Thesis submitted in fulfilment of the requirements for the degree of Master of Technology: Chemical Engineering, In the Faculty of Engineering, Cape Peninsula University of Technology 2014 / Energy efficiency has become an important feature in the design of process plants due to the rising cost of energy and the more stringent environmental regulations being implemented worldwide. In South Africa as in other African countries, most of the chemical plants were built during the era of cheap energy with little emphasis placed on energy efficiency due to the abundance of cheap utility sources such as coal and crude oil. In most of these plants, there exists significant potential for substantial process heat recovery by conceptual integration of the plant’s heat exchangers. Pinch Technology (PT) has been demonstrated to be a simple and very effective technique for heat integration and process optimization. This study applies the PT approach to retrofit the heat exchangers network of the Crude Distillation Unit (CDU), of a complex petroleum refinery with the aim to reduce utilities requirement and the associated gaseous pollutants emission. This objective is accomplished by firstly conducting an energy audit of the unit to scope for potential energy saving. The existing Heat Exchanger Network (HEN) was re-designed using the remaining problem analysis (RPA) to achieve improved process energy recovery while making maximum use of the existing exchangers. The aim is to maintain the existing plant topology as much as possible. This network was later relaxed trading heat recovery with number of heat transfer unit so as to optimize the capital cost. These were implemented in AspenPlus v7.2 environment. The cost implications of the retrofitted and evolved networks including the capital and operating costs were determined on a 5 years payback time basis. The Problem Table (PT) analysis revealed that the minimum utilities requirements are 75 MW and 55 MW for the hot and cold utilities respectively. Compared to the existing utilities requirements of 103 MW for hot utility and 83 MW for cold utility, this represent a potential savings of about 26 % and 33 % savings for the hot and cold utilities respectively. The target utilities usage in the re-designed network after applying Remaining Problem Analysis (RPA) was found to be 55 MW for the cold utility and 75 MW for hot utility. The relaxed HEN required a cold utility of 62.5 MW and hot utility of 81 MW. From the total cost estimation, it was found that, although an energy saving of 34% can be achieved by the re-designed network before relaxation, the capital cost, US$ 1670000 is significantly higher than for the existing network (about US$ 980000). The final relaxed network gave an energy saving of 34% and with total cost of US$ 1100000. It was recommended from the study after cost comparisons of the four different networks (the original network, the MER network, the relaxed network and a grass-root design) that the best network for the retrofit purpose was the relaxed HEN, because there is no major shift in deviation from the topology of the original network. From the analysis it was found that a 34% saving in energy cost could be achieved from this retrofit. The Total Annual Cost (TAC) for this network gives credence to the fact that this retrofit which applied the rules of pinch analysis can bring about real saving in energy usage.

Owing to the advantages of high power density, fast charge/discharge rates as well as long lifetime, micro-supercapacitor (MSC) has drawn much attention for its potential application in miniaturized electronics. Many efforts have been devoted to the design and fabrication of high-performance MSCs. On the other hand, the integration of MSCs with multiple functional materials and devices has emerged with the development of portable and wearable microelectronics. To date, the biggest challenge in research is to develop a reliable and smart fabrication technology/strategy, which can integrate diverse objective materials into compact devices. Rolled-up nanotechnology is a unique approach to self-assemble 2D nanomembranes into 3D structures by using strain engineering. This self-assembly process smartly combines top-down and bottom-up methods to pattern functional nanomaterials into ordered 3D micro- and nanostructure arrays. One promising advantage of this approach is that such a self-assembled structure can endow micro-devices with functionality and high performance under a limited footprint area. The first part of this thesis focuses on the fabrication of planar interdigital MSCs with thermo-responsive function. Based on this work, the second part involves the research on novel tubular MSC which was fabricated by employing shapeable materials and strain engineering. A polymeric framework consisting of swelling hydrogel and polyimide layers ensures excellent ion transport between electrodes and provides efficient self-protection of the tubular MSC against external compression. Such tubular device also exhibits excellent areal capacitance, and an improved cycling stability compared to that of planar MSCs. The third part introduces the step-by-step experiments towards the fabrication and optimization of inorganic strained layer-based tubular MSC. Al2O3/Ni/Cr/Al2O3 strained nanomembrane is designed and can successfully drive the rolling up of MnO2 electrodes with a high yield under magnetic fields.:Chapter 1. Introduction 1 1.1. General background 1 1.2. Motivation of this work 2 1.2.1. Integration of micro-supercapacitors 2 1.2.2. Thermo-responsible micro-supercapacitors 2 1.2.3. 3D tubular functional micro-supercapacitors 2 1.3. Dissertation structure 3 Chapter 2. Overview of micro-supercapacitors 5 2.1. Introduction to MSCs 5 2.1.1. Capacitor 5 2.1.2. Electric double-layer capacitor 5 2.1.3. Pseudocapacitor 7 2.2. MSC configuration 8 2.3. Fabrication strategies of interdigital MSCs 9 2.4. Fabrication methods of active materials 12 2.5. Functionalization of supercapacitors 15 2.5.1. Tribo/piezoelectric driven self-charging function 15 2.5.2. Solar cell driven self-charging function 16 2.5.3. Electrochromic function 18 2.5.4. Self-healing function 19 2.5.5. Sensing function 20 2.5.6. Stretchable function 21 2.5.7. Thermo-responsive function 22 2.5.8. Photo-switchable function 23 2.6. Conclusion and outlook 23 Chapter 3. Overview of rolled-up technology 27 3.1. 3D self-assembly of the inorganic nanomembrane 27 3.1.1. Introduction 27 3.1.2. Rolled-up nanomembranes for capacitors 28 3.1.2. Rolled-up nanomembranes for Li-ion batteries 30 3.2. 3D self-assembly of the polymeric layers 32 3.2.1. Introduction 32 3.2.2. Self-assembled polymeric layers for microelectronics 35 Chapter 4. Experimental methods 39 4.1. Deposition methods 39 4.1.1. Photolithography 39 4.1.2. Electron beam evaporation 39 4.1.3. Atomic layer deposition 40 4.1.4. Electrochemical deposition 41 4.2. Characterization methods 43 4.2.1. Scanning electron microscopy and focused ion beam milling 43 4.2.2. Electrochemical characterization 43 Chapter 5. An integrated MSC with thermo-responsible function 47 5.1. Introduction 47 5.2. Fabrication and characterization of thermo-responsible MSCs 47 5.2.1. Single thermo-responsible MSCs 47 5.2.2. The array of thermo-responsible MSC 51 5.3. Conclusion 53 Chapter 6. Self-assembly of 3D tubular MSCs 55 6.1. Introduction 55 6.2. Fabrication of tubular MSCs 57 6.2.1. Diagram of processing flow 57 6.2.2. Polymeric layer stack 58 6.2.3. Microelectrodes, self-assembly and capsulation 59 6.3. Results and discussion 60 6.3.1. On-chip and free-standing sample morphology 60 6.3.2. Electrochemical characterization of tubular MSCs 64 6.3.3. Self-protection function of tubular structures 72 6.3.4. Assembly of tubular structures in series/parallel 76 6.4. Conclusion 80 Chapter 7. Tubular nanomembranes for MSCs 81 7.1. Introduction 81 7.2. Self-assembly of Al2O3/Ti/Cr/Al2O3 strained nanomembranes 82 7.2.1. Fabrication method 82 7.2.2. Results and discussion 83 7.3. Self-assembly of Al2O3/Ni/Cr/Al2O3 strained nanomembranes 87 7.3.1. Fabrication method 87 7.3.2. Results and discussion 88 7.4. Conclusion 92 Chapter 8. Summary and outlook 93 8.1. Summary 93 8.2. Outlook 94 Bibliography 95 List of Figures 109 List of Tables 117 Theses 119 Acknowledgment 121 Publications and presentations 123 Curriculum Vita 125

D. Tech. Industrial Engineering. / Discusses purpose of this study is to derive a new model capable of advanced diagnosis and analysis of energy usage to determine the possible energy efficiency potential through the following in a single model: Analysis of industrial historical data; Prediction of the industrial energy baseline; Computation of the industrial energy efficiency; and Optimization of the industrial energy consumption usage. In this context, the development of a new model involves: Carrying out literature survey; Carrying out Mathematical Analysis of the dynamics of energy efficiency in an industry; Critically analyzing and testing existing models; Evolve a new and novel model; Test the model using data from specific industry; Apply the model to eleven industrial sectors in South Africa. This thesis on energy efficiency potential will be a milestone for different stakeholders, policymakers and decision makers in the energy sector at national and international levels who are, or will be interested in reducing energy input and still produce the observed output levels, by becoming technically efficient. The approach adopted by the study is the integration of Index Decomposition Analysis (IDA), Artificial Neural Network (ANN) and Data Envelopment Analysis (DEA) into a single model.This methodology combines modeling, which is at the core of an energy-management technique, with a wider interpretation of activity growth, structure and efficiency changes which contribute to changes in energy consumption.