Comparing the Kinetic Hydrate Inhibition Performance of Linear versus Branched Polymers

Kinetic hydrate inhibitors (KHIs) are a chemical method of preventing gas hydrate plugging of oil and gas production flow lines. The main ingredient in a KHI formulation is one or more water-soluble amphiphilic polymers. Poly(N-vinyl caprolactam) (PVCap) is an unbranched polymer and a well-known industrial KHI, often used as a yardstick to compare the performance of new polymers. The effect of branching PVCap on KHI performance has been investigated by polymerizing the VCap monomer in the presence of varying amounts of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, or bis-pentaerythritol hexaacrylate cross-linkers to give PVCap polymers with 3, 4, and 6 branches, respectively. If the ratio of cross-linker to VCap was too high (6:1 to 8:1), gelling and/or poor water solubility was observed, giving short polymer chains and poor KHI efficacy. For higher ratios (30:1 to 60:1), it was found that the concentration of the polymer needed to give total inhibition of structure II tetrahydrofuran hydrate crystal growth could be lowered by using tribranched rather than linear PVCap. Slow constant cooling (1 °C/h) gas hydrate experiments with a synthetic natural gas in steel rocking cells at 76 bar were also carried out. A small improvement in KHI performance was observed for one of the branched PVCaps compared with a linear PVCap. Branched and linear poly(N-isopropylmethacrylamide) (PNIPMAm) polymers were also investigated in the gas hydrate system, but there was no benefit observed when branching this polymer class.