HMF (5-hydroxymethylfurfural) is one of the bio renewable materials that can be used as an important platform chemical to produce biofuel and various chemical products. The main application of HMF in the chemical industry is a platform chemical for the production of plant-based polyethylene terephthalate (PET). HMF is produced through hexose dehydration which fructose or glucose is arranged as a feedstock. Liquid-liquid extraction can be applied in HMF production to enhance the selectivity and yield of HMF. HMF can be extracted from aqueous solution into the organic phase which prevents the degradation of HMF. Furthermore, it has been recognized that ionic liquid (IL) and deep eutectic solvent (DES) can be used as stabilizing agent in HMF production by suppressing the formation of side-products, hence increase the HMF yield as well. However, research on the systematic thermodynamics of HMF extraction is quite limited and needed to be developed. The thermodynamic data, such as phase equilibrium data and partitioning of HMF into organic phase are needed as basis for a rational design and optimal separation of HMF from the aqueous solution.
The objective of this research is systematically study the effect of biphasic system constituents on the liquid-liquid extraction of HMF at 313.15 K and atmospheric pressure (0.1 MPa). The extraction performance was evaluated based on the values of separation factor and HMF distribution coefficient which were determined from liquid-liquid equilibrium (LLE) data. The experimental LLE data of the investigated systems were also correlated well using thermodynamics models. The NRTL and UNIQUAC models were used to correlate the ternary experimental LLE data, whilst the experimental LLE data containing salt, IL, DES, and sugar were correlated using the NRTL model. We used aqueous-organic biphasic systems, and also added IL [EMIM][BF4] (1-ethyl-3-methylimidazolium tetrafluoroborate) or DES ChCl-urea (choline chloride-urea) in the aqueous phase. The effect of the addition of sugar (fructose) and salt in the variety of cation (Na+, K+) and anion (Cl-, SO4 2-) were also studied. Three different extraction solvents, methyl isobutyl ketone (MIBK), 2-pentanol, and tributyl phosphate (TBP), were used for the comparison.
According to the results in this study, it indicated that for 2-pentanol the HMF distribution coefficient is up to 1.4 times higher than MIBK. Besides, MIBK has a 2-3 times higher separation factor than 2-pentanol. While TBP is more selective as extraction solvent than the other two solvents, TBP is also superior in terms of HMF distribution coefficient. The salting-out strength of salts for organic solvent (MIBK or 2-pentanol)-HMF-water-salt systems are in the order NaCl > Na2SO4 > KCl > K2SO4. NaCl was found superior in both separation factor and distribution coefficient of HMF compared to the other salts studied. Furthermore, the separation factor and HMF distribution coefficient decreased with the increase of IL [EMIM][BF4] and DES (ChCl-urea) concentrations. However, DES (ChCl-urea) decreased the extraction performance less than IL [EMIM][BF4]. The addition of salt (NaCl) enhanced the separation factor and the distribution coefficient of HMF, enabling compensation of the IL and DES effects. The presence of salt can enhance both the extraction performance parameters up to 2-4 times for all the investigated systems studied using three different organic
solvents and also in the presence of IL or DES. While, the presence of fructose in the solution had limited effect on the extraction performance. In general, it can be inferred that by taking the advantage of IL/DES as stabilizing agent, aqueous IL/DES with NaCl is a good combination applied in HMF extraction process to achieve good extraction performance.@en

Innovation is an important determinant for success in a fast changing world. For innovation to take place, scientific knowledge that has a proven working principle needs to find an application. The process in which applications are generated or identified has been identified as an important aspect of the innovation process. However, scientific literature on application generation or identification is underdeveloped. The aim of this thesis was to develop a framework to generate or identify applications for organic molecules in a systematic way. This has been formulated into a research question as “Can a framework be developed to systematically search for applications for organic molecules?”. Before this framework for organic molecules was developed, first a general framework to generate or identify applications for technology was created. Apart from the main research question, three sub research questions are answered in this research: Can a framework to systematically search for applications for technology be developed? How can such a framework be translated to a framework for organic molecules? How can this/these framework(s) be validated? The framework was created using a design approach. The thesis draws on interviews with experts, scientific literature on application generation/identification frameworks and a discussion with experts. In the preliminary literature study, the notion that the literature on the subject of application generation or identification is underdeveloped was confirmed. The available literature provided insufficient base to build this thesis, so a design approach was taken as alternative. The first step in this approach was a series of interviews with experts on innovation and application generation/identification. With the data from these interviews, a first version of the general framework was created. This first version was validated and improved by comparing it to frameworks from literature, by conducting a second series of interviews and by a discussion with experts. The next step envisioned in the research was a translation of the general framework into a framework that can be used to generate or identify applications for organic molecules. A start was made on the translation of the framework by providing methods that can be used in subsequent research to translate the framework. The translation chapter used information from the second series of interviews as a starting point. Following this research, four recommendations were made for future research project. The first recommendation is to further develop the framework created in this research project, for example by exploring creativity methods. Secondly, it is recommended to conduct a full systematic literature review, using the vocabulary learned throughout this thesis. Thirdly, the framework created in this thesis should be translated. Before translation can take place, it has to be researched what the best method for this translation is. The translation methods provided in this thesis could be used. Alternatively, new methods for translation could be devised and implemented. Finally, in future research, several concept used in this research should be defined more carefully. Obtaining more clear and workable definitions for these concept will decrease the ambiguity of future research using these concepts. In conclusion, in this thesis, a framework to systematically generate or identify applications for technology (or rather, a concept in between scientific knowledge and technology) has been developed. Recommendations have been provided on how this framework could be further improved. On top of that, this research proposes methods for translation of this framework into a framework to systematically generate or identify applications for organic molecules. The actual translation has to take place in subsequent research.

Extractive distillation with organic solvents as entrainers is one of the most commonly used separation techniques for azeotropic mixtures in the chemical industry. To reduce the large energy requirements, and the secondary pollution problems, both of which are associated with the use of organic solvents, the search for alternative entrainers has received much attention. Recently, deep eutectic solvents that are known as green and non-volatile components have been considered as entrainers for extractive distillation processes. However, research focuses mainly on vapour-liquid equilibrium measurements, and an economic comparison with the conventional organic solvents has not been done yet. This work investigates extractive distillation with deep eutectic solvents where a conceptual process design is carried out for the separation of ethanol and water, as well as isopropanol and water with the aid of Aspen Plus as process simulator. In order to fulfil the research aim of exploring whether deep eutectic solvents reduce both cost and overall energy consumption, first, a database for the investigated deep eutectic solvents is created. Based on the effect of the deep eutectic solvents on the vapour-liquid equilibrium, choline chloride:urea (1:2) and choline chloride:triethylene glycol (1:3) are chosen for the ethanol system and isopropanol system, respectively. Subsequently, different entrainer recycle alternatives are investigated, and a sensitivity analysis of the design variables is performed. For both systems, it is found that a series of two evaporators are the most economical entrainer regeneration option. Last, a consistent comparison of the final processes with the process using the conventional organic solvents and ionic liquids is carried out. The results show that the considered deep eutectic solvents are not only beneficial in terms characteristics such as biodegradability, toxicity and selectivity, but also regarding specific energy requirements and the total annual costs. The process using conventional organic solvents is improved by at least 20.1% from an energetical perspective and by a minimum of 16.6% from an economic perspective for both systems. The replacement of ionic liquids by deep eutectic solvents also results in an energy reduction of a minimum of 6%. The additional use of heat integration further improves the final processes by 8 to 10% with respect to specific energy requirements in steam and therefore reduces the carbon footprint. Finally, it is concluded that the extractive distillation using deep eutectic solvents outperforms the process using conventional organic solvents and ionic liquids in both separations; ethanol and water, and isopropanol and water.

5-hydroxymethylfurfural (HMF) is a versatile renewable base chemical, which can be produced by the acid-catalyzed dehydration of fructose. At this time HMF cannot yet compete with oil-based analogues, such as p-xylene, due to the high costs of production. Future incentives to encourage the transition to a bio-based economy may increase the feasibility of investing in a HMF production process, but only if an efficient and cost-effective production method is designed. Previous research showed promising results using a reactive extraction unit. However, the selection of the organic solvent has a large influence on both the overall yield, as well as on the energy requirements in the final recovery of the HMF in a subsequent separation step. In this work, an intrinsically better, but hard to separate solvent, tri-butyl phosphate (TBP), was compared to methyl isobutyl ketone (MIBK), a solvent which is easy to separate from the HMF by distillation. The chosen method of separation for the TBP-HMF reaction mixture is back-extraction, using an anti-solvent to transfer the HMF back to an aqueous phase. By using backextraction, it was possible to lower the energy (steam) requirements of a TBP-based process under the benchmark calculated for a MIBK-based process by 18%. A drawback of the TBP-based process is its increased complexity, leading to higher capital costs. A model was developed to assess the balance between reduced steam demands and increased capital and operational costs. It was found that even if an optimistic scenario for the effectiveness of the anti-solvent was used, the MIBK-based process was superior across nearly all key performance indicators. Most indicative of the relative feasibility is the minimum selling price of HMF (at a production of 20 kton/year), which is €1.85/kg or €1.64/kg, for a TBP- and MIBK-based process respectively. The only area where the TBP-based process performs slightly better is sustainability, with calculated emissions of 1.90 kgCO2eq/kg HMF compared to 1.97 kgCO2eq/kg HMF for a MIBK-based process.

Economic aspects are a major player in assessing design alternatives for chemical plants. The study focusses on capital cost estimation by factorial techniques originating from the early works of Lang and Hand. A literature study is conducted on consecutively developed techniques, these are categorised and compared among others on the basis of appliance strategies, cost item inclusions and statistical backing. Similarities were observed: It was found that methods are especially proximate in estimating off-site costs and indirect costs, and systematically lack statistical analyses. The latter may be overcome in future methods with the help of cost estimation software. Quantifiable results were obtained from case study experiments with six factorial techniques applied to twelve cases. The chance that a technique successfully estimated the actual construction value, measured with reference values, appeared to be more dependent on case type than factorial method type; the database behind the method had a larger influence than factors applied.

Vibrotactile wearable devices are a non-intrusive and inexpensive means to provide haptic feedback directly on the user’s skin. These devices utilize one or multiple vibrotactile actuators to generate vibrations across the skin and into the tissue. Combining these vibrations in amplitude can create the illusion of a funneled sensation on the skin at another location than at the actual sites of stimulation. This allows for the placement of virtual actuators on the skin, such that fewer actuators need to be deployed. However, the illusion does not take into account that the waves originating from the actuator attenuate and disperse due to the viscoelastic properties of the skin. We hypothesize that this diffusion of the elastic energy in the skin is affecting the perception of this illusion. Therefore, if we correct for the wave propagation speed, and temporally focus the stimulation, we hypothesized that the specificity of the stimulation on the skin could be drastically improved. In this paper, a novel technique, which is named the inverse filter technique, was introduced that enables to focus the amplitude, frequency and phase of vibrations to one location while cancelling them at the remaining nearby positions. We developed a wearable device for the volar surface of the forearm on which we could independently control arbitrary waveforms at any position between a set of four physical actuators. A human-subject study found that the performance in terms of localization confidence was improved significantly, whereas the precision and accuracy of the task did not improve compared to when we did not correct for the wave attenuation and dispersion. These results show that focusing waves towards a target location has a direct influence on our confidence of localizing vibrotactile stimuli on the arm. Therefore, we anticipate that our findings can benefit industries int Biorefineries are considered an integral part in the transition to sustainable bio-based economies as they can convert renewable biological resources into various bio-based products, while co-products are recycled and energy is produced out of the residuals. In this thesis, it is suggested to apply this biorefinery concept to revive the sugar industry of Jamaica, where currently only raw sugar is produced. For this, the development of a conceptual process design itself and the feasibility of the implementation is studied as the entire chain of utilizing biomass is influenced by both technical, environmental, social and economic aspects. With the Technological Innovation System (TIS) framework, the information obtained during the fieldwork about how (new) technologies function in the Jamaican agricultural industry are translated into context-specific design constraints. Those design constraints are used in the development of the context-specific conceptual process design for the Jamaican sugar industry. Three scenarios of the proposed design including the material balances and financial viability are discussed. The "status-quo" scenario predicts the bankruptcy of some of the sugar factories due to the reduced possibility to sell raw sugar, which will also leave the farmers without income. The "engineering-view" scenario was found to fail due to the unrealistic assumptions that all the products can be sold, that the farming yields can be improved, and that the Jamaican sugar sector can be seen as one. In the "most-realistic" scenario, it is considered that the energy generation from bagasse covers the energy demand for the processes and that the amount of plantation white sugar, anhydrous bio-ethanol and bio-pellets annually produced from 30,000 hectares of sugarcane land are considered to be 100,000 tonnes, 51 million liters, and 80,600 tonnes, respectively. It is suggested that this "most-realistic" scenario is able to revive the Jamaican sugar industry and to support the establishment of the sustainable bio-based economy, however the financial viability of the project and the inclusiveness of the various actors have to be taken into account.erested in including localized vibrotactile feedback on the human body surface.