Vreugdenhil, Andrew AV

Naphthenic acids are a major contaminant of concern and a focus of much research around remediation of oil sand process affected waters, OSPW. Using activated carbon adsorbents are an attractive option given their low cost of fabrication and implementation. A deeper evaluation of the effect naphthenic acid structural differences have on uptake affinity is warranted. In this thesis an in-depth exploration of naphthenic acid adsorption onto activated carbon is provided including many more model naphthenic acid species than what have been assessed previously in adsorption studies. Both adsorption kinetics and isotherms at the relevant alkaline pH of OSPW using several different carbon adsorbents with pH buffering to simulate the behaviour of real OSPW were evaluated. Given the time sensitive application of most adsorbents towards treating contaminated waters such as OSPW, achieving fast adsorption rates for model naphthenic acids is an important goal worth considering. Textural properties of activated carbon most conducive for fast adsorption kinetics were assessed using several candidate model species. Clear evidence is presented, demonstrating the influence of both the pore size distribution and particle size of porous adsorbents on uptake rates of naphthenic acids, demonstrating that careful optimization of these adsorbent properties can result in adequate uptake rates. Adsorption isotherms were used to assess model naphthenic acid affinity towards activated carbon. Uptake for the model naphthenic acids varied considerably regardless of the activated carbon used, ranging from 350 mg g-1 to near zero highlighting recalcitrant species. The equilibrium data was explored to identify important structural features of these species and key physiochemical properties that influence adsorption. It was demonstrated that certain naphthenic acids are resistant to adsorption when hydrophobic adsorbents are used. Adsorption isotherm modelling helped explore interactions occurring at the interface between naphthenic acids and adsorbent surfaces. Naphthenic acid hydrophobicity was identified as an importance physiochemical property for achieving high adsorption capacities onto activated carbon. Evidence is also presented that indicates favorable hydrogen bonding between naphthenic acids and surface site hydroxyl groups, demonstrating the importance of adsorbent surface functionality for naphthenic acid uptake. The adsorption mechanism was further explored through use of a thermodynamic analysis of the model naphthenic acid system using activated carbon. Standard state enthalpy and isosteric enthalpy of adsorption values were used to further support the proposed mechanisms occurring between model species and activated carbons. This research highlights the challenges associated with removing naphthenic acids from OSPW through adsorption and identifies how adsorbent surface chemistry modification will need to be used to increase the removal efficiency of recalcitrant naphthenic acid species when using activated carbon.

Author Keywords: Activated Carbon, Isotherms, Kinetics, Modelling, Naphthenic Acids, Thermodynamics

The replacement of petroleum with renewable feedstock for energy and materials has become a priority because of concerns over the environment and finite nature of petroleum. The structures of the available natural biomass feedstocks fall short in delivering key functionality required in materials such as lubricants and phase change energy storage materials (PCMs). The approach taken in this thesis was to combine select functional groups with vegetable oil derivatives to create novel PCMs and lubricantswhich deliver desired functionality. One series of diester PCMs were prepared with terephthalic acid and fatty alcohols to address known shortcomings of esters. The second class of PCMs are sulfones prepared from oxidation of fatty sulfides to improve thermal energy storage. Overall, the new PCMs presented narrow phase change temperature ranges, high transition temperature (between 67 to 110℃), high transition enthalpy (210 to 266J/g), minimal supercooling and congruent phase transitions unaffected by cooling rates. They also demonstrated higher thermal degradation stability with onset of degradation from 290 to 310℃. The series of lubricants studied consists of sulfide and sulfonyl functional groups attached to the unsaturation sites of oleyl oleate as pendant groups to improve the thermal and flow properties. The new lubricants present subzero crystallization temperatures, very low crystallization enthalpy and dynamic viscosity as high as 180mPas.

Furthermore, they also presented high onset of degradation (up to 322℃) and oxidation (up to 298℃). The PCMs and lubricants of the present thesis demonstrate that select functional groups can be used with common structural elements of vegetable oil such as fatty acids, ester groups and unsaturation sites to make a variety of molecular structures capable of delivering desired properties

Author Keywords: Crystal Structure, Lubricant, Phase Change Material, Renewable, Structure-Property Relationships, Vegetable Oil