate. Immobilisation of the enzyme mixtures on different supports was performed with the aim of increasing stability and enabling reuse of the enzymes. Immobilisation methods were selected based on the chemical properties of the supports, availability, cost and applicability on heterogeneous and insoluble substrate like apple pomace. These methods included crosslinked enzyme aggregates (CLEAs), immobilisation on various supports such as nylon mesh, nylon beads, sodium alginate beads, chitin and silica gel beads. The immobilisation strategies were unsuccessful, mainly due to the low percentage of immobilisation of the enzyme on the matrix and loss of activity of the immobilised enzyme. Free enzymes were therefore used for the remainder of the study. Hydrolysis conditions for apple pomace degradation were optimised using different temperatures and buffer systems in 1 L volumes mixed with compressed air. Hydrolysis at room temperature, using an unbuffered system, gave a better performance as compared to a buffered system. Reactors operated in batch mode performed better (4.2 g/L (75% yield) glucose and 16.8 g/L (75%) reducing sugar) than fed-batch reactors (3.2 g/L (66%) glucose and 14.6 g/L (72.7% yield) reducing sugar) over 100 h using Viscozyme L and Celluclast 1.5L. Supplementation of β- glucosidase activity in Viscozyme L and Celluclast 1.5L with Novozyme 188 resulted in a doubling of the amount of glucose released. The main products released from apple pomace hydrolysis were galacturonic acid, glucose and arabinose and low amounts of galactose and xylose. These products are potential raw materials for biofuel and biorefinery chemical production. An artificial neural network (ANN) model was successfully developed and used for predicting the optimum conditions for apple pomace hydrolysis using Celluclast 1.5L, Viscozyme L and Novozyme 188. Four main conditions that affect apple pomace hydrolysis were selected, namely temperature, initial pH, enzyme loading and substrate loading, which were taken as inputs. The glucose and reducing sugars released as a result of each treatment and their combinations were taken as outputs for 1–100 h. An ANN with 20, 20 and 6 neurons in the first, second and third hidden layers, respectively, was constructed. The performance and predictive ability of the ANN was good, with a R² of 0.99 and a small mean square error (MSE). New data was successfully predicted and simulated. Optimal hydrolysis conditions predicted by ANN for apple pomace hydrolysis were at 30% substrate (wet w/v) and an enzyme loading of 0.5 mg/g and 0.2 mg/mL of substrate for glucose and reducing sugar, respectively, giving sugar concentrations of 6.5 mg/mL and 28.9 mg/mL for glucose and reducing sugar, respectively. ANN showed that enzyme and substrate loadings were the most important factors for the hydrolysis of apple pomace.
  • Full Text:
  • Date Issued: 2014

Development of a bench scale single batch biomass to liquid fuel facility

  • Authors: Zhang, Yusheng
  • Date: 2014
  • Subjects: Biomass energy , Renewable energy sources , Energy conversion , Electric power production
  • Language: English
  • Type: Thesis , Masters , MSc (Chemistry)
  • Identifier: http://hdl.handle.net/10353/811 , vital:26499 , Biomass energy , Renewable energy sources , Energy conversion , Electric power production
  • Description: The research described in this dissertation was motivated by the global demand for energy that is not dependent on coal, oil, natural gas and other non-renewable fossil fuels. The technology used in this project is related to the use of biomass to produce a viable alternative to conventional sources of fuel. A bench scale biomass to liquid (BTL) facility was built and tested. This produced results confirming the feasibility of the BTL process. The findings of the pilot study outlined in this dissertation justified the conclusion that the next step will be to expand the capacity and productivity of the BTL pilot plant to an industrial scale. Biomass comes from a variety of renewable sources that are readily available. In this case, the material used in the fixed bed biomass gasification facility to generate wood gas was agricultural and forestry waste, such as straw and wood chips. The gasifier had the capacity to produce up to 10 cubic metres/hr of gas with a carbon monoxide and hydrogen content of between 20–40% by volume, when it was operated at ambient pressure and with air as the oxidizer. The gas, produced at a temperature above 700º C, was cooled in a quench/water scrubber in order to remove most of the mechanical impurities (tars and water-soluble inorganic particles), condensed and dried with corn cobs before being compressed in cylinders at over 100 bar (g) for use in the Fischer-Tropsch Synthesis (FTS). The syngas was subjected further to a series of refining processes which included removal of sulphur and oxygen. The sulphur removal technology chosen entailed applying modified activated carbon to adsorb H2S with the help of hydrolysis in order to convert organic sulphur impurities into H2S which reduced the sulphur content of the gas to less than 5 ppbv. Supported cobalt catalyst (100 grams), were loaded into a single-tube fixed bed FT reactor with an inner diameter of 50 mm. The reactor was fitted with a heating jacket through which, heated oil ran to cool the reactor during a normal reaction occurring at < 250 ºC, while nitrogen was used in the heating jacket during reduction, which occurred at temperatures up ~ 350 ºC. The FTS reaction was carried out at different pressures and temperatures. Liquid and wax products were produced from the facility. The properties of the liquid and solid hydrocarbons produced were found to be the same as FT products from other feed stocks, such as natural gas and coal.
  • Full Text:
  • Date Issued: 2014

Ethanol production from lignocellulosic sugarcane leaves and tops

  • Authors: Dodo, Charlie Marembu
  • Date: 2014
  • Subjects: Biomass energy , Ethanol as fuel , Lignocellulose
  • Language: English
  • Type: Thesis , Masters , MSc (Chemistry)
  • Identifier: vital:11347 , http://hdl.handle.net/10353/d1019839 , Biomass energy , Ethanol as fuel , Lignocellulose
  • Description: Various methods for the production of bioethanol using different feedstocks have been researched on. In most work on bioethanol synthesis from sugar cane, tops and leaves have been regarded as waste and generally removed and thrown away. In this work, lignocellulosic sugarcane leaves and tops were not discarded but instead used as biomass to evaluate their hydrolyzate content. The leaves and tops were hydrolysed using different methods, namely concentrated acid, dilute acid pre-treatment with subsequent enzyme hydrolysis and compared with a combination of oxidative alkali pretreatment and enzyme hydrolysis. Subsequent fermentation of the hydrolyzates into bioethanol was done using the yeast saccharomyces cerevisae. Acid hydrolysis has the problem of producing inhibitors, which have to be removed and this was done using overliming with calcium hydroxide and compared to sodium hydroxide neutralization. Oxidative alkali pre-treatment with enzyme hydrolysis gave the highest yields of fermentable sugars of 38% (g/g) using 7% (v/v) peroxide pre-treated biomass than 36% (g/g) for 5% (v/v) with the least inhibitors. Concentrated and dilute acid hydrolysis each gave yields of25% (g/g) and 22% (g/g) yields respectively although for acid a neutralization step was necessary and resulted in dilution. Alkaline neutralization of acid hydrolyzates using sodium hydroxide resulted in less dilution and loss of fermentable sugars as compared to overliming. Higher yields of bioethanol, 13.7 (g/l) were obtained from enzyme hydrolyzates than 6.9 (g/l) bioethanol from dilute acid hydrolyzates. There was more bioethanol yield 13.7 (g/l) after 72h of fermentation with the yeast than 7.0 (g/l) bioethanol after 24h. However, the longer fermentation period diminishes the value of the increase in yield by lowering the efficiency of the process.
  • Full Text:
  • Date Issued: 2014

The large scale bioinformatics analysis of auxiliary activity family 9 enzymes

  • Authors: Moses, Vuyani
  • Date: 2014
  • Subjects: Bioinformatics -- Analysis , Cellulose -- Biodegradation , Biomass energy
  • Language: English
  • Type: Thesis , Masters , MSc
  • Identifier: vital:4145 , http://hdl.handle.net/10962/d1016356
  • Description: Biofuels have been proposed to be a suitable replacement to the already depleting fossil fuels. The complex structures of plant biomasses present a challenge the production of biofuels due to recalcitrance. The complex cellulose structure and hydrogen bonding between repeat units of cellulose is believed to be a major contributor to the recalcitrance of cellulose. Fungal organisms come equipped with various oxidative enzymes involved in degradation of plant biomass. The exact mechanism of cellulose degradation remains elusive. The GH61 is a group of proteins which are PMOs. GH61 sequences where previously described as endoglucanases due to weak endoglucanase activity. These enzymes were later found not possess any enzyme activity of their own however they could enhance the activity of other cellulose degrading enzymes. As a result reclassification of these enzymes as AA9 has been implemented. AA9 proteins have been reported to share structural homology with the bacterial AA10 group of enzymes. Based on cleavage products that are produced when AA9 proteins interact with cellulose, AA9 proteins have been grouped into three types. To date the exact mechanism and the sequence and structural basis for differentiating between the various AA9 types remains unknown. Using various bionformatic techniques sequence and structural elements were identified for distinguishing between the AA9 types. A large dataset of sequences was obtained from the Pfam database from UNIPROT entries. Due to high divergence of AA9 sequences, a smaller dataset with the more divergent sequences removed was created. The inclusion of the reference sequences to the data set was done to observe which sequences belong to a certain type. Phylogenetic analysis was able to group AA9 proteins into three distinct groups. MSA and motif analysis revealed that the N-Terminus of these proteins is mostly responsible for type specificity. Structural analysis of AA9 PDB structures and homology models allowed the effect of physicochemical properties to be gauged structurally. The presence of 310 helices and aromatic residues the surface of AA9 sequences is an observation which still warrants further investigation.
  • Full Text:
  • Date Issued: 2014

The biota of the Swartkops Solar Saltworks and their potential for producing biofuels

  • Authors: De Lauwere, Monique Simone
  • Date: 2012
  • Subjects: Organisms , Biomass energy
  • Language: English
  • Type: Thesis , Masters , MSc
  • Identifier: vital:10625 , http://hdl.handle.net/10948/d1011657 , Organisms , Biomass energy
  • Description: The Swartkops and Missionvale salinas in Port Elizabeth on the east coast of South Africa are surrounding by large informal settlements. The runoff from these settlements contributes largely to the eutrophication of the solar saltworks which in turn has an effect on the biotic functioning of the systems, ultimately affecting the quantity and quality of the salt produced. Inorganic nutrients and organic composition, as well as important biological groups were examined within the brine with the aim of comparing the current condition of the same salinas to their condition twelve years ago. Comparisons between inorganic nutrient concentrations and biological groups showed significantly higher inorganic nutrients, with chlorophyll a concentrations in the Swartkops salina in 2011 being significantly higher than in 2012 and the 1999 and 2011 chlorophyll a concentrations being significantly higher than 2012 in the Missionvale salina. Microalgae found in the salinas were cultured in four different growth media. Cells were stained with Nile Red fluorescent dye in order to estimate the extent of lipids production. Five of the most promising lipid producing species were isolated into a monoculture and grown at different salinities to establish the growth and lipid production in response to salinity. Halamphora coffeaeformis and Navicula sp. were found to be the best candidate species. They grew best at salinities between 50 and 70 psu and produced lipid vesicles consuming approximately 10 percent of the cell.
  • Full Text:
  • Date Issued: 2012

Bioethanol production from waste paper through fungal biotechnology

  • Authors: Voigt, Paul George
  • Date: 2010
  • Subjects: Biomass energy , Cellulose -- Biodegradation , Waste paper -- Recycling , Biomass chemicals -- Economic aspects , Renewable energy sources , Fungi -- Biotechnology , Enzymes -- Biotechnology
  • Language: English
  • Type: Thesis , MSc , Masters
  • Identifier: vital:3861 , http://hdl.handle.net/10962/d1013447
  • Description: Bioethanol is likely to be a large contributor to the fuel sector of industry in the near future. Current research trends are geared towards utilizing food crops as substrate for bioethanol fermentation; however, this is the source of much controversy. Utilizing food crops for fuel purposes is anticipated to cause massive food shortages worldwide. Cellulose is the most abundant renewable resource on earth and is subject to a wide array of scientific study in order to utilize the glucose contained within it. Waste paper has a high degree of cellulose associated with it, which makes it an ideal target for cellulose biotechnology with the ultimate end goal of bioethanol production. This study focussed on producing the necessary enzymes to hydrolyse the cellulose found in waste paper and using the sugars produced to produce ethanol. The effects of various printing inks had on the production of sugars and the total envirorunental impact of the effluents produced during the production line were also examined. It was found that the fungus Trichoderma longibrachiatum DSM 769 grown in Mandel's medium with waste newspaper as the sole carbon source at 28 °C for 6 days produced extracellular cellulase enzymes with an activity of 0.203 ± 0.009 FPU.ml⁻¹, significantly higher activity as compared to other paper sources. This extracellular cellulase was used to hydrolyse waste newspaper and office paper, with office paper yielding the highest degree of sugar production with an end concentration of 5.80 ± 0.19 g/1 at 40 °C. Analysis by HPLC showed that although glucose was the major product at 4.35 ± 0.12 g/1, cellobiose was also produced in appreciable amounts (1.97 ± 0.71 g/1). The sugar solution was used as a substrate for Saccharomyces cerevisiae DSM 1333 and ethanol was produced at a level of 1.79 ± 0.26 g/1, the presence of which was confirmed by a 600 MHz NMR spectrum. It was found that cellobiose was not fermented by this strain of S. cerevisiae. Certain components of inks (the PAHs phenanthrene and naphthalene) were found to have a slight inhibitory effect (approximately 15% decrease) on the cellulase enzymes at very high concentrations (approximately 600 μg/1 in aqueous medium), while anthracene had no effect. Whole newsprint ink was shown not to sorb glucose. The environmental analysis of the effluents produced showed that in order for the effluents to be discharged into an aqueous ecosystem they would have to be diluted up to 200 times. They were also shown to have the potential to cause severe machinery damage if reused without proper treatment.
  • Full Text:
  • Date Issued: 2010

Synthesis of bioethanol from lignocellulosic materials: A focus on grass and waste paper as raw materials

  • Authors: Vala, Mavula Kikwe
  • Date: 2009-12
  • Subjects: Ethanol as fuel , Biomass energy , Lignocellulose -- Biotechnology
  • Language: English
  • Type: Master's theses , text
  • Identifier: http://hdl.handle.net/10353/24499 , vital:63049
  • Description: Biofuels are currently recognized as not only a necessity, but an inevitable pathway to secure the planet future energy needs. Food crops have been used (so far) as the biomass for bioethanol and biodiesel production. This has increased concerns over food security and led to the search for diversification and alternative feedstocks for biofuel production. The use of lignocellulosic materials, the most abundant, low cost and easy feedstock to harvest for bioethanol purpose, involves challenging production processes. Several approaches have been used to facilitate the breakdown of the biopolymer structure to produce fermentable sugars that can be converted to ethanol. Most of the approaches have used high temperatures and pressures and have often led to the production of inhibitors of fermentation. In this study, lignocellulosic materials from grass and newsprint were investigated as sources of biomass for bioethanol production using a chemical route (sulfuric acid hydrolysis) which made use of temperatures below 100°C at normal atmospheric pressure. Fermentation of toxic lignocellulosic hydrolyzates was possible after the development of a method for inhibitors removal. The method used treated wood chips as a stationary phase in a chromatographic column to remove inhibitors. This method is expected to be extended to applications such as in municipal wastewater treatment. Sugar yields of 22.26 and 8.9 g/L of hydrolyzate; and an ethanol yield of 184.5 and 130.4 mg/mL of must were achieved for 5g grass and newsprint respectively using optimum conditions of 2percent H2SO4 at 97.5°C for grass and 0.5percent H2SO4 at 97.5°C for newsprint during the hydrolysis process. Pure cellulose was used as a control for the biomass where 254.1 g/L of fermentable sugars were recovered from soluble cellulose and the yield of ethanol was 201.8 mg/mL. , Thesis (MSc) -- Faculty of Science and Agriculture, 2009
  • Full Text:
  • Date Issued: 2009-12
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