The current societal needs for fuels and chemical commodities strongly depend on fossil resources. This dependence can lead to economic instabilities, political problems and insecurity of supplies. Moreover, global warming, which is associated with the massive use of fossil resources, is a dramatic “collateral damage” that endangers the future of the planet. Biomass is the main renewable source available today that can, produce various liquid, gaseous and solid products. Due to their lignocellulosic origin are considered CO2 neutral and thus can generate CO2 credits. Biomass processing can meet to the challenge of reducing of fossil resources by producing a liquid feedstock that can lessen the “fossil dependence” and /or meet the increased demand via a rapidly emerging thermochemical technology: pyrolysis. The ultimate goal of this process is to produce liquid with improved properties that could directly be used as liquid fuel, fuel additive and/or feedstock in modern oil refineries and petrochemical complexes. However, the liquids derived from biomass thermal processing are problematic with respect to their handling and end use applications. Thus, alternative routes of advanced liquid feedstock production are needed. Heterogeneous catalysis has long served the oil refining and petrochemical industries to produce a wide range of fuels and products. The combination of biomass pyrolysis and heterogeneous catalysis (by bringing in contact the produced vapours/liquids with suitable catalysts) is a very promising route. In this dissertation, the exploitation of biomass to produce of liquid feedstock via pyrolysis over a multifunctional catalyst and in a steam atmosphere is investigated.  Steam pyrolysis in a fixed bed reactor demonstrated that steam can be considered a reactive agent even at lower temperatures affecting the yields and the composition of all the products. The devolatilisation accelerates and the amount of final volatile matter in the char. Fast pyrolysis in the presence of steam results in improved and controlled thermal decomposition of the biomass; higher liquid yields and slightly deoxygenated liquid products are also obtained. Steam pyrolysis over a bi-metallic Ni-V catalyst can produce liquids of improved quality (lower O content) and also provide routes for selective deoxygenation. However, a decrease in liquid yield was observed. The combination of metal and acid catalysts (Ni-V/HZSM5) shows enhanced deoxygenation activity and increased H preservation in the produced liquid. The final O content in the liquid was 12.83wt% at a zeolite (HZSM5) loading of~75wt%; however, the yield of the obtained liquid was substantially decreased. Moreover, increased coke formation on the catalyst was observed at highest zeolite rate. The increased catalyst space time (τ) results in a lower liquid yield with reduced oxygen (7.79 wt% at τ =2h) and increased aromatic content. The coke deposited per unit mass of catalyst is lower for longer catalyst space times, while the char yield seems to be unaffected. The evaluation of the stability of the hybrid catalyst showed no significant structural defects and activity loss when the catalyst was regenerated at a low temperature (550οC). / Det nuvarande samhällets behov av bränslen och kemiska produkter är starkt knutet till fossila resurser. Detta beroende kan leda till ekonomisk instabilititet, politiska svårigheter och osäker leveranssäkerhet. Dessutom riskeras allvarliga skador i framtiden på grund av global uppvärmning, vilket är relaterat till det ökande och massiva användandet av fossila bränslen.   Biomassa är en förnybar resurs som är tillgänglig idag, möjlig att utnyttja för produktion av diverse flytande, gasformiga och fasta produkter. Dessa produkter, beroende på biogeniskt ursprung, betraktas som koldioxidneutrala och kan därför generera koldioxidkrediter. Processande av biomassa kan möta utmaningen av minskad fossilbränsleanvändning, genom produktion av flytande råvara som kan reducera beroendet och/eller möta ökad efterfrågan, via en snabbt expanderande termokemisk teknik - pyrolys.    Det slutgiltiga målet med en sådan process är att producera en flytande produkt med förbättrade egenskaper som direkt skulle kunna användas som flytande bränslen, bränsleadditiv och/eller som råmaterial i moderna oljeraffinaderier och petrokemiska komplex. Vätskor som utvinns från termiska processer är problematiska med avseende på hantering och slutanvändningen i olika applikationer, därmed behövs olika spår för produktion av avancerade flytande råvaror. Heterogena katalysen har länge tjänat raffinaderi- och petrokemisk industri, som producerar ett brett utbud av bränslen och produkter, lämpliga för säker användning. Kombinationen av biomassapyrolys och heterogen katalys  (genom att bringa pyrolysångorna i kontakt med en lämplig katalysator) är ett väldigt lovande spår. I denna avhandling undersöks användningen av biomassa för produktion av flytande råvara, via pyrolys över en flerfunktionel katalysator i ångatmosfär. Ångpyrolys i en fastbäddsreaktor visade att ånga kan betraktas som ett reaktivt medium,  även vid låga temperaturer, som påverkar utbyten och sammansättning av alla produkter. Avgasningen sker snabbare och den slutliga flykthalten i kolresterna blir lägren vid användning av ånga. Snabbpyrolys i ångatmosfär resulterar i förbättrad och mer kontrollerad termisk nedbrytning av biomassa, vilket ger ett högre vätskeutbyte och en något deoxygenerad flytande produkten. ångpyrolys i kombination med bimetalliska NiV-katalysatorer, ger upphov till en flytande råvara med förbättrad kvalitet och selektiv deoxygenering. Dock med ett minskande utbyte som följd. Kombinationen av metall och en sur katalysator (Ni-V/HZSM5) visade förstärkt deoxygenering med bibehållen vätehalt i den flytande produkten. Den slutliga syrehalten i vätskan var 12.83 vikt% vid en zeolithalt (HZSM5) på 75 vikt%, dock med ett kraftigt minskande vätskeutbyte. Dessutom noterades ökad koksbildning på katalysatormaterialet med den högsta zeolithalten. Ökad rymd-tid  för katalysatorn (τ) ger ett lägre vätskeutbyte med reducerad syrehalt (7.79 vikt% vid τ=2h) och ökad aromathalt. Koksbildning på ytan, per massenhet katalysatormaterial, minskade vid längre rymd-tider medan utbytet av kolrester förblev opåverkat.  Undersökningen av stabiliteten hos hybridkatalysatorn visade inga strukturella defekter och ingen signifikant minskad aktivitet efter regenerering vid låg temperatur (550οC). / Οι σύγχρονες ανάγκες της κοινωνίας για παραγωγή υγρών καυσίμων και χημικών προϊόντων εξαρτώνται από τους ορυκτούς πόρους. Αυτή η εξάρτηση μπορεί να οδηγήσει σε οικονομικά προβλήματα, πολιτκή αστάθεια, όπως επίσης και αβεβαιότητα στις προμήθειες της ενεργειακής εφοδιαστικής αλυσίδας. Επιπροσθέτως, μια δραματική «παράπλευρη απώλεια» η οποία θέτει σε κίνδυνο το μέλλον του πλανήτη είναι η υπερθέρμανσή του, η οποία έχει συσχετισθεί με την εκτεταμένη χρήση ορυκτών πόρων. Σήμερα, η βιομάζα είναι η μόνη ανανεώσιμη πηγή από την οποία μπορούν να παραχθούν υγρά, αέρια και στερεά προϊόντα, που λόγω της λιγνοκυταρρινικής τους προελεύσεως, η συνεισφορά τους στις εκομπές CO2 θεώρειται μηδενική. Η θερμοχημική επεξεργασία της βιομάζας συνεισφέρει στον περιορισμό της χρήσης ορυκτών πόρων, με την παραγωγή υγρών προϊόντων, τα οποία μπορούν να μειώσουν την εξάρτηση ή /και την αυξημένη ζήτηση μέσω μιας ταχέως αναπτυσόμενης τεχνολογίας, της πυρόλυσης. Στόχος της διεργασίας είναι η παραγωγή υγρών προϊόντων με ιδιότητες, που επιτρέπουν την απευθείας χρήση τους ως υγρά καύσιμα ή ως πρώτη ύλη, για την παραγώγη χημικών προϊόντων σε συγχρονες μονάδες διύλισης πετρελαίου και σε πετροχημικά συγκτροτήματα. Εν τούτοις, τα υγρά προϊόντα της θερμικής διάσπασης (πυρόλυση) είναι προβληματικά στη διαχείρηση και στις τελικές τους εφαρμογές, λόγω της σύστασής τους. Ως εκ τούτου, απαιτούνται νέες τεχνικές για παραγωγή προηγμένων υγρών προοϊόντων. Η ετερογενής κατάλυση έχει επιτυχώς εφαρμοσθεί στην πετρελαϊκή και χημική βιομηχανία, παράγοντας ένα μεγάλο εύρος προϊόντων. Ο συνδυασμός της με την πυρόλυση (φέρνοντας σε επαφη τα υγρά/ατμούς με κατάλληλο καταλύτη) αποτελεί μια πολλά υποσχόμενη ενναλακτική. Στην παρούσα διατριβή μελετάται η αξιοποίηση βιομάζας για παραγωγή υγρών προϊόντων μέσω καταλυτικής πυρόλυσης, με χρήση πολυλειτουρικού καταλύτη (multi-functional catalyst) υπό την παρουσία ατμού. Η χρήση ατμου κατά τη διαρκειά πυρόλυσης βιομαζας σε αντιδραστήρα σταθερής κλίνης, μεταβάλει τη σύσταση των επιμέρους προϊόντων. Η παρουσία ατμού έχει ως αποτέλεσμα την ταχύτερη αποπτητικοποίηση του υλικού, ενώ παράλληλα η περιεκτικότητα του υπολειπόμενου εξανθρακώματος σε πτητικά είναι μικρότερη. Τα πειραματικά αποτελέσματα ταχείας πυρόλυσης σε αντιδραστήρα ρευστοστερεάς κλίνης δείχνουν ό,τι η χρήση ατμού βελτιώνει την θερμική διάσπαση της βιομαζας, αυξάνοντας την απόδοση σε υγρά προϊοντά, ενώ παράλληλα βοηθάει στην αποξυγόνωσή τους. Ο συνδυασμός της πυρόλυσης υπό την παρουσία ατμού και διμεταλλικού καταλύτη νικελίου–βαναδίου μπορεί να  βελτιώσει την ποιότητα των παραγόμενων υγρών (αποξυγόνωση) με παραλλήλη μείωση της απόδοσής τους, ενώ μπορεί να  παράγει προϊόντα εκλεκτικής αποξυγόνωσης. Συνδυασμός μεταλλικών και ζεολιθικών καταλυτών (Ni-V/HZSM5) εμφανίζει βελτιωμένη δραστικότητα στις αντιδράσεις αποξυγόνωσης, με παράλληλη συγκράτηση υδρογόνου (Η) στα υγρά προϊόντα. Η τελική περιεκτικότητα των υγρών προϊόντων σε οξυγόνου (Ο) μετά από 90 min αντίδρασης είναι 12.83 wt%, με περιεκτικότητα ζεόλιθου (ΗZSΜ5) ~75 wt% στον καταλύτη. Ωστόσο, η αυξηση της περεικτικότητας σε ζεόλιθο έχει ως αποτέλεσμα την αύξηση των επικαθήσεων άνθρακα επάνω στον κατάλυτη, καθώς και την σημαντική μειώση της απόδοσης των υγρών προϊόντων (24.35wt% επι ξηρής βιομάζας).  Η αύξηση του χώρου χρόνου του καταλύτη (τ) έχει ως αποτέλεσμα: τη μείωση των υγρών προϊόντων, τη μείωση του περιεχόμενου Ο στα υγρά προϊόντα (7.79 wt% at τ =2h), την αύξηση των αρωματικών υδρογονανθράκων και τη μείωση του επικαθήμενου κωκ ανά μονάδα μάζας καταλύτη. Η απόδοση του εξανθρακώματος παρέμεινε πρακτικά αμετάβλητη. Η αναγέννηση του υβριδικού καταλύτη σε χαμηλές θερμοκρασιές (550οC) δεν επέφερε σημαντικές δομικές αλλαγές και απώλεια δραστικότητας. / <p>QC 20140306</p>

Renewable energy sources such as biomass are becoming more and more important as alternative to fossil fuels. One of the most exciting new sources of biomass is microalgae. The Hartbeespoort Dam, located 37 km west of South Africa’s capital Pretoria, has one of the dense populations of microalgae in the world, and is one of the largest reservoirs of micro-algal biomass in South Africa. The dam has great potential for micro-algal biomass production and beneficiation due to its high nutrient loading, stable climatic conditions, size and close proximity to major urban and industrial centres. There are five major steps in the production of biodiesel from micro-algal biomass-derived oil: the first two steps involve the cultivation and harvesting of micro-algal biomass; which is followed by the extraction of oils from the micro-algal biomass; then the conversion of these oils via the chemical reaction transesterification into biodiesel; and the last step is the separation and purification of the produced biodiesel. The first two steps are the most inefficient and costly steps in the whole biomass-to-liquids (BTL) value chain. Cultivation costs may contribute between 20–40% of the total cost of micro-algal BTL production (Comprehensive Oilgae Report, 2010), while harvesting costs may contribute between 20–30% of the total cost of BTL production (Verma et al., 2010). Any process that could optimize these two steps would bring a biomass-to-liquids process closer to successful commercialization. The aim of this work was to study the cultivation and harvesting of micro-algal biomass from the Hartbeespoort Dam for the production of biodiesel. In order to do this a literature study was done and screening experiments were performed to determine the technical and economical feasibility of cultivation and harvesting methods in the context of a new integrated biomass-to-liquids biodiesel process, whose feasibility was also studied. The literature study revealed that the cyanobacterium Microcystis aeruginosa is the dominant micro-organism species in the Hartbeespoort Dam. The study also revealed factors that promote the growth of this species for possible incorporation into existing and new cultivation methods. These factors include stable climatic conditions, with high water temperatures around 25oC for optimal Microcystis growth; high nutrient loadings, with high phosphorus (e.g. PO43-) and nitrogen concentrations (e.g. NO3-); stagnant hydrodynamic conditions, with low wind velocities and enclosed bays, which promote the proliferation of Microcystis populations; and substrates like sediment, rocks and debris which provide safe protective environments for Microcystis inoculums. The seven screening studies consisted of three cultivation experiments, three harvesting experiments and one experiment to determine the combustion properties of micro-algal biomass. The three cultivation experiments were conducted in three consecutively scaled-up laboratory systems, which consisted of one, five and 135-litre bioreactors. The highest productivity achieved was over a period of six weeks in the 5-litre Erlenmeyer bioreactors with 0.0862 g/L/d at an average bioreactor day-time temperature of 26.0oC and an aeration rate of 1.5 L/min. The three cultivation experiments revealed that closed-cultivation systems would not be feasible as the highest biomass concentrations achieved under laboratory conditions were too low. Open-cultivation systems are only feasible if the infrastructure already exists, like in the case of the Hartbeespoort Dam. It is recommended that designers of new micro-algal BTL biodiesel processes first try to capitalize on existing cultivation infrastructure, like dams, by connecting their processes to them. This will reduce the capital and operating costs of a BTL process significantly. Three harvesting experiments studied the technical feasibility and determined design parameters for three promising, unconventional harvesting methods. The first experiment studied the separation of Hartbeespoort Dam micro-algal biomass from its aqueous phase, due to its natural buoyancy. Results obtained suggest that an optimum residence time of 3.5 hours in separation vessels would be sufficient to concentrate micro-algal biomass from 1.5 to 3% TSS. The second experiment studied the aerial harvesting yield of drying micro-algal biomass (3% TSS) on a patch of building sand in the sun for 24 hours. An average aerial harvesting yield of 157.6 g/m2/d of dry weight micro-algal biomass from the Hartbeespoort Dam was achieved. The third experiment studied the gravity settling harvesting yield of cultivated Hartbeespoort Dam-sourced microalgae as it settles to the bottom of the bioreactor after air agitation is suspended. Over 90% of the micro-algal biomass settled to the bottom quarter of the bioreactor after one day. Cultivated micro-algal biomass sourced from the Hartbeespoort Dam, can easily be harvested by allowing it to settle with gravity when aeration is stopped. Results showed that gravity settling equipment, with residence times of 24 hours, should be sufficient to accumulate over 90% of cultivated micro-algal biomass in the bottom quarter of a separation vessel. Using this method for primary separation could reduce the total cost of harvesting equipment dramatically, with minimal energy input. All three harvesting methods, which utilize the natural buoyancy of Hartbeespoort Dam microalgae, gravity settling, and a combination of sand filtration and solar drying, to concentrate, dewater and dry the micro-algal biomass, were found to be feasible and were incorporated into new integrated BTL biodiesel process. The harvesting processes were incorporated and designed to deliver the most micro-algal biomass feedstock, with the least amount of equipment and energy use. All the available renewable power sources from the Hartbeespoort Dam system, which included wind, hydro, solar and biomass power, were utilized and optimized to deliver minimum power loss, and increase power output. Wind power is utilized indirectly, as prevailing south-easterly winds concentrate micro-algal biomass feedstock against the dam wall of the Hartbeespoort Dam. The hydraulic head of 583 kPa of the 59.4 meter high dam wall is utilized to filter and transport biomass to the new integrated BTL facility, which is located down-stream of the dam. Solar power is used to dry the microalgae, which in turn is combusted in a furnace to release its 18,715 kW of biochemical power, which is used for heating in the power-intensive extraction unit of the processing facility. Most of the processes in literature that cover the production of biodiesel from micro-algal biomass are not thermodynamically viable, because they consume more power than what they produce. The new process sets a benchmark for other related ones with regards to its net power efficiency. The new process is thermodynamically efficient, exporting 20 times more power than it imports, with a net power output of 5,483 kilowatts. The design of a new integrated BTL process consisted of screening the most suitable methods for harvesting micro-algal biomass from the Hartbeespoort Dam and combining the obtained design parameters from these harvesting experiments with current knowledge on extraction of oils from microalgae and production of biodiesel from these oils into an overall conceptual process. Three promising, unconventional harvesting methods from Brink and Marx (2011), a micro-algal oil extraction process from Barnard (2009), and a process from Miao and Wu (2005) to produce biodiesel through the acid-catalyzed transesterification of micro-algal oil, were combined into an integrated BTL process. The new integrated biomass-to-liquids (BTL) process was developed to produce 2.6 million litres of biodiesel per year from harvested micro-algal biomass from the Hartbeespoort Dam. This is enough to supply 51,817 medium-sized automobiles per year or 142 automobiles per day of environmentally friendly fuel. The new BTL facility consists of three sections: a cultivation section where microalgae grow in the 20 km2 Hartbeespoort Dam to a concentration of 160 g/m2 during the six warmest months of the year; a harvesting section where excess water is removed from the micro-algal biomass; a reaction section where fatty acid oils are extracted from the microalgae and converted to biodiesel, and dry biomass rests are combusted to supply heat for the extraction and biodiesel units of the reaction section. The cultivation section consist of the existing Hartbeespoort Dam, which make up the cultivation unit; the harvesting section is divided into a collection unit (dam wall part of the Hartbeespoort Dam), a concentration unit, a filtration unit, and a drying unit; the reaction section consists of an oil extraction unit, a combustion unit, and a biodiesel unit. At a capital cost of R71.62 million (R1.11/L) (±30%), the new proposed BTL facility will turn 933,525 tons of raw biomass (1.5% TSS) into 2,590,856 litres of high quality biodiesel per year, at an annual operating cost of R11.09 million (R4.28/L at 0% producer inflation), to generate R25.91 million (R10.00/L) per year of revenue. At the current diesel price of R10.00/L, the new integrated BTL process is economically feasible with net present values (NPV) of R368 million (R5.68/L) and R29.30 million (R0.45/L) at discount rates of 0% and 10%, respectively. The break-even biodiesel prices are R5.34/L and R7.92/L, for a zero NPV at 0% and 10% discount rates, respectively. The cultivation of micro-algal biomass from the Hartbeespoort Dam is only economical if the growth is allowed to occur naturally in the dam without any additional cultivation equipment. The cultivation of micro-algal biomass in either an open or a closed-cultivation system will not be feasible as the high cost of cultivation will negate the value of biodiesel derived from the cultivated biomass. The utilization of the three promising harvesting methods described in this work is one of the main drivers for making this process economically feasible. At a capital cost of R13.49 million (R37.77/ton of dry weight micro-algal biomass) and a operating cost of R2.00 million per year (R210.63/ton of dry weight micro-algal biomass) for harvesting micro-algal biomass from the Hartbeespoort Dam, harvesting costs account for only 19% and 18% of the overall capital and operating costs of the new process, respectively. This is less than harvesting costs for other comparative processes world-wide, which contribute between 20 and 30% of the overall cost of biomass-to-liquids production. At current fuel prices, the cultivation of micro-algal biomass from and next to the Hartbeespoort Dam is not economical, but the unconventional harvesting methods presented in this thesis are feasible, if incorporated into the new integrated biomass-to-liquids biodiesel process set out in this work. / Thesis (Ph.D. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2011.

Renewable energy sources such as biomass are becoming more and more important as alternative to fossil fuels. One of the most exciting new sources of biomass is microalgae. The Hartbeespoort Dam, located 37 km west of South Africa’s capital Pretoria, has one of the dense populations of microalgae in the world, and is one of the largest reservoirs of micro-algal biomass in South Africa. The dam has great potential for micro-algal biomass production and beneficiation due to its high nutrient loading, stable climatic conditions, size and close proximity to major urban and industrial centres. There are five major steps in the production of biodiesel from micro-algal biomass-derived oil: the first two steps involve the cultivation and harvesting of micro-algal biomass; which is followed by the extraction of oils from the micro-algal biomass; then the conversion of these oils via the chemical reaction transesterification into biodiesel; and the last step is the separation and purification of the produced biodiesel. The first two steps are the most inefficient and costly steps in the whole biomass-to-liquids (BTL) value chain. Cultivation costs may contribute between 20–40% of the total cost of micro-algal BTL production (Comprehensive Oilgae Report, 2010), while harvesting costs may contribute between 20–30% of the total cost of BTL production (Verma et al., 2010). Any process that could optimize these two steps would bring a biomass-to-liquids process closer to successful commercialization. The aim of this work was to study the cultivation and harvesting of micro-algal biomass from the Hartbeespoort Dam for the production of biodiesel. In order to do this a literature study was done and screening experiments were performed to determine the technical and economical feasibility of cultivation and harvesting methods in the context of a new integrated biomass-to-liquids biodiesel process, whose feasibility was also studied. The literature study revealed that the cyanobacterium Microcystis aeruginosa is the dominant micro-organism species in the Hartbeespoort Dam. The study also revealed factors that promote the growth of this species for possible incorporation into existing and new cultivation methods. These factors include stable climatic conditions, with high water temperatures around 25oC for optimal Microcystis growth; high nutrient loadings, with high phosphorus (e.g. PO43-) and nitrogen concentrations (e.g. NO3-); stagnant hydrodynamic conditions, with low wind velocities and enclosed bays, which promote the proliferation of Microcystis populations; and substrates like sediment, rocks and debris which provide safe protective environments for Microcystis inoculums. The seven screening studies consisted of three cultivation experiments, three harvesting experiments and one experiment to determine the combustion properties of micro-algal biomass. The three cultivation experiments were conducted in three consecutively scaled-up laboratory systems, which consisted of one, five and 135-litre bioreactors. The highest productivity achieved was over a period of six weeks in the 5-litre Erlenmeyer bioreactors with 0.0862 g/L/d at an average bioreactor day-time temperature of 26.0oC and an aeration rate of 1.5 L/min. The three cultivation experiments revealed that closed-cultivation systems would not be feasible as the highest biomass concentrations achieved under laboratory conditions were too low. Open-cultivation systems are only feasible if the infrastructure already exists, like in the case of the Hartbeespoort Dam. It is recommended that designers of new micro-algal BTL biodiesel processes first try to capitalize on existing cultivation infrastructure, like dams, by connecting their processes to them. This will reduce the capital and operating costs of a BTL process significantly. Three harvesting experiments studied the technical feasibility and determined design parameters for three promising, unconventional harvesting methods. The first experiment studied the separation of Hartbeespoort Dam micro-algal biomass from its aqueous phase, due to its natural buoyancy. Results obtained suggest that an optimum residence time of 3.5 hours in separation vessels would be sufficient to concentrate micro-algal biomass from 1.5 to 3% TSS. The second experiment studied the aerial harvesting yield of drying micro-algal biomass (3% TSS) on a patch of building sand in the sun for 24 hours. An average aerial harvesting yield of 157.6 g/m2/d of dry weight micro-algal biomass from the Hartbeespoort Dam was achieved. The third experiment studied the gravity settling harvesting yield of cultivated Hartbeespoort Dam-sourced microalgae as it settles to the bottom of the bioreactor after air agitation is suspended. Over 90% of the micro-algal biomass settled to the bottom quarter of the bioreactor after one day. Cultivated micro-algal biomass sourced from the Hartbeespoort Dam, can easily be harvested by allowing it to settle with gravity when aeration is stopped. Results showed that gravity settling equipment, with residence times of 24 hours, should be sufficient to accumulate over 90% of cultivated micro-algal biomass in the bottom quarter of a separation vessel. Using this method for primary separation could reduce the total cost of harvesting equipment dramatically, with minimal energy input. All three harvesting methods, which utilize the natural buoyancy of Hartbeespoort Dam microalgae, gravity settling, and a combination of sand filtration and solar drying, to concentrate, dewater and dry the micro-algal biomass, were found to be feasible and were incorporated into new integrated BTL biodiesel process. The harvesting processes were incorporated and designed to deliver the most micro-algal biomass feedstock, with the least amount of equipment and energy use. All the available renewable power sources from the Hartbeespoort Dam system, which included wind, hydro, solar and biomass power, were utilized and optimized to deliver minimum power loss, and increase power output. Wind power is utilized indirectly, as prevailing south-easterly winds concentrate micro-algal biomass feedstock against the dam wall of the Hartbeespoort Dam. The hydraulic head of 583 kPa of the 59.4 meter high dam wall is utilized to filter and transport biomass to the new integrated BTL facility, which is located down-stream of the dam. Solar power is used to dry the microalgae, which in turn is combusted in a furnace to release its 18,715 kW of biochemical power, which is used for heating in the power-intensive extraction unit of the processing facility. Most of the processes in literature that cover the production of biodiesel from micro-algal biomass are not thermodynamically viable, because they consume more power than what they produce. The new process sets a benchmark for other related ones with regards to its net power efficiency. The new process is thermodynamically efficient, exporting 20 times more power than it imports, with a net power output of 5,483 kilowatts. The design of a new integrated BTL process consisted of screening the most suitable methods for harvesting micro-algal biomass from the Hartbeespoort Dam and combining the obtained design parameters from these harvesting experiments with current knowledge on extraction of oils from microalgae and production of biodiesel from these oils into an overall conceptual process. Three promising, unconventional harvesting methods from Brink and Marx (2011), a micro-algal oil extraction process from Barnard (2009), and a process from Miao and Wu (2005) to produce biodiesel through the acid-catalyzed transesterification of micro-algal oil, were combined into an integrated BTL process. The new integrated biomass-to-liquids (BTL) process was developed to produce 2.6 million litres of biodiesel per year from harvested micro-algal biomass from the Hartbeespoort Dam. This is enough to supply 51,817 medium-sized automobiles per year or 142 automobiles per day of environmentally friendly fuel. The new BTL facility consists of three sections: a cultivation section where microalgae grow in the 20 km2 Hartbeespoort Dam to a concentration of 160 g/m2 during the six warmest months of the year; a harvesting section where excess water is removed from the micro-algal biomass; a reaction section where fatty acid oils are extracted from the microalgae and converted to biodiesel, and dry biomass rests are combusted to supply heat for the extraction and biodiesel units of the reaction section. The cultivation section consist of the existing Hartbeespoort Dam, which make up the cultivation unit; the harvesting section is divided into a collection unit (dam wall part of the Hartbeespoort Dam), a concentration unit, a filtration unit, and a drying unit; the reaction section consists of an oil extraction unit, a combustion unit, and a biodiesel unit. At a capital cost of R71.62 million (R1.11/L) (±30%), the new proposed BTL facility will turn 933,525 tons of raw biomass (1.5% TSS) into 2,590,856 litres of high quality biodiesel per year, at an annual operating cost of R11.09 million (R4.28/L at 0% producer inflation), to generate R25.91 million (R10.00/L) per year of revenue. At the current diesel price of R10.00/L, the new integrated BTL process is economically feasible with net present values (NPV) of R368 million (R5.68/L) and R29.30 million (R0.45/L) at discount rates of 0% and 10%, respectively. The break-even biodiesel prices are R5.34/L and R7.92/L, for a zero NPV at 0% and 10% discount rates, respectively. The cultivation of micro-algal biomass from the Hartbeespoort Dam is only economical if the growth is allowed to occur naturally in the dam without any additional cultivation equipment. The cultivation of micro-algal biomass in either an open or a closed-cultivation system will not be feasible as the high cost of cultivation will negate the value of biodiesel derived from the cultivated biomass. The utilization of the three promising harvesting methods described in this work is one of the main drivers for making this process economically feasible. At a capital cost of R13.49 million (R37.77/ton of dry weight micro-algal biomass) and a operating cost of R2.00 million per year (R210.63/ton of dry weight micro-algal biomass) for harvesting micro-algal biomass from the Hartbeespoort Dam, harvesting costs account for only 19% and 18% of the overall capital and operating costs of the new process, respectively. This is less than harvesting costs for other comparative processes world-wide, which contribute between 20 and 30% of the overall cost of biomass-to-liquids production. At current fuel prices, the cultivation of micro-algal biomass from and next to the Hartbeespoort Dam is not economical, but the unconventional harvesting methods presented in this thesis are feasible, if incorporated into the new integrated biomass-to-liquids biodiesel process set out in this work. / Thesis (Ph.D. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2011.

Há uma demanda global pelo abastecimento de combustíveis veiculares menos poluentes, tanto por questões energéticas quanto sócio-ambientais. Uma potencial alternativa, que traduz a possibilidade de um biocombustível sem as limitações da Primeira Geração, é a rota tecnológica conhecida como Biomass-to-Liquids (BTL) que, através da gaseificação e da síntese Fischer-Tropsch, possibilita a obtenção de biocombustíveis líquidos, como o óleo diesel sintético, provenientes da biomassa moderna, nesse estudo, a biomassa lignocelulósica. Para a produção em escala comercial de um biocombustível da Segunda Geração, um complexo planejamento e altos investimentos são demandados dado seu pioneirismo e ausência de histórico de mercado ou modelos precisos. Uma metodologia desenvolvida em 2006 pelo pesquisador Harold Boerrigter propõe o dimensionamento ideal de uma planta BTL a partir de uma planta Gas-to-Liquids (GTL); são aqui propostas correções e atualizações para esta metodologia, sugerindo-se uma curva capaz de apontar a influência da economia de escala em plantas BTL e uma fórmula para o cálculo estimado do Total Capital Investment (TCI) destas plantas até o momento o Brasil não dispõe de nenhuma planta que opere pela rota BTL. Segue-se com considerações sobre a oferta de resíduos florestais no território brasileiro e a constatação de que a mesma seria insuficiente como matéria-prima para sustentar grandes plantas BTL, fazendo-se necessário o emprego de culturas planejadas na forma de florestas energéticas. Uma vez feita tal análise, apresenta-se o histórico, desde sua concepção até o seu fechamento, da primeira planta a operar pela rota BTL e a produzir o designer fuel batizado de SunDiesel®: construída na Alemanha, a CHOREN Industritechnik contribui com sua experiência de anos e também com a tecnologia de gaseificação Carbo-V® para as pesquisas com os biocombustíveis sintéticos. Seu exemplo pode sinalizar um alerta com relação ao dispêndio de esforços em projetos desta natureza dadas as incertezas econômicas que circundam as fronteiras tecnológicas dos combustíveis da Segunda Geração. / There is a global demand for the supply of less polluting vehicular fuels as much by energy issues as socio-environmental. A potential alternative meaning the possibility of a biofuel without the limitations from the First Generation is the technological route known as Biomass-to-Liquids (BTL) which via gasification and the Fischer-Tropsch synthesis turns possible to obtain liquid biofuels such synthetic diesel oil from modern biomass, in this study, the lignocellulosic biomass. For commercial-scale production of a Second Generation biofuel, a complex planning and high investments are required given its pioneering and absence of market history or precise models. A methodology developed in 2006 by researcher Harold Boerrigter proposes the ideal sizing for a BTL plant assuming a Gas-to-Liquids (GTL) plant; here are proposed corrections and updates for this methodology, suggesting a curve able to point the influence of economy of scale in BTL plants and a formula for the calculation of an estimated Total Capital Investment (TCI) of these plants by the present time Brazil has no plant operating by BTL route. The research follows up with issues regarding forest residues provision in the Brazilian territory and conlcuding that the same would be insufficient as a raw material to sustain large BTL plants, making necessary the use of planned crops in the form of energy forests. Once made such analysis, it is presented the history since its beginning until its closing for the first plant to operate by the BTL route and to produce the designer fuel called SunDiesel®: built in Germany, the CHOREN Industritechnik contributes with its experience of years and also with the gasification technology Carbo-V® for researches with synthetic biofuels. Such example may indicates an alert regarding the expenditure of efforts on projects of this nature, given the economic uncertainties that surround the Second Generation fuels technological frontiers.

Há uma demanda global pelo abastecimento de combustíveis veiculares menos poluentes, tanto por questões energéticas quanto sócio-ambientais. Uma potencial alternativa, que traduz a possibilidade de um biocombustível sem as limitações da Primeira Geração, é a rota tecnológica conhecida como Biomass-to-Liquids (BTL) que, através da gaseificação e da síntese Fischer-Tropsch, possibilita a obtenção de biocombustíveis líquidos, como o óleo diesel sintético, provenientes da biomassa moderna, nesse estudo, a biomassa lignocelulósica. Para a produção em escala comercial de um biocombustível da Segunda Geração, um complexo planejamento e altos investimentos são demandados dado seu pioneirismo e ausência de histórico de mercado ou modelos precisos. Uma metodologia desenvolvida em 2006 pelo pesquisador Harold Boerrigter propõe o dimensionamento ideal de uma planta BTL a partir de uma planta Gas-to-Liquids (GTL); são aqui propostas correções e atualizações para esta metodologia, sugerindo-se uma curva capaz de apontar a influência da economia de escala em plantas BTL e uma fórmula para o cálculo estimado do Total Capital Investment (TCI) destas plantas até o momento o Brasil não dispõe de nenhuma planta que opere pela rota BTL. Segue-se com considerações sobre a oferta de resíduos florestais no território brasileiro e a constatação de que a mesma seria insuficiente como matéria-prima para sustentar grandes plantas BTL, fazendo-se necessário o emprego de culturas planejadas na forma de florestas energéticas. Uma vez feita tal análise, apresenta-se o histórico, desde sua concepção até o seu fechamento, da primeira planta a operar pela rota BTL e a produzir o designer fuel batizado de SunDiesel®: construída na Alemanha, a CHOREN Industritechnik contribui com sua experiência de anos e também com a tecnologia de gaseificação Carbo-V® para as pesquisas com os biocombustíveis sintéticos. Seu exemplo pode sinalizar um alerta com relação ao dispêndio de esforços em projetos desta natureza dadas as incertezas econômicas que circundam as fronteiras tecnológicas dos combustíveis da Segunda Geração. / There is a global demand for the supply of less polluting vehicular fuels as much by energy issues as socio-environmental. A potential alternative meaning the possibility of a biofuel without the limitations from the First Generation is the technological route known as Biomass-to-Liquids (BTL) which via gasification and the Fischer-Tropsch synthesis turns possible to obtain liquid biofuels such synthetic diesel oil from modern biomass, in this study, the lignocellulosic biomass. For commercial-scale production of a Second Generation biofuel, a complex planning and high investments are required given its pioneering and absence of market history or precise models. A methodology developed in 2006 by researcher Harold Boerrigter proposes the ideal sizing for a BTL plant assuming a Gas-to-Liquids (GTL) plant; here are proposed corrections and updates for this methodology, suggesting a curve able to point the influence of economy of scale in BTL plants and a formula for the calculation of an estimated Total Capital Investment (TCI) of these plants by the present time Brazil has no plant operating by BTL route. The research follows up with issues regarding forest residues provision in the Brazilian territory and conlcuding that the same would be insufficient as a raw material to sustain large BTL plants, making necessary the use of planned crops in the form of energy forests. Once made such analysis, it is presented the history since its beginning until its closing for the first plant to operate by the BTL route and to produce the designer fuel called SunDiesel®: built in Germany, the CHOREN Industritechnik contributes with its experience of years and also with the gasification technology Carbo-V® for researches with synthetic biofuels. Such example may indicates an alert regarding the expenditure of efforts on projects of this nature, given the economic uncertainties that surround the Second Generation fuels technological frontiers.