Energy & Fuels, Vol.32, No.10, 10639-10648, 2018
Polymers of N-(Pyrrolidin-1-yl)methacrylamide as High Cloud Point Kinetic Hydrate Inhibitors
Formation of gas hydrates is a major problem in flowlines where gas and water are transported together, and can lead to blockages, downtime, economic losses, and potential accidents. One way of preventing gas hydrates from forming is by injection of kinetic hydrate inhibitors (KHIs). KHIs are typically water-soluble polymers, often containing amide pendant groups. Based on our previous work on high cloud point polymers of N,N-dimethylhydrazidoacrylamide (polyDMHAM) and N,N-dimethylhydrazidomethacrylamide (polyDMHMAM), we have now synthesized a series of N-(pyrrolidin-1-yl)methacrylamide polymers (polyNPyMA) which contains a pyrrolidine-substituted hydrazido pendant group. These polymers show improvement on all previous hydrazido polymers as they exhibit improved KHI performance while having no cloud point in deionized water or 7 wt % aqueous NaCl up to 95 degrees C. Their performance as KHIs have been investigated using a high-pressure gas hydrate rocker rig at a pressure of 76 bar using a structure II forming natural gas mixture and slow temperature ramping experiments. The best performing polymer, polyNPyMA-II, was kept in the reaction mixture of aqueous isopropyl alcohol and gave an average onset temperature of T-o = 8.1 degrees C at 2500 ppm. We have shown that isopropyl alcohol functions as a synergist with polyNPyMA, reducing the To of polyNPyMA-IV from 10.0 to 9.0 degrees C when added at 7875 ppm. A common synergist for different KHIs, n-butyl glycol ether (BGE), was found to not significantly improve the performance of polyNPyMA. An interesting feature of hydrazidoacrylamide polymers such as polyNPyMA is that they can be protonated and therefore their solubility characteristics can change with pH. PolyNPyMA was shown to perform better at neutral and high pHs, and less well at low pH. The effect of pH was observed to be smaller than previously reported for polyDMHAM and polyDMHMAM, suggesting that the hydrophilicity obtained by protonation of the hydrazido group affects the polymer less when the hydrazido moiety contains bigger hydrophobic groups. Finally, given the fact that KHI polymer performance is dependent on the molecular weight distribution, this paper also highlights that M-n, and M-w, values determined by size exclusion chromatography (SEC) using calibration standards can give very different results compared to absolute methods such as multiangle light scattering (MALS).