Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: In the developed and developing world, the use of lipids for the production of alkyl esters, also known as biodiesel, showed phenomenal growth during the ten year period up to the end of 2007. The main sources for these lipids are the oils extracted from oil seeds such as soya-, palm-, and rape seed, but other products in the food chain such as waste cooking oil (yellow grease) and animal fats are also used. In Africa and Asia vast tracks of land not previously tilled, are now being cultivated to yield oils which are not edible and in a number of countries intensive research is focused on lipid producing species such as algae. Meanwhile more evidence is coming to the fore pronouncing biodiesel and other first generation biofuels not to be the panacea for the predicament the world is facing on unbridled population growth, energy security concerns and environmental issues such as indirect land use changes, global warming and climate changes. The acceptance of the National Biofuels Industrial Strategy at Cabinet level has not yet resulted in significant commensurate activity in South Africa. The availability, other uses and volumes of selected feed stocks for biodiesel production invite debate on the choice between food- and energy security and the appropriateness of some identified socio-economical and socio-political drivers for a viable industry. Somehow the unique characteristics of South Africa and its resources seem not to feature in debate and constraints on the production of biodiesel, as described in this dissertation. The conventional process routes for commercial biodiesel production are based on a mature technology which has inherent pollution and economical limitations. This called for a detailed critical evaluation on process routes more environmentally friendly or involving fewer unit processes generating more desirable products, albeit with more severe process conditions. By comparison, the homogeneous alkali catalyst alcoholysis (HACA), the enzymatic catalyst alcoholysis (ECA) and the super critical alcoholysis (SCA) process routes as developed in this study, are found to be competitive on total manucturing costs as assessed, if results emanating from selected sensitivity analyses and optimisation studies, are accepted. The total manufacturing and operating costs in the selected process routes as estimated, assuming the same capacities for commercial biodiesel production, are dominated by feed stock costs. Incentives on depreciation and fuel levies are deemed not effective, if costs are compared to the price of fossil diesel at the retail level – October 2011. It is concluded that using the feed stocks indicated in the Strategy, commercial biodiesel production is not economically feasible in South Africa at present. In this study process routes and feed stocks were identified that can change this position. Note should be taken of the intensive research activities being conducted on second generation technologies and biorefineries in the developed world, as discussed in this dissertation. / AFRIKAANSE OPSOMMING: In die ontwikkelde en ontwikkelende wêreld het die gebruik van vette vir die produksie van alkielesters, ook bekend as biodiesel, in die tienjaarperiode tot die einde van 2007 fenomenale groei getoon. Die hoofbronne vir hierdie lipiede is die olies onttrek van oliesade soos soja-, palm-, en raapsaad, maar ander produkte in die voedselketting soos gebruikte kookolie en dierevette word ook gebruik. In Afrika en Asië word uitgestrekte stukke grond voorheen onbewerk, nou bewerk om olies wat nie eetbaar is nie, op te lewer, en in verskeie lande word intensiewe navorsing op vetproduserende spesies soos alge gedoen. Intussen kom meer bewyse na vore wat verklaar dat biodiesel en ander eerste-generasie biobrandstowwe nie die wondermiddel is vir die moeilike posisie wat die wêreld in die gesig staar oor onbeteuelde bevolkingsaanwas, kwellings oor energiesekuriteit en omgewingskwessies soos indirekte grondverbruike, aardverwarming en klimaatsveranderings nie . Die aanvaarding van die Nasionale Biobrandstowwe Industriële Strategie op kabinetsvlak het nog nie verhoogde soortgelyke aktiwiteite in Suid-Afrika tot gevolg gehad nie. Die beskikbaarheid, gebruike en volumes van gekose grondstowwe, lok debatte uit oor die keuse tussen voedsel- en energiesekuriteit en die toepaslikheid van sekere geïndentifiseerde sosio-ekonomiese en sosio-politieke stimulante vir ‘n lewensvatbare nywerheid. Op een of ander manier is die unieke kenmerke van Suid- Afrika en sy bronne nog nie in die debat op die knelpunte van biodiesel nie, soos beskryf in hierdie proefskrif. Die gewone prosesroetes vir kommersiële produksie van biodiesel is gebaseer op ‘n beproefde tegnologie met inherente besoedelings- en ekonomiese beperkings. Dit het gevra vir ‘n uitvoerige kritiese evaluasie van meer omgewingsvriendelike- en minder eenheidsprosesse wat meer gewensde produkte genereer, al is dit met erger prosesbepalings. By vergelyking, is dit bevind dat die homogene alkali-katalisator- alkoholisis (HAKA), ensiem-katalisator-alkoholisis (EKA) en die superkritiese-alkoholisis (SKA) prosesroetes soos in hierdie studie ontwikkel, mededingend is op ‘n totale vervaardigingskoste-vlak, as die resultate wat spruit uit geselekteerde sensiwiteitsanalises en optimiseringsstudies, aanvaar word. Die totale vervaardigings- en bedryfskostes soos beraam vir die gekose prosesroetes vir kommersiële biodieselvervaardiging vir dieselfde deursette, word oorheers deur grondstofkostes. Aansporings op afskrywings en brandstofheffings word gesien as nie effektief nie, as kostes vergelyk word met die prys van fossieldiesel op kleinhandelsvlak – Oktober 2011. Die gevolgtrekking word gemaak dat met die grondstowwe aangedui in die Strategie, kommersiële biodieselvervaardiging tans nie ekonomies gangbaar is vir Suid-Afrika nie. In hierdie studie is prosesroetes en grondstowwe geïdentifiseer wat die posisie kan verander. Kennis moet geneem word van die intensiewe navorsingsaktiwiteite op tweede-geslag tegnologieë en bioraffinaderye in die ontwikkelde wereld, soos in hierdie proefskrif bespreek.