The effects of changes in temperature, mobile phase composition, flow rate, and stationary phase upon the enantiomeric separation of several racemic mixtures are investigated. The changes in capacity factor (k'), selectivity (α), and efficiency (N) and enantiomeric resolution (R), are explored. Resolution is then shown to be controlled by the specific combination of chiral stationary phase (CSP), solute, mobile phase and temperature. The key to optimizing chiral resolution lies in understanding the retention mechanism(s) for a given CSP. The proposed retention mechanisms for the two CSP used in the optimization studies are evaluated using chromatographic/thermodynamic data. Inferences are made which support the well-characterized "Pirkle"-type R-dinitrobenzoylphenylglycine retention mechanism, which depends solely on attractive-repulsive interactions to establish two diasteriomeric complexes having unequal internal energy, and therefore eluting at different times from the chromatographic system. For comparison, a more complicated CSP composed of a tris cellulose(3,5- dimethylphenylcarbamate) coated to a silica gel support is also examined. For this CSP the proposed mechanisms, which include both attractive-repulsive interactions and inclusion complex types, are evaluated according to the chromatographic optimization data, and compared to similar data for the single-mechanism "Pirkle" CSP. In contrast to the above"macromolecular"-level inferences about retention mechanisms drawn from chromatographic data, a second study was initiated using a model CSP attached to a l000-Å gold surface, with Fourier-Transform Infrared Spectrometry in a Reflectance-Absorbance mode, to probe the specific molecular interactions which make possible the diasteriomeric complex. This <i>in situ</i> experiment, in contrast to previous <i>ex situ</i>, stationary phase work, is designed to show that hydrogen bonding is, as predicted, a principal force holding the complexes together, and that a measurable difference exists between the weaker R-trifluoroanthrylethanol (TFAE) and the stronger S-TFAE complexes due to their different stereo-geometry. A further experiment to characterize the difference in mechanisms between the "Pirkle" and cellulose CSPs involves relating their chromatographic retention behavior to their structure, known as Qualitative Structure Retention Relationships (QSRR). Some structure-specific physical-organic chemistry parameters are determined using an EPA-developed computer program and correlations are made between retention on a given CSP and some of the parameters. / Ph. D.

Three rain events were sampled from a storm drain at Manassas Mall in Manassas, Virginia. The urban runoff samples obtained were placed into lab-scale Plexiglas~ settling columns to monitor removal of total hydrocarbons (THC) by extended quiescent settling. Samples were collected from the columns at specific depths and times over the 48-hour settling period. The samples were analyzed for total hydrocarbon content on a Horiba oil content analyzer. Hydrocarbon values were averaged at each column depth in order to construct average THC concentration and average THC percent removal profiles over settling time. Maximum average THC removals were 77.8%,32.5%, and 73.6%, respectively, for Storms #1, 2, and 3 after 48 hours of quiescent settling. These average removals corresponded to depths of -2 feet, -1 foot, and -3 feet in the 5-foot tall columns. According to traditional sedimentation theory, pollutants settle out of water to the bottom of the container of interest. This did not appear to be solely the case in this hydrocarbon sedimentation study. It appeared that sedimentation was not the sole removal mechanism at work. Some fractions of oil and grease seemed to reorganize into low-density sub-groups and float to upper regions of the column. Also, the majority of THe removal occurred within the first 18 hours of settling for two of the three storms sampled. / Master of Science

Expert systems are being used more daily in chemical engineering. This work continues the development of an EXpert system for SEParation flowsheet synthesis named EXSEP. Written in Prolog, it can generate flowsheets for four multicomponent separations: distillation, absorption, stripping and liquid-liquid extraction. For these separations, we describe a large collection of heuristics (or rules) that are used for flowsheet synthesis. EXSEP uses several of these heuristics and the Kremser equation to test the thermodynamic feasibility of separation tasks. EXSEP requires only basic input data such as the expected component flow rates in each product and the component K-values. With those data, EXSEP searches for the sets of the number of theoretical stages, solvent flow rate, and component-recovery ratios that characterize a number of feasible and economical flowsheets. The use of the component assignment matrix (CAM) combined with Prolog list processing makes EXSEP very fast (several seconds) to generate solutions. We test EXSEP with several examples of industrial separation processes and compare the results with the literature. We also compare EXSEP results with rigorous simulations using commercial CAD software (e.g., DESIGN II). In most cases, EXSEP gives very similar and even better flowsheets. However, EXSEP is limited to dilute solvent-based separations and cannot solve problems where the major feed component is also the solvent (e.g. sour-water steam stripper). The development of EXSEP on IBM-PC makes it very "user friendly". In the future, EXSEP should be expanded with additional modules such as extractive and azeotropic distillation, and bulk absorption. It should also include modules for separation method and solvent selections, which are great challenges in flowsheet synthesis. / Master of Science

Thesis (MScMedSc)-- Stellenbosch University, 2013. / ENGLISH ABSTRACT: Preconceptual sex selection is an ethically justifiable process whereby X- and Y-chromosome bearing spermatozoa are isolated prior to fertilization of the oocyte in order to generate either a male or a female offspring. Although various separation techniques are available, none can guarantee 100% accuracy. There are various physiological differences between X- and Y-chromosome bearing spermatozoa which can be used to separate these two populations of sperm. For the purpose of this study, X- and Y-chromosome bearing spermatozoa were separated based on (1) their respective abilities to remain viable when subjected to adverse environments, including extreme pH values, increased temperatures and various hydrogen peroxide (H2O2) concentrations; (2) the ability of Y-chromosome bearing spermatozoa to swim faster and/or more progressively than X-chromosome bearing spermatozoa; and (3) the X-chromosome bearing spermatozoa’s increased size and weight when compared to the Y-chromosome bearing spermatozoa. The efficacy of live and dead cell separation through (i) Magnetic Antibody Cell Separation (MACS) and (ii) a modified swim-up technique was also assessed and compared. Changes in the sex-chromosome ratio of samples were established by double-label fluorescent in situ hybridization (FISH) before and after processing. Sperm motility (CASA) and viability (eosin/nigrosin) was assessed before and after each intervention. Ethical clearance for this study was granted by the Health Research Ethics Committee 1 (Ethics #: S13/04/068). The results indicated successful enrichment of X-chromosome bearing spermatozoa upon incubation in acidic media, increased temperatures, and H2O2. In contrast, Y-chromosome bearing spermatozoa were successfully enriched through a direct swim-up method as well as discontinuous gradient centrifugation. In conclusion, this study demonstrated the potential role for physiological differences between X- and Y-chromosome bearing spermatozoa in the development of preconceptual gender selection through sperm sorting. / AFRIKAANSE OPSOMMING: Prekonsepsie geslagselektering is 'n eties regverdigbare proses waardeur X- en Y- chromosoom draende spermatosoë geïsoleer word voordat bevrugting van die oösiet plaasvind, om óf 'n manlike óf 'n vroulike nageslag te genereer. Alhoewel verskeie skeidingstegnieke beskikbaar is, kan geeneen 100% akkuraatheid waarborg nie. Daar bestaan verskeie fisiologiese verskille tussen X- en Y- chromosoom draende spermatosoë wat skeiding van hierdie twee groepe spermatosoë moontlik kan maak. Vir die doel van hierdie studie is skeidingsmetodes vir die X- en Y- chromosoom draede spermatosoë gebaseer op (1) hul onderskeie vermoëns om lewensvatbaar te bly tydens blootstelling aan ‘n ongunstige milieu, insluitend ekstreme pH waardes, verhoogde temperature en verskeie waterstofperoksied (H2O2) konsentrasies; (2) die vermoë van die Y-chromosoom draende spermatosoon om vinniger en/of meer progressief as X-chromosoom draende spermatosoë te swem; en (3 ) die X-chromosoom draende spermatosoon se verhoogde grootte en gewig in vergelyking met die Y- chromosoom draende spermatosoon. Die effektiwiteit van die (i) Magnetiese Anti-liggaam Sel Skeidingstegniek (MACS) en (ii) 'n aangepaste weergawe van die op-swem tegniek om lewendige en dooie selle te skei is ook bepaal en vergelyk. Veranderinge in die geslagschromosoom verhouding van die monsters is bepaal deur dubbel-etiket fluoresensie in situ hibridisering (FISH) voor en na verwerking. Spermmotiliteit (CASA) en lewensvatbaarheid (eosien/nigrosin) is bepaal voor en na elke intervensie. Etiese goedkeuring vir hierdie studie is verleen deur die Gesondheids-Navorsingsetiekkomitee 1 (Etiese # : S13/04/068). Die resultate dui suksesvolle verryking van X-chromosoom draende spermatosoë deur inkubasie in suur media, verhoogde temperature, en H2O2. Y-chromosoom draende spermatosoë is verryk deur middel van 'n direkte op-swem metode sowel as diskontinue gradiënt sentrifugering . Ten slotte, hierdie studie toon die potensiële rol vir fisiologiese verskille tussen X- en Y- chromosoom draende spermatosoë in die ontwikkeling van prekonsepsie geslagselektering metodes deur skeiding van X- en Y-chromosoom draende sperme.

A waste acid stream is being produced by a local petrochemical company (SASOL) at a rate of 10 000 -12 000 tons per annum and contains approximately 44-mole % butyric acid, 20 % isobutyric acid and 10 % valeric acid. Whilst this stream is currently being incinerated, SASOL has requested an investigation into the possibility of separating and purifying butyric acid and isobutyric acid from this waste acid stream. The goal of this project was to determine a separation and purification route for butyric acid and isobutyric acid from SASOL'S waste acid stream. In order to achieve this, vacuum distillation and freeze crystallization were chosen for the recovery and purification of the acids respectively. Vapour-liquid equilibrium data for key component pairs present in the waste acid stream (propionic acid + butyric acid, isobutyric acid + butyric acid, butyric acid + isovaleric acid and butyric acid + hexanoic acid) were experimentally determined in a dynamic VLE still. The measured VLE data was successfully correlated us ing the gamma-phi approach. with the NRTL activity coefficient model representing the liquid phase and the virial equation of state describing the vapour phase. Using these equations. the VLE data obtained from the experimental work was then regressed to provide interaction coefficients for the NRTL model. which were then used in the Hysys process simulator to explore a range of design alternatives for distillation. Hysys simulations showed that greater than 80 % butyric acid and isobutyric acid can be recovered from the waste acid stream in a single distillation column containing 18 theoretical stages and an optimum reflux ratio of 3.8. The simulation was performed at a pressure of 58kPa and a maximum operating tempe rature of 150°C. Batch distillation experiments performed in a batch rectification column at 250kPa recovered more than 90% of both the butyric acid and isobutyric acid from a 450ml sample of the waste acid stream. A subsequent batch experiment concentrated the recovered acids into a distillate containing more than 95 % butyric acid and isobutyric acid combined. To investigate freeze crystallization as a suitable operation for purifying butyric acid and isobutyric acid a solid-liquid phase equilibrium curve for the system was generated us ing the Van Hoft equation. The generated curve showed that butyric acid and isobutyric acid could be theoretically purified (>98%) by operating two crystallizers at -20°C and -55°C respectively. A simple freeze crystallization experiment produced butyric acid with greater than 94% purity. An economic feasibility study conducted on the process showed that separation and purification of the acids by this process (distillation and crystallization) could create a business opportunity with revenue of approximately R47 million per annum. Preliminary estimates for capital investment amounted to approximately R5.4 million. for which the payback period was estimated at less than one year. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2001.

Abstract not available

Metal-organic frameworks are a new class of porous materials that have potential applications in gas storage, separations, catalysis, sensors, non-linear optics, displays and electroluminescent devices. They are synthesized in a "building-block" approach by self-assembly of metal or metal-oxide vertices interconnected by rigid linker molecules. The highly ordered nature of MOF materials and the ability to tailor the framework's chemical functionality by modifying the organic ligands give the materials great potential for high efficiency adsorbents. In particular, MOFs that selectively adsorb CO₂ over N₂, and CH₄ are very important because they have the potential to reduce carbon emissions from coal-fired power plants and substantially diminish the cost of natural gas production. Despite their importance, MOFs that show high selective gas adsorption behavior are not so common. Development of MOFs for gas adsorption applications has been hindered by the lack of fundamental understanding of the interactions between the host-guest systems. Knowledge of how adsorbates bind to the material, and if so where and through which interaction, as well as how different species in adsorbed mixture compete and interact with the adsorption sites is a prerequisite for considering MOFs for adsorptive gas separation applications. In this work, we seek to understand the role of structural features (such as pore sizes, open metal site, functionalized ligands, pore volume, electrostatics) on the adsorptive separation of CO₂, CO and N₂ in prototype MOFs with the help of molecular modeling studies (GCMC simulations). Our simulation results suggest that the suitable MOFs for CO₂ adsorption and separation should have small size, open metal site, or large pore volume with functionalized groups. Some of the experimental challenges in the MOF based adsorbents for CO₂ capture include designing MOFs with smaller pores with/without open metal sites. Constructing such type of porous MOFs can lead to greater CO₂ capacities and adsorption selectivities over mixtures of CH₄ or N₂. Therefore, in the second project, we focused on design and development of small pore MOFs with/without open metal sites for adsorptive separation of carbon dioxide from binary mixtures of methane and nitrogen. We have synthesized and characterized several new MOFs (single ligand and mixed ligand MOFs) using different characterization techniques like single-crystal X-ray diffraction, powder X-ray diffraction, TGA, BET, gravimetric adsorption and examined their applicability in CO₂/N₂ and CO₂/CH₄ mixture separations. Our findings from this study suggest that further, rational development of new MOF compounds for CO₂ capture applications should focus on enriching open metal sites, increasing the pore volume, and minimizing the size of large pores. Flue gas streams and natural gas streams containing CO₂ are often saturated by water and its presence greatly reduces the CO₂ adsorption capacities and selectivities. So, in the third project, we investigated the structural stability of the developed MOFs by measuring water vapor adsorption isotherms on them at different humid conditions to understand which type of coordination environment in MOFs can resist humid environments. The results of this study suggest that MOFs connected through nitrogen-bearing ligands show greater water stability than materials constructed solely through carboxylic acid groups.

Robust industrially relevant membranes for CO₂ removal from aggressive natural gas feed streams were developed and characterized. Asymmetric hollow fiber membranes with defect-free selective skin layers on an optimized porous support substructure were successfully spun and subsequently stabilized by covalent crosslinking within the economical membrane formation process. Thermal treatment conditions, which promote sufficient crosslinking without introducing defects or undesired substructure resistance, were identified. It was found that crosslinking improves membrane efficiency and plasticization resistance as well as mechanical strength of fibers. The capability to maintain attractive separation performance under realistic operating conditions and durability against deleterious impurities suggests that the crosslinked fibers have great potential for use in diverse aggressive applications, even beyond the CO₂/CH₄ example explored in this work.

Adsorption separation processes are extremely important to the chemical industry, especially in the manufacturing of food, pharmaceutical, and fine chemical products. This work addresses three main topics: first, systematic decision-making between rival gas phase adsorption processes for the same separation problem; second, process development for liquid phase simulated moving bed chromatography (SMB); third, accelerated startup for SMB units. All of the work in this thesis uses model-based optimization to answer complicated questions about process selection, process development, and control of transient operation. It is shown in this thesis that there is a trade-off between productivity and product recovery in the gaseous separation of enantiomers using SMB and pressure swing adsorption (PSA). These processes are considered as rivals for the same separation problem and it is found that each process has a particular advantage that may be exploited depending on the production goals and economics. The processes are compared on a fair basis of equal capitol investment and the same multi-objective optimization problem is solved with equal constraints on the operating parameters. Secondly, this thesis demonstrates by experiment a systematic algorithm for SMB process development that utilizes dynamic optimization, transient experimental data, and parameter estimation to arrive at optimal operating conditions for a new separation problem in a matter of hours. Comparatively, the conventional process development for SMB relies on careful system characterization using single-column experiments, and manual tuning of operating parameters, that may take days and weeks. The optimal operating conditions that are found by this new method ensure both high purity constraints and optimal productivity are satisfied. The proposed algorithm proceeds until the SMB process is optimized without manual tuning. In some case studies, it is shown with both linear and nonlinear isotherm systems that the optimal performance can be reached in only two changes of operating conditions following the proposed algorithm. Finally, it is shown experimentally that the startup time for a real SMB unit is significantly reduced by solving model-based startup optimization problems using the SMB model developed from the proposed algorithm. The startup acceleration with purity constraints is shown to be successful at reducing the startup time by about 44%, and it is confirmed that the product purities are maintained during the operation. Significant cost savings in terms of decreased processing time and increased average product concentration can be attained using a relatively simple startup acceleration strategy.

Along with knowledge of the interactions unique to microscale devices, designers of microelectromechanical systems (MEMS) require information about complex fabrication and packaging techniques in order to fully complete a successful design. To that end, the successful design of MEMS requires the collaboration of experts and designers in a variety of engineering fields. From the decision-based design perspective, MEMS designers require a means to sort the input and information generated in a collaborative design process. While the potential for the use of languages and part libraries have been addressed in the literature as a means to solve this problem, a means to embody these principles has not been addressed. The use of modular, executable, decision-centric templates to rapidly compose, solve, archive, and reuse compromise Decision Support Problems (cDSP) for specific design problems has been proposed in the literature. The result of this work is a means of separating procedural design knowledge from declarative knowledge and parsing the cDSP into a set of computer-interpretable templates. A stated need in this work is the extension of the templates to accommodate the coupled solution of two cDSPs utilizing game theoretic principles. In this thesis, the theoretical structures of decision-centric templates are applied to the needs of MEMS designers. Computer interpretable, decision-centric templates, used to save, reuse, and aid in design decisions, are extended to permit MEMS designers and fabricators to collaborate via coupled cDSPs, using game theoretic principles of cooperative, noncooperative, and leader-follower games. This approach is illustrated through its application to the design and prototype fabrication of microscale gas chromatography separation channels. The outcome of this work is twofold: first, MEMS designers and fabricators will have a means to compose, collaboratively solve, archive, and reuse compromise Decision Support Problems in a computer interpretable manner, and second, decision templates will be extended through the use of game theoretic principles.