Advanced Polymer Flocculants for Solid-Liquid Separation in Oil Sands Tailings.

The generation of tailings as a by product of the bitumen extraction process is one of the largest environmental footprints of oil sands operations. Most of the tailings treatment technologies use polymer flocculants to induce solid-liquid separation. However, due to the complex composition of tailings, conventional flocculants cannot reach the same performance achieved in other wastewater treatments. Over the last couple of decades, the oil sands industry has used acrylamide-based flocculants to treat tailings, achieving major progress in process optimization and integration with mechanical operations, but they still could not reach the required land reclamation targets. Over the last 5 years, the group designed, synthesized, and tested several novel polymer flocculants tailored for oil sands tailings treatment. This feature article communicates recent developments in these innovative polymers. The article first provides a background on tailings generation and treatment, followed by the description of advanced polymer flocculants categorized according to their microstructures such as linear, branched, and graft. The other tailings remediation technologies and one of the initial works on modeling of tailings flocculation is discussed.

Polymer reaction engineering tools to design multifunctional polymer flocculants.

A series of multifunctional terpolymers, poly(N-isopropyl acrylamide/2-(methacryloyloxy) ethyl trimethyl ammonium chloride/N-tert-butylacrylamide) [P(NIPAM-MATMAC-BAAM)], were designed to flocculate and dewater oil sands mature fine tailings (MFT). The hydrophobic BAAM comonomer helped in expelling water from the sediments, while the cationic MATMAC comonomer promoted the charge neutralization of negatively charged particles suspended in MFT. The chemical composition distributions of these terpolymers were designed based on the knowledge of the reactivity ratios of all comonomers, instead of by trial and error, as usually done for most polymer flocculants. The binary reactivity ratios of the comonomers were estimated by synthesizing the binary copolymers with various mole fractions of each comonomer in the feed and experimentally measuring the corresponding fraction of comonomer in the copolymers. Polymer reaction engineering tools were used to minimize compositional drift and guarantee the synthesis of terpolymers with narrow chemical composition distributions suitable for MFT dewatering. Focused beam reflectance measurement (FBRM) experiments showed that terpolymers promoted the formation of large MFT flocs (120 µm). The initial settling rate decreased with the increase in flocculant hydrophobicity, likely because the hydrophobic terpolymer segments did not take part in the bridging of the MFT particles. In contrast, the sediment dewaterability increased with the increase in terpolymer hydrophobicity. This study provides guidelines to design a polymer flocculant from first principles and demonstrates the potential of using hydrophobically modified cationic polymers to flocculate MFT effectively.

A novel hydrophobically-modified polyelectrolyte for enhanced dewatering of clay suspension.

This work investigates the effect of multifunctional poly (N-isopropyl acrylamide/acrylic acid/N-tert-butylacrylamide) [p(NIPAM-AA-NTBA)] ternary polymer on the sedimentation of kaolin clay - a major fraction of oil sands tailings. A series of linear, uncross-linked p(NIPAM), p(NIPAM/AA), and p(NIPAM/AA/NTBM) were synthesized as random copolymers, where all monomer units were randomly arranged along the polymer backbone and connected by covalent bonds. The ternary copolymer, used as a flocculant, exhibited thermo-sensitivity, anionic nature, and hydrophobic association due to NIPAM, AA, and NTBM, respectively. As the ternary polymer is thermosensitive, it undergoes extended to coil-like conformation, i.e. hydrophilic to hydrophobic transition, above its lower critical solution temperature (LCST). The comonomers NIPAM (above LCST) and NTBM help expel water out of sediments due to their hydrophobicity, while AA promotes charge neutralization of the kaolin clay particles. The effect of number average molecular weight, charge density, and concentration of NTBM on settling behavior of kaolin suspension was examined. Settling test at 50 °C resulted in significantly higher settling rates compared to that at room temperature. Further, the quality of water recovered in each experiment was tested in terms of its turbidity. These results indicate that this novel ternary polymer can be employed to enhance the recovery of water from oil sands tailings containing clays.

Dewatering Oil Sands Tailings with Degradable Polymer Flocculants.

We synthesized hydrolytically degradable cationic polymers by micellar radical polymerization of a short-chain polyester macromonomer, polycaprolactone choline iodide ester methacrylate (PCL2ChMA) with two polyester units, and used them to flocculate oil sands mature fine tailings (MFT). We evaluated the flocculation performance of the homopolymer and copolymers with 30 mol % acrylamide (AM) by measuring initial settling rate (ISR), supernatant turbidity, and capillary suction time (CST) of the sediments. Flocculants made with trimethylaminoethyl methacrylate chloride (TMAEMC), the monomer corresponding to PCLnChMA with n = 0, have improved performance over poly(PCL2ChMA) at equivalent loadings due to their higher charge density per gram of polymer. However, MFT sediments flocculated using the PCL2ChMA-based polymers are easier to dewater (up to an 85% reduction in CST) after accelerated hydrolytic degradation of the polyester side chains. This study demonstrates the potential of designing cationic polymers that effectively flocculate oil sands tailings ponds, and also further dewater the resulting solids through polymer degradation.