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Synthesis of β-cyclodextrin and chitosan-based copolymers for the removal of naphthenic acids



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Naphthenic acids (NAs) are a group of carboxylic acids that are found in hydrocarbon deposits such as the oil sands bitumen. These compounds are a well-known corrosive agent and a toxic component in the oil sands process water (OSPW). Due to Alberta’s zero discharge policy, OSPW cannot be released and must be stored until toxic components like NAs are remediated. One technique that has shown potential is to physically adsorb NAs onto a copolymer generated from economical biomaterials. Therefore, the project can be divided into three sections: 1) Synthesis of β-cyclodextrin (β-CD) copolymer for the sorption of p-nitrophenol (PNP); 2) Synthesis of chitosan-based copolymers (Chi-Glu) for the sorption of PNP; 3) Sorption of carboxylates and NAs using Chi-Glu copolymers. PNP sorption was used as a probe to understand the physicochemical properties of the copolymers. In the first section, β-CD was reacted with sebacoyl chloride (SCl) and terephthaloyl chloride (TCl) at various mole ratios. Characterization was done using Fourier Transform Infrared Spectroscopy (FT-IR), thermogravimetric analysis (TGA), 1H NMR spectroscopy (1H NMR), elemental analysis (CHN), and nitrogen porosimetry. Copolymers synthesized at mole ratios of β-CD to SCl from 1:1 to 1:3 were hydrolyzed at acidic and basic conditions. Therefore, sorption studies were not done at these ratios. The same occurred for 1:1 to 1:3 TCl copolymers. Sorption studies with PNP at pH 4.6 demonstrated enhanced sorption capacity when comparing with a standard: granular activated carbon (GAC). The sorption capacity, Qm (mmol/g), ordered from largest to smallest is 1:9 SCl>1:9 TCl>1:6 SCl> GAC> 1:6 TCl. Chi-Glu copolymers were synthesized by cross-linking glutaraldehyde with pristine chitosan. A systematic study on the effects reaction conditions have on the sorption capacity of the materials was done. Three conditions were changed: pH, temperature, and mole ratios. Chi-Glu copolymers were synthesized at various chitosan to glutaraldehyde mole ratios (1:400, 1:700, 1:1000). Sufficient time was allowed for the aging process. Characterization was done using TGA, FT-IR, CHN, and nitrogen porosimetry. Sorption study with PNP were done at pH = 7.0 and 9.0. At pH = 7.0 sorption capacity appears to correlate to the quantity of homo-polymerized glutaraldehyde: 1:700>1:1000>1:400. While at pH = 9.0, the sorption capacity is inversely proportional to the degree of crosslinking: 1:400>1:700>1:1000. By increasing the pH at the shrinkage phase, PNP was weakly bound onto the Chi-Glu copolymer. Varying temperature before gelation caused a decrease in the sorption capacity with PNP. Sorption studies involving carboxylates and NAs were done at pH = 9.0 at ambient temperature using Chi-Glu copolymers (1:400, 1:700, and 1:1000) and chitosan. Three carboxylates were chosen to reflect the diverse components in NAs. Varying degrees of cyclization (Z = 0, -2, -4) and lipophilic surface area were the main criteria for carboxylates. The sorption capacity depended mainly on the lipophilic surface area (LSA) with sorption capacity highest for 2-hexyldecanoic acid (S1) which has the largest LSA and lowest for, trans-4-pentylcyclohexanecarboxylic acid (S2) and dicyclohexylacetic acid (S3). Unfortunately, cross-linking with glutaraldehyde does not enhance sorption as pristine chitosan retained a higher sorption capacity compared to Chi-Glu copolymers. Acros and Fluka NAs were chosen for sorption and no significant sorption was recorded for any copolymers. Problems involving the micellization process can explain the lack of sorption.



Chitosan, Cyclodextrin, β-Cyclodextrin, sorption, adsorption, naphthenic acids, naphthenate, oil sands, nitrophenol



Master of Science (M.Sc.)






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