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Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The reactive absorption rate of CO2 into non-aqueous solvents containing the primary amine, mono-ethanolamine (MEA) is recognised as a suitable method for measuring the effective interfacial mass transfer area of separation column internals such as random and structured packing. Currently, this method is used under conditions where the concentration of MEA in the liquid film is unaffected by the reaction and the liquid phase reaction is, therefore, assumed to obey pseudo first order kinetics with respect to CO2. Under pseudo first order conditions, the effect of surface depletion and renewal rates are not accounted for. Previous research indicated that the effective area available for mass transfer is also dependent upon the rate of surface renewal achieved within the liquid film. In order to study the effect of surface depletion and renewal rates on the effective area, a method utilising a fast reaction with appreciable depletion of the liquid phase reagent is required. The homogeneous liquid phase reaction kinetics of CO2 with MEA n-Propanol as alcoholic solvent was investigated in this study. A novel, in-situ Fourier Transform Infra-Red (FTIR) method of analysis was developed to collect real time concentration data from reaction initiation to equilibrium. The reaction was studied in a semi-batch reactor set-up at ambient conditions (T = 25°C, 30°C and 35°C, P = 1 atm (abs)). The concentration ranges investigated were [MEA]:[CO2] = 5:1 and 10:1. The concentration range investigated represents conditions of significant MEA conversion. The reaction kinetic study confirmed the findings of previous research that the reaction of CO2 with MEA is best described by the zwitterion reactive intermediate reaction mechanism. Power rate law and pseudo steady state hypothesis kinetic models (proposed in literature) were found to be insufficient at describing the reaction kinetics accurately. Two fundamentally derived rate expressions (based on the zwitterion reaction mechanism) provided a good quality model fit of the experimental data for the conditions investigated. The rate constants of the full fundamental model were independent of concentration and showed an Arrhenius temperature dependence. The shortened fundamental model rate constants showed a possible concentration dependence, which raises doubt about its applicability. The specific absorption rates (mol/m2.s) of CO2 into solutions of MEA/n-Propanol (0.2 M and 0.08 M, T = 25°C and 30°C, P = ±103 kPa) were investigated on a wetted wall experimental setup. The experimental conditions were designed for a fast reaction in the liquid film to occur with a degree of depletion of MEA in the liquid film. Both interfacial depletion and renewal of MEA may be considered to occur. The gas phase resistance to mass transfer was determined to be negligible. An increase in liquid turbulence caused an increase in the specific absorption rate of CO2 which indicated that an increase in liquid turbulence causes an increase in effective mass transfer area. Image analysis of the wetted wall gas-liquid interface confirmed the increase in wave motion on the surface with an increase in liquid turbulence. The increase in wave motion causes an increase in both interfacial and effective area. A numerical solution strategy based on a concentration diffusion equation incorporating the fundamentally derived rate expressions of this study is proposed for calculating the effective area under conditions where surface depletion and renewal rates are significant. It is recommended that the reaction kinetics of CO2 with MEA in solvents of varying liquid properties is determined and the numerical technique proposed in this study used to calculate effective area from absorption rates into these liquids. From the absorption data an effective area correlation as a function of liquid properties may be derived in future. / AFRIKAANSE OPSOMMING: Die reaktiewe absorpsie van CO2 in nie-waterige oplossings van die primêre amien, monoetanolamien (MEA) word erken as ‘n geskikte metode om die effektiewe massaoordragsarea van gepakte skeidingskolomme te bepaal. Tans word die metode gebruik onder vinnige pseudo eerste orde reaksietoestande met betrekking tot CO2. Die pseudo eersteorde aanname beteken dat die konsentrasie van MEA in die vloeistoffilm onbeduidend beïnvloed word deur die reaksie en effektief konstant bly. Onder pseudo eerste orde toestande word oppervlakverarming- en oppervlakvernuwingseffekte nie in ag geneem nie, juis as gevolg van die konstante konsentrasie van MEA in die vloeistoffilm. Daar is voorheen bevind dat oppervlakverarming en oppervlakvernuwing ‘n beduidende invloed het op die beskikbare effektiewe massaoordragsarea. Hierdie invloed kan slegs bestudeer word met ‘n vinnige reaksie in die vloeistoffilm wat gepaard gaan met beduidende oppervlakverarming van die vloeistoffase reagens. Die homogene vloeistoffase reaksiekinetika van CO2 met MEA in die alkohol oplosmiddel, n- Propanol, is in hierdie studie ondersoek. ‘n Nuwe, in-situ Fourier Transform Infra-Rooi (FTIR) metode van analiese is ontwikkel in hierdie ondersoek. Die reaksie is ondersoek in ‘n semienkelladings reaktor met MEA wat gevoer is tot die reaktor om met die opgeloste CO2 te reageer. Die FTIR metode meet spesiekonsentrasie as ‘n funksie van tyd sodat die konsentrasieprofiele van CO2, MEA en een van die soutprodukte van die reaksie gebruik kan word om verskillende reaksiesnelheidsvergelykings te modelleer. Die reaksie is ondersoek onder matige toestande (T = 25°C, 30°C and 35°C, P = 1 atm (abs)). Die konsentrasiebereik van die ondersoek was [MEA]:[CO2] = 5:1 en 10:1. Hierdie bereik is spesifiek gebruik sodat daar beduidende omsetting van MEA kon plaasvind. Die reaksiekinetieka studie het, ter ondersteuning van bestaande teorie, bevind dat die reaksie van CO2 met MEA in nie-waterige oplosmiddels soos alkohole, beskyf word deur ‘n zwitterioon reaksiemeganisme. Die bestaande reaksiesnelheids modelle (eksponensiële wet en pseudo gestadigde toestand hipotese) kon nie die eksperimentele data met genoegsame akuraatheid beskryf nie. Twee nuwe reaksiesnelheidsvergelykings, afgelei vanaf eerste beginsels en gebaseer op die zwitterioon meganisme, word voorgestel. Hierdie volle fundamentele model het goeie passings op die eksperimentele data getoon oor die volledige temperatuur en konsentrasiebereik van hierdie studie. Die reaksiekonstantes van die fundamentele model was onafhanklik van konsentrasie en tipe oplosmiddel en het ‘n Arrhenius temperatuurafhanklikheid. Die verkorte fundamentele model se reaksiekonstantes het ‘n moontlike konsentrasieafhanlikheid gewys. Dit plaas onsekerheid op die fundamentele basis van hierdie model en kan dus slegs as ‘n eerste benadering beskou word. Die spesifieke absorpsietempos (mol/m2.s) van CO2 in MEA/n-Propanol oplossings (0.2 M en 0.08 M MEA, T = 25°C and 30°C, P = ±103 kPa) is ondersoek met ‘n benatte wand (‘wetted wall’) eksperimentele opstelling. Die eksperimentele toestande is gekies sodat daar ‘n vinnige reaksie in die vloeistoffilm plaasgevind het, met beide beduidende en nie-beduidende MEA omsetting. Die doel met hierdie eksperimentele ontwerp was om die invloed van intervlakverarming en intervlakvernuwing op die spesifieke absorpsietempo te ondersoek. Gas fase weerstand was nie-beduidend onder die eksperimentele toestande nie. Beide intervlakverarming en intervlakvernuwing gebeur gelyktydig en is waargeneem vanuit die eksperimentele data. ‘n Beeldverwerkingstudie van die gas-vloeistof intervlak van die benatte wand het bevind dat daar ‘n toename in golfaksie op die vloeistof oppervlak is vir ‘n toename in vloeistof turbulensie. Hierdie golfaksie dra by tot oppervlakvernuwing en ‘n toename in effektiewe massaoordragsarea. ‘n Numeriese metode word voorgestel om die effektiewe area van beide die benatte wand en gepakte kolomme te bepaal vanaf reaktiewe absorpsietempos. Die metode gebruik die fundamentele reaksiesnelheidsvergelykings, bepaal in hierdie studie, in a konsentrasie diffusievergelyking sodat oppervlakverarming en vernuwing in ag geneem kan word. Daar word voorgestel dat die reaksiekinetika van CO2 met MEA in oplossings met verskillende fisiese eienskappe (digtheid, oppervlakspanning en viskositeit) bepaal word sodat die numeriese metode gebruik kan word om ‘n effektiewe area korrelasie as ‘n funksie van hierdie eienskappe te bepaal.

Formaldehyde-based adhesives have been reported to be detrimental to health. Petrochemical-based adhesives are non-renewable, limited and costly. Therefore, the improvement of environmental-friendly adhesive from natural agricultural products has awakened noteworthy attention. A novel adhesive for wood application was successfully prepared with enhanced shear strength and water resistance. The Fourier transmform infrared spectra showed the surface functionalities of the functionalized carbon nanotubes (FCNTs) and soy protein isolate nanocomposite adhesive. The attachment of carboxylic functional group on the surface of the carbon nanotubes (CNTs) after purification contributed to the effective dispersion of the CNTs in the nanocomposite adhesive. Hence, enhanced properties of FCNTs were successfully transferred into the SPI/CNTs nanocomposite adhesive. These unique functionalities on FCNTs however, improved the mechanical properties of the adhesive. The shear strength and water resistance of SPI/FCNTs was higher than that of the SPI/CNTs. SEM images showed the homogenous dispersion of CNTs in the SPI/CNTs nanocomposite adhesive. The carbon nanotubes were distributed uniformly in the soy protein adhesive with no noticeable clusters at relatively reduced fractions of CNTs as shown in the SEM images, which resulted into better adhesion on wood surface. Mechanical (shear) mixing and ultrasonication with 30 minutes of shear mixing both showed an improved dispersion of CNTs in the soy protein matrix. However, ultrasonication method of dispersion showed higher tensile shear strength and water resistance than in mechanical (shear) mixing method. Thermogravimetric analysis of the samples also showed that the CNTs incorporated increases the thermal stability of the nanocomposite adhesive at higher loading fraction. Incorporation of CNTs into soy protein isolate adhesive improved both the shear strength and water resistance of the adhesive prepared at a relatively reduced concentration of 0.3%.The result showed that tensile shear strength of SPI/FCNTs adhesive was 0.8 MPa and 7.25MPa at dry and wet state respectively, while SPI/CNTs adhesive had 6.91 MPa and 5.48MPa at dry and wet state respectively. There was over 100% increase in shear strength both at dry and wet state compared to the pure SPI adhesive. The 19% decrease in value of the new adhesive developed compared to the minimum value of ≥10MPa of European standard for interior wood application may be attributed to the presence of metallic particles remaining after purification of CNTs. The presence of metallic particles will prevent the proper penetration of the adhesive into the wood substrate. The type of wood used in this study as well as the processing parameters could also result into lower value compared to the value of European standard. Therefore, optimization of the processing parameter as well as the conversion of carboxylic acid group on the surface of the CNTs into acyl chloride group may be employed in future investigation. However, the preparation of new nanocomposite adhesive from soy protein isolate will replace the formaldehyde and petrochemical adhesive in the market and be of useful application in the wood industry. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

Formaldehyde-based adhesives have been reported to be detrimental to health. Petrochemical-based adhesives are non-renewable, limited and costly. Therefore, the improvement of environmental-friendly adhesive from natural agricultural products has awakened noteworthy attention. A novel adhesive for wood application was successfully prepared with enhanced shear strength and water resistance. The Fourier transmform infrared spectra showed the surface functionalities of the functionalized carbon nanotubes (FCNTs) and soy protein isolate nanocomposite adhesive. The attachment of carboxylic functional group on the surface of the carbon nanotubes (CNTs) after purification contributed to the effective dispersion of the CNTs in the nanocomposite adhesive. Hence, enhanced properties of FCNTs were successfully transferred into the SPI/CNTs nanocomposite adhesive. These unique functionalities on FCNTs however, improved the mechanical properties of the adhesive. The shear strength and water resistance of SPI/FCNTs was higher than that of the SPI/CNTs. SEM images showed the homogenous dispersion of CNTs in the SPI/CNTs nanocomposite adhesive. The carbon nanotubes were distributed uniformly in the soy protein adhesive with no noticeable clusters at relatively reduced fractions of CNTs as shown in the SEM images, which resulted into better adhesion on wood surface. Mechanical (shear) mixing and ultrasonication with 30 minutes of shear mixing both showed an improved dispersion of CNTs in the soy protein matrix. However, ultrasonication method of dispersion showed higher tensile shear strength and water resistance than in mechanical (shear) mixing method. Thermogravimetric analysis of the samples also showed that the CNTs incorporated increases the thermal stability of the nanocomposite adhesive at higher loading fraction. Incorporation of CNTs into soy protein isolate adhesive improved both the shear strength and water resistance of the adhesive prepared at a relatively reduced concentration of 0.3%.The result showed that tensile shear strength of SPI/FCNTs adhesive was 0.8 MPa and 7.25MPa at dry and wet state respectively, while SPI/CNTs adhesive had 6.91 MPa and 5.48MPa at dry and wet state respectively. There was over 100% increase in shear strength both at dry and wet state compared to the pure SPI adhesive. The 19% decrease in value of the new adhesive developed compared to the minimum value of ≥10MPa of European standard for interior wood application may be attributed to the presence of metallic particles remaining after purification of CNTs. The presence of metallic particles will prevent the proper penetration of the adhesive into the wood substrate. The type of wood used in this study as well as the processing parameters could also result into lower value compared to the value of European standard. Therefore, optimization of the processing parameter as well as the conversion of carboxylic acid group on the surface of the CNTs into acyl chloride group may be employed in future investigation. However, the preparation of new nanocomposite adhesive from soy protein isolate will replace the formaldehyde and petrochemical adhesive in the market and be of useful application in the wood industry. / Civil and Chemical Engineering / M. Tech. (Chemical Engineering)

Plastskräp har blivit ett global problem på grund av nedskräpning och otillräcklig avfallshantering. Användning av biologiskt nedbrytbart material kan underlätta problemet, även om det inte är en universallösning. Produkter gjorda av biologiskt nedbrytbart material skall ändå till avfallshantering eftersom nedbrytningen kan vara långvarig och variera mycket beroende av omgivningen. Därmed är användningen av biologiskt nedbrytbart material endast berättigat då det är svårt att samla in materialet eller avskilja det från organiskt material. Studiens mål var att undersöka biologiskt nedbrytbara material som kan användas i produkter som fungerar under många olika driftsförhållanden och inte kan återställas efter användning. I den litterära delen av denna studie definieras nedbrytning genom egenskaper och förhållanden som påverkar nedbrytningsprocessen. Nedbrytning av polyestrar och cellulosa och de standardprocessarna som används i nedbrytningsexperimenten betraktades. Standardprocesserna för nedbrytning studerades för att få en klarare inblick i den eftertraktade nedbrytningsgraden och de standardiserade förhållandena för nedbrytningen i olika miljöer. En sammanfattning av olika nedbrytningsexperiment och analysmetoder är också inkluderade för att försäkra att experimenten som utfördes är både giltiga och jämförbara med andra forskningsresultat inom fältet. I detta forskningsprojekt utfördes nedbrytningsexperiment i färskvatten- och hemkompostmiljöer. Målet med projektet var att bedöma ifall materialen kunde brytas ned i ett brett spektrum av miljöer, ifall de var mindre skadliga för naturen än konventionella material som används av dagens industri och för att uppskatta nedbrytningstakten. Nedbrytningstiden var 140 dagar och experimentet utfördes med 10 olika material: betecknade som A-J. Materialen analyserades 8 gånger under nedbrytningsperioden förutom materialen I och J som analyserades en gång efter 140 dagar. Materialen analyserades mekaniskt, strukturellt och termiskt med hjälp av dragprovning, FTIR och DSC. Provernas viktförändring bestämdes också. Nedbrytning observerades visuellt från provernas yta och genom mekaniska prover. Materialen som placerades i hemkomposten visade klara tecken på nedbrytning då färgen hade förändrats och förstärkningsfibrerna hade blivit synliga. Materialen som placerats i hemkompostmiljö visade också klara tecken på tillväxt av mikroorganismer och biomassa som uppstått på ytan av materialen. Sammanfattningsvist, visade materialen B, C och G de mest lovande resultaten med klara tecken på biologisk nedbrytning och de hade en snabbare nedbrytningstakt än de andra materialen som undersöktes. Material D visade klara tecken på biologisk nedbrytning på ytan men dess nedbrytningstakt var uppskattad att vara mycket långsammare. Därmed rekommenderas det att använda material A, B, D och G istället för konventionella icke biologiskt nedbrytbara material. Dessa material har potential att sänka den negativa inverkan och de långsiktiga riskerna av plastskräp för miljön. / Plastic debris has become a global crisis due to littering and misplaced waste management. The use of biodegradable materials can ease the problem, but it is not always the answer. Products made of biodegradable materials are still to be waste managed since biodegradation can be a long process and is highly dependent on the environment conditions. Hence, the use of biodegradable materials is justified only when retrieving the product after use is impossible or prohibitively expensive or separating it from organic matter is difficult. This study was made to investigate biodegradable materials that can be used in products that are operating in broad range of operational conditions and cannot be retrieved back after use in most cases. In the literature part of this study the biodegradation is defined along with properties and conditions that affect the biodegradation process. Biodegradation of polyesters and cellulose, and standards used in the biodegradation experiments were reviewed. Biodegradation standards were studied in order to have a clearer picture of the pursued degree of biodegradation and standardized properties in the biodegradation experiments. Review of different biodegradation tests and analysis methods are included as well to ensure that the experiments performed in this work are valid and comparable with other biodegradation studies.  In this study, the biodegradation experiment was conducted in freshwater and home compost environments. The aim was to determine if the materials were able to biodegrade in wide range of environments, to make sure they are less harmful than the conventional materials used in the industry and to estimate the rate of biodegradation. The duration of the experiments were 140 days with 10 different materials: A – J. The materials were analyzed 8 times during the aging period, except materials I and J, which were analyzed only once after 140 days. The samples were analyzed mechanically, structurally, and thermally using tensile test, FTIR and DSC measurements, respectively. Also, the samples weight changes were analyzed.  The degradation was visually observed from the surfaces of the samples and from mechanical testing in both experimental environments. Home compost environment showed clear signs of biodegradation where reinforcement fibers became visible and changed the color of some of the samples. Also, home compost samples had microorganisms growing on them, and biomass was developing around them. To conclude, material B, C and G had the most promising results with clear signs of biodegradation and had faster estimated biodegradation rate compared with the other studied materials. Material D had signs of biodegradation on the surface as well. However, the biodegradation rate was estimated to be much slower. In conclusion, it is recommended to use the studied materials A, B, D and G instead of the conventional non-biodegradable polymers. These materials have potential to lower the negative impact and long-term risks of plastic debris to the environment.