Thermoresponsive Microcarriers for Smart Release of Hydrate Inhibitors under Shear Flow.

The hydrate formation in subsea pipelines can cause oil and gas well blowout. To avoid disasters, various chemical inhibitors have been developed to prevent or delay the hydrate formation and growth. Nevertheless, direct injection of the inhibitors results in environmental contamination and cross-suppression of inhibition performance in the presence of other inhibitors against corrosion and/or formation of scale, paraffin, and asphaltene. Here, we suggest a new class of microcarriers that encapsulate hydrate inhibitors at high concentration and release them on demand without active external triggering. The key to the success in microcarrier design lies in the temperature dependence of polymer brittleness. The microcarriers are microfluidically created to have an inhibitor-laden water core and polymer shell by employing water-in-oil-in-water (W/O/W) double-emulsion drops as a template. As the polymeric shell becomes more brittle at a lower temperature, there is an optimum range of shell thickness that renders the shell unstable at temperature responsible for hydrate formation under a constant shear flow. We precisely control the shell thickness relative to the radius by microfluidics and figure out the optimum range. The microcarriers with the optimum shell thickness are selectively ruptured by shear flow only at hydrate formation temperature and release the hydrate inhibitors. We prove that the released inhibitors effectively retard the hydrate formation without reduction of their performance. The microcarriers that do not experience the hydration formation temperature retain the inhibitors, which can be easily separated from ruptured ones for recycling by exploiting the density difference. Therefore, the use of microcarriers potentially minimizes the environmental damages.