Thesis (PhD)--University of Stellenbosch, 2002. / ENGLISH ABSTRACT: This study describes the design, construction, complete industrialisation and operation of a dual bed vacuum swing adsorption (VSA) demonstration plant, which operates at atmospheric and sub-atmospheric conditions. All design objectives as set out initially were met. The plant removes contaminants such as methanol and water from neutral wine spirit. Neutral wine spirit is a key component of various local and international spirituous products which include liqueurs, gin, vodka, fortified wines and brandy. Neutral wine spirit can chemically be described as the azeotropic mixture of ethanol and water, which occurs at an ethanol content of 96.4 vol. %. Methanol is naturally present in all products from the vine. Fermentation and distillation concentrate methanol even more, and due to physical and chemical characteristics, its separation consumes as much as 45 % of total production costs. Neutral wine spirit is produced by the proven technology of continuous atmospheric distillation. Continuous improvement of the distillation process is limited due to the physical constraints of an old facility, but also due to previous design philosophies and approaches. The VSA plant consists of two adsorbers, packed to a total height of 1.71 m and a diameter of 0.4 m. Adsorption took place at 100 °C and regeneration at the same bed temperature with purified nitrogen gas at 170 °C and a vacuum of 17 kPa (abs). Experiments were divided into Group I and Group II experiments. Group I investigated the ability to separate methanol and water from the azeotrope and to which efficiency it occurred. It consisted of 120 adsorption cycles of 5 minutes each and 60 samples were drawn for analyses. Breakthrough was not allowed to occur. The azeotropic feed was consistently dehydrated to a water content < 0.05 wt %, while methanol was reduced to < 4 mg/100mLAA. The type of 3A molecular sieve (MS 564 CS) was specifically selected to ensure analytic as well as organoleptic compliance with the product specification. Molecular sieve 4A was removed due to organoleptic problems with the product. Group" experiments were performed in the format of a sensitivity analysis. The effects of various process parameters on the methanol breakthrough curves were individually assessed. Eighteen experiments were performed over a period of 8 days, with 86 samples drawn. The duration of an adsorption cycle was 30 minutes, allowing methanol breakthrough to occur. Water was preferentially adsorbed. Negative methanol bed loadings during high water loadings confirmed that water was able to displace methanol molecules. In the presence of water, molecular sieve 3A was capable of adsorbing 0.6 mg methanol/100mLAA, while in the absence of water with synthetically dosed methanol, molecular sieve 3A achieved a maximum loading of 12.3 mg methanol/100mLAA. The latter corresponded with a maximum methanol feed content of 1118 mg/100mLAA. In general, quicker breakthrough occurred at higher flow rates and feed concentrations. Continuous breakthrough caused bed contamination and a 24-hour thermal regeneration was performed following experiment 12. The feed flow rate was increased from the theoretical 50 f/hr to 70 f/hr without any additional capital layout. Selected process conditions were found to be effective in continuously separating methanol from ethanol. Depending on the strategy of integration, profitability studies shows a Return on Investment of between 110.1% - 220.8% for the adsorption project. Adsorption is superior to distillation in the separation of methanol. Due to the level of innovation involved, it is recommended that the contents of this study remain confidential and patent protection is to be extended. This dissertation speaks to both the wine making as well as the chemical engineering fraternity. It seeks to provide credibility to both parties, by clarifying the unknown issues fundamental to the respective disciplines. / AFRIKAANSE OPSOMMING: Hierdie studie definieer die ontwerp, vervaardiging en volledige industrialisasie van 'n dubbelbed vakuum adsorpsie demonstrasie aanleg (VSA) wat by atmosferiese en sub-atmosferiese kondisies bedryf word. Alle ontwerpsdoelwitte is bereik. Die aanleg verwyder selektief metanol en water vanuit neutrale wynspiritus. Neutrale wynspiritus is 'n sleutelkomponent van verskeie spiritualieë in die plaaslike en internasionale wyn en spiritus bedryf. Hierdie produkte sluit in likeurs, jenewer, vodka, gefortifiseerde wyne en brandewyn. Chemies, kan neutrale wynspiritus beskryf word as die azeotropiese mengsel van etanol en water teen 96.4 vol. %. Metanol het 'n natuurlike teenwoordigheid in alle produkte vanaf die wynstok. Gisting en distillasie konsentreer metanol tot 'n hoër mate en weens fisiese en chemiese eienskappe word metanol teen hoë koste vanaf die etanol stroom geskei. Die metanol verwyderingskomponent beloop soveel as 45 % van die produksiekoste van die totale proses. Neutrale wynspiritus word deur die gevestigde tegnologie van kontinue atmosferiese distillasie geproduseer. Kontinue verbetering van die proses word beperk deur die fisiese ouderdom en toestand van die fasiliteite, maar is ongelukkig ook die resultaat van vorige ontwerpsfilosofieë en benaderings. Die adsorbeerders is gepak tot 'n hoogte van 1.71 m met 'n deursnit van 0.4 m. Adsorpsie het by 100°C plaasgevind en regenerasie by dieselfde bedtemperatuur met stikstofgas by 170°C en 'n vakuum van 17 kPa (abs). Eksperimentele werk is in Groep I en Groep II eksperimente verdeel. Groep I het die effektiewe prosesvermoë om metanol en water vanuit die azeotroop te verwyder ondersoek. Dit het bestaan uit 120 adsorpsie siklusse van 5 minute elk. Sestig monsters is getrek vir analise. Deurbreek van metanol was nie toe gelaat om plaas te vind nie. Die azeotropiese toevoer is konsekwent tot 'n water inhoud < 0.05 massa % gedehidrateer is. 'n Metanol inhoud < 4 mg/100 mLAA is bereik. Die tipe 3A molekulêre sif (MS 564 CS) was spesifiek vir die toepassing geselekteer om sodoende 'n analities sowel as organolepties aanvaarbare produk te lewer. Molekulêre sif 4A was verwyder weens die vorming van produk wangeure. Groep II eksperimente is in die vorm van 'n sensitiwiteits analise uitgevoer. Die effek van verskeie veranderlikes is individueel op die metanol deurbreekkurwe getoets. Agtien eksperimente is oor 'n tydperk van 8 dae gedoen, met 'n totaal van 86 monsters wat getrek is. 'n Adsorpsie siklus het 30 minute geduur en het deurbreek van metanol toegelaat. Water is by voorkeur geadsorbeer. Negatiewe metanol bed ladings tydens hoë waterteenwoordigheid toon dat water wel metanolmolekule op 'n adsorpsie-posisie kan verplaas. In die teenwoordigheid van water is 'n bedlading van 0.6 mg metanol/100mLAA verkry, met 'n maksimum van 12.3 mg metanol/100mLAA in die afwesigheid van water. Laasgenoemde verteenwoordig 'n toevoer met 'n metanol inhoud van 1118 mg/100mLAA. In die algemeen is gevind dat 'n toename in toevoer vloeitempo en konsentrasie die tyd vir deurbreek verkort. Kontinue deurbreek het kontaminasie van die bed teweeg gebring en 'n termiese regenerasie is vir 24 ure na eksperiment 12 gedoen. Die teoretiese ontwerps vloeitempo was 50 .elhr, maar resultate het getoon dat die aanleg tot 70 .t'/hr kan verwerk sonder addisionele koste. Die geselekteerde proseskondisies was effektief in die versekering van die kontinue skeiding van metanol en etanol. Die lewensvatbaarheidstudie toon, afhangende van die strategie van integrasie, 'n Opbrengs op Belegging van tussen 110.1% - 220.8%. Adsorpsie het 'n beter skeidingsvermoë as konvensionele distillasie vir die verwydering van metanol vanuit etanol. Weens die vlak van innovasie betrokke, word dit voorgestel dat die inhoud van hierdie studie vertroulik gehou word en dat patent beskerming verleng sal word. Hierdie verhandeling spreek tot beide die wynmaak sowel as chemiese ingenieurs dissiplines. Daar is gepoog om geloofwaardigheid vir beide partye te skep deur die onbekende aspekte van albei dissiplines aan te spreek.

Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: In this study, two novel ligands were synthesized and separately two crown ether derivatives were all immobilized onto four different silica substrates. These immobilized ligand systems were used to extract six different metal and metalloid ions in water. The extraction capacity of the different immobilized ligands was compared with each other to determine whether the substrates had any influence on the extraction capabilities of these ligands. After the extraction experiments, recovery of the immobilized ligands was attempted by re-protonating the ligands so as to displace the metal ions. Two free parent ligands, 1,4,7-tris-[(S)-2-hydroxypropyl]-1,4,7-tri-azacyclodecane (THTD) and 1,4,8-tris-[(S)-2-hydroxypropyl]-1,4,8-tri-azacycloundecane (THTUD), were synthesized. Previous formation constant data indicated that THTD and THTUD form very stable complexes with Cd2+ which should make these ligands ideal for the extraction of Cd2+. These two ligands are less symmetric due to the carbon bridges between the nitrogen atoms, which differ in length. This gives the ligands the special feature that they can form five - and six membered rings during complexation with the metal ions. The ligands were fully characterized by NMR, mass spectrometry and elemental analysis. Characterization of the silica substrates was done using BET, low angle X-ray diffraction and FTIR. MCM-41 has the highest surface area, followed by SBA-15, Si gel (60 Å) and HMS. Although MCM-41 has the largest surface area, it was not the best support to use. HMS and Si gel (60 Å) have the smallest and almost identical surface areas. Yet, Si gel (60 Å) was a far better support to use than HMS, and even better than MCM-41. The worst supports were SBA-15 and HMS. A spacer, 3-Glycidyloxypropyl-trimethoxysilane (glymo), was introduced to immobilize the ligands to the silica substrates. Solid state NMR and FTIR analysis confirmed that the spacer could indeed be successfully immobilized on the various silica supports. The immobilized ligands were fully characterized with the use of solid state NMR and FTIR. The thermal stability of the immobilized ligands was determined by means of TGA. The immobilized ligands are stable up to 200ºC where after they started to disintegrate. According to literature, 15-crown-5 and 18-crown-6 are suitable ligands for the extraction of Sr2+ and UO22+. Since these ligands were to be immobilized, (2-aminomethyl)-15-crown-5 and (2-aminomethyl)-18-crown-6 were used because of the amino group that can be used as an anchor for immobilization. To immobilize these ligands onto the activated silica substrates, two methods were used: 1) directly onto the substrate by using the amino groups at the end of the carbon arm and 2) by means of the glymo spacer which connects the (2-aminomethyl)-15-crown-5 and (2-aminomethyl)-18-crown-6 to the silica substrates. The immobilization was confirmed and the ligand-substrate moiety fully characterized by solid state NMR and FTIR. The thermal stability of the immobilized crown ethers was determined by means of TGA as stable up to 200ºC where after they disintegrated. Extraction experiments were conducted at 25ºC and atmospheric pressure. The extractions were done at pH values of 4.5 and 5.9. The extraction capacity of the immobilized ligands was determined by ICP analysis. As expected, the extraction done at pH 5.9 was significantly better than at pH 4.5. Cr6+ was the best-extracted metal ion. The best extraction results were obtained with Si gel (60 Å) as support. It was also noticeable that the extraction capacity increased with a spacer added to the support, except for the extraction of UO22+. Better extraction for the uranyl was obtained using the 15-crown-5 and 18-crown-6 immobilized directly onto the supports, rather than with a spacer added. Recovery of the metal ions and the immobilized ligands was attempted, but without success. This aspect will be examined again in future work. In conclusion, ligands were successfully synthesized and immobilized. These immobilized ligands produced moderate extraction results with a number of metal ions from aqueous solution. / AFRIKAANSE OPSOMMING: Hierdie studie behels die sintetisering van 2 nuwe ligande en die immobilisering daarvan, te same met 2 kroon eters, op vier verskillende silika substrate. Die geïmobiliseerde ligande is gebruik vir die ekstraksie van verskillende metaal - en metaloied ione uit water. Die ekstraksie kapasiteit van die onderskeie geïmobiliseerde ligande is vergelyk om te bepaal of die substrate ‘n uitwerking op die ekstraksie vermoeë van die ligande het. Herwinnings eksperimente is uitgevoer deur die verplasing van die geadsordeerde metaal ione deur middel van reprotonasie van die ligande. Twee nuwe azamakrosikliese basis ligande, 1,4,7-tris-[(S)-2-hidroksipropiel]-1,4,7-tri-azasiklodekaan (THTD) en 1,4,8-tris-[(S)-2-hidroksipropiel]-1,4,8-tri-azasikloundekaan (THTUD), is gesintetiseer. Vormings konstante data dui daarop dat THTD en THTUD uiters stabiele komplekse met Cd2+ vorm wat hierdie ligande dus geskik behoort te maak vir die ekstraksie van Cd2+. Die twee ligande toon ook ‘n mindere mate van simmetrie as gevolg van die verskillende lengtes van die koolstof brûe tussen die stikstof atome. Hierdie eienskap verskaf aan die ligande die moontlikheid om beide vyf- en sesledige ringe vorm tydens kompleksering met die metaal ione. Die ligande is ten volle gekarakteriseer deur middel van KMR-metings, massa-spekstroskopie en element analise. Karakterisering van die silika substrate [Si gel (60 Å), MCM-41, SBA-15, and HMS] sluit in BET, lae hoek X-straaldiffraksie en FTIR. MCM-41 het die grootste oppervlakte, gevolg deur SBA-15, Si gel (60 Å) en HMS. Ten spyte van die feit dat MCM-41 die grootste oppervlakte het, was dit egter nie die beste subtraat om te gebruik nie. Die interne areas van die uiters groot porie-oppervlaktes van MCM-41 is nie toeganklik vir immobilisering nie a.g.v. die uiter klein porie-openinge. Si gel (60 Å) en HMS het die kleinste oppervlak areas. Si gel (60 Å) is ‘n baie beter substraat om te gebruik as HMS, en selfs ook beter as MCM-41 aangesien die totale oppervlakte van die Si gel (60 Å) gebruik kan word. Die mees ongeskikte substrate was SBA-15 en HMS. Die alreeds klein oppervlak areas word verder “verklein” a.g.v. die klein porie openinge wat die interne oppervlekte van die porieë ontoegangklik maak. ‘n Verbinder, 3-Glysidieloksipropiel-trimetoksisilaan (glymo) is gebruik om die ligande op die silika substrate te immobiliseer. Vaste toestand KMR en FTIR analise het bevestig dat die verbinder suksesvol geïmmobiliseer is op die onderskeie silika substrate. Die geïmmobiliseerde aza makrosikliese ligande is ten volle gekarakteriseer deur vaste toestand KMR en FTIR. Die termiese stabiliteit is bepaal d.m.v GTA en die geïmmobiliseerde ligande is stabiel tot 250ºC. Die basis ligande 15-kroon-5 an 18-kroon-6 is uiters geskik vir die ekstraksie van Sr2+ en UO22+. Om hierdie kroon eters te immobiliseer, is (2-aninometiel)-15-kroon-5 en (2-aninometiel)-18-kroon-6 gebruik. Die amino groep dien as anker vir die immobilisering. Twee metodes van immobilisering op silika is gebruik: 1) direkte immobilisering op die substraat en 2) immobilisering d.m.v. die glymo verbinder. Die immobilisering is bevestig en die ligand-substraat funksionel groep is gekarakteriseer d.m.v. vaste toestand KMR en FTIR. Die termiese stabiliteit van die geïmmobiliseerde kroon eters is bepaal d.m.v. GTA en is stabiel tot 200ºC. Ekstraksie eksperimente is uitgevoer by 25ºC en atmosferiese druk. Die ekstraksies is uitgevoer by pH waardes van 4.5 en 5.9. Die adsorpsie kapasiteit van die geïmmobiliseerde ligande is bepaal d.m.v. IGP analise. Soos verwag is die ekstraksie by pH 5.9 beter as by pH 4.5. Cr6+ ekstrksie was die hoogste met al die die ligande geïmmobiliseerd op die onderskeie substrate. Si gel (60 Å) was die beste substraat om te gebruik. Die ekstraksie kapasiteit van al die metaal ione het verbeter met die toevoeging van ‘n verbinder, behalwe vir UO22+. Beter ekstraksie van die UO22+ is verkry met die gebruik van die kroon eters wat direk op die substrate geïmmobiliseer is, eerder as met ‘n verbinder toegevoeg. Herwinning van die metaal ione en die ligande is probeer deur standard filtrasie. Na die filtrasie is die geïmmobiliseerde ligande en substrate met water gewas. Die filtreerpapier en ligande is met HNO3 behandel, maar van die metaal ione het egter op die filtreer papier agter gebly en die IGP resultate het ‘n hoër herwinning getoon as wat tydens die ekstraksie verkry is. Hierdie aspek sal weer in die toekoms ondersoek moet word. Die ligande is suksesvol gesintetiseer en geïmmobiliseer. Hierdie geïmmobiliseerde ligande toon gemiddelde ekstraksie resultate met ‘n aantal metaal ione uit waterige medium by ‘n pH van 5.9.

Current research in natural products has heavily focused on the identification of potent biologically active compounds, specifically for drug development. The project detailed in this thesis focuses on the extraction of compounds from marine invertebrates as well as defining the absolute configuration for a compound. Utilizing marine invertebrates, the sonications method developed in this thesis provides an alternative approach to rapidly extract compounds for primary screening. This method is viable compared to a traditional overnight extraction method, without suffering compound degredation... Previously, clathric acid was isolated from an unknown Clathria sp. This compound is a bibyblic C-21 terpenoid shown to have mild antimicrobial activity against gram positive bacteria. With only its relative configuration established, additional amounts of clathric acid were required to define the overall absolute configuration. Identifying the Clathria sp. to be Clathria compressa, through spicule analysis, additional sponge tissues were then collected off the coast of Boca Raton, Florida to isolate additional quatities of clathric acid. The absolulte configuration was determined through circular dichroism and the octant rule to establish a final configuration for clathric acid's four carbon stereocenters to be: (3S, 7S, 8R, and 12S). / by Rolando Rueda de Leâon. / Thesis (M.S.)--Florida Atlantic University, 2012. / Includes bibliography. / Mode of access: World Wide Web. / System requirements: Adobe Reader.

No description available.

Thesis (M.S.)--University of North Carolina at Wilmington, 2006. / Includes appendix pages: [42]-63. Includes bibliographical references (leaves: 39-41)

Spent nuclear fuel (SNF) resultant from the generation of nuclear power is a chemically and radiologically diverse system which is advantageous to chemically process prior to geologic disposal. Hydrometallurgy is the primary technology for chemical processing for light water reactor spent fuels, where spent fuel is dissolved in an acid for liquid based separations. The primary means for recovery of desired metals from the SNF solution is liquid-liquid extraction which is based on distribution (partitioning) of the metal ions between two immiscible phases based on thermodynamic favorability. One of the means of increasing this favorability is by designing extractant molecules to be either "harder" or "softer" bases, which will more preferentially extract harder or softer metal ions respectively. This technique is used in designing extractant molecules for targeted extraction as actinides are slightly softer than lanthanides, and precious metals produced in significant quantities from the fission process are especially soft metals. The work performed in this thesis involved the synthesis of a novel soft electron donor organic extractant molecule for testing of targeted soft metal extraction. The molecule synthesized was bis-dibutanethiolthiophosphinato-methane, or S6, a bidentate neutral extractant molecule with significant thiolysis for a softer electron environment. The synthesis technique was refined and the molecule composition and structure was confirmed by ¹H NMR, ³¹P NMR, and elemental analysis. Two metal groups, f-elements (actinides and lanthanides) and soft transition metals were tested for their extractability from nitric acid solutions into an S6 solution in n-dodecane. Aqueous solutions of nitric acid and n-dodecane as an organic diluent are typical liquid-liquid extraction conditions in spent nuclear fuel reprocessing. As extraction experiments were performed with radiotracers, for the soft metal extraction experiment, a mixture of the selected metals was neutron-activated in the OSU TRIGA reactor, as was europium to create a lanthanide radiotracer. Actinides and lanthanides were not seen to effectively extract into the organic or form a precipitate at all, making their partitioning with this extractant seemingly ineffective. Through gamma spectroscopy of an irradiated metal solution post-extraction, it is seen that only silver and palladium preferentially complex in the mixed metal samples into an insoluble organic ligand, dropping out of solution. This effect was more pronounced at higher acid concentrations, but silver was seen to slightly extract to the organic phase at all acid concentrations as well. This testing has shown that the S6 extractant can be used to recover silver and palladium from a mixed metal aqueous solution, such as one resultant from advanced spent nuclear fuel reprocessing operations. This result shows promise for future development of sulfur based organophosphate ligands for targeted extraction of precious metals from solutions. / Graduation date: 2013

Extractants and extraction methodologies play a vital role in many industrial processes, from the concentration of precious metals from ores to the separation of longlived nuclei from radioactive waste as well as the removal of heavy metals from soils and water for remediation. The vast majority of extractants rely on the use of nitrogen, oxygen, sulfur or selenium as Lewis base donor atoms to form coordination complexes with the metal ions of interest. These extractants often make use of the chelate effect and/or the macrocyclic effect in order to form stable complexes. Some of the best known types of chelate extractants include polyaminopolycarboxylic acids (N and O donors), polyamines (N donors), dithiocarbamate (S donors) and aminopolythias (N and S donors). The most extensively investigated types of macrocycles include crown ethers (O donors), thia crowns (S donors), aza crowns (N donors) and thiacrown ethers (S and O donors). A conspicuous omission from the list of donor atoms is phosphorus. It is noted that phosphorus has been employed as a backbone atom in the development of extractants, primarily in phosphonates, phosphates and phosphine oxides. The omission of phosphorus is interesting from two points. First, many of the precious and heavy metal ions of interest (Pd2+, Ag+, Pt2+, Pb2+, Cd2+and Hg2+) can be classified as soft Lewis acids, according to Pearson’s HSAB theory. The relative softness of phosphorus as a Lewis base as compared to oxygen and nitrogen indicates that phosphorus would be a very good donor atom toward these soft metal cations. Secondly, chelating agents containing phosphorus donors form stable complexes with transition metal cations in a variety of oxidation states due to their versatile bonding capability. The !-donor characteristics of the phosphine donor coupled with the ability to " accept from filled or partially filled d orbitals of the metal cations result in strong phosphine-metal bonds.

Tez (Yüksek Lisans) - Süleyman Demirel Üniversitesi, Fen Bilimleri Enstitüsü, Kimya Anabilim Dalı, 2007. / Kaynakça var.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references. Also available on the Internet.