Polyelectrolyte Multilayered Nanoparticles as Nanocontainers for Enzyme Breakers During Hydraulic Fracturing Process

Abstract In this study, Layer-by-Layer (LbL) assembled polyelectrolyte multilayered nanoparticles were developed as a technique for targeted and controlled release of enzyme breakers. Polyelectrolyte multilayers (PEMs) were assembled by means of alternate electrostatic adsorption of polyanions and polycations using colloidal structure of polyelectrolyte complexes (PECs) as LbL building blocks. High enzyme concentrations were introduced into polyethyleneimine (PEI), a positively charged polyelectrolyte solution, to form an electrostatic PECs with dextran sulfate (DS), a negatively charged polyelectrolyte solution. Under the right concentrations and pH conditions, PEMs were assembled by alternating deposition of PEI with DS solutions at the colloidal structure of PEI-DS complexes. Stability and reproducibility of PEMs were tested over time. This work demonstrates the significance of PEMs as a technique for the targeted and controlled release of enzymes based on their high loading capacity, high capsulation efficiency, and extreme control over enzyme concentration. Entrapment efficiency (EE%) of polyelectrolyte multilayered nanoparticles were evaluated using concentration measurement methods as enzyme viscometric assays. Controlled release of enzyme entrapped within PEMs was sustained over longer time periods (> 18 hours) through reduction in viscosity, and elastic modulus of borate-crosslinked hydroxypropyl guar (HPG). Long-term fracture conductivity tests at 40℃ under closure stresses of 1,000, 2,000, and 4,000 psi revealed high fracture clean-up efficiency for fracturing fluid mixed with enzyme-loaded PEMs nanoparticles. The retained fracture conductivity improvement from 25% to 60% indicates the impact of controlled distribution of nanoparticles in the filter cake and along the entire fracture face as opposed to the randomly dispersed unentrapped enzyme. Retained fracture conductivity was found to be 34% for fluid systems containing conventional enzyme-loaded PECs. Additionally, enzyme-loaded PEMs demonstrated enhanced nanoparticle distribution, high loading and entrapment efficiency, and sustained release of the enzyme. This allows for the addition of higher enzyme concentrations without compromising the fluid properties during a treatment, thereby effectively degrading the concentrated residual gel to a greater extent. Fluid loss properties of polyelectrolyte multilayered nanoparticles were also studied under static conditions using a high-pressure fluid loss cell. A borate-crosslinked HPG mixed with nanoparticles was filtered against core plugs with similar permeabilities. The addition of multilayered nanoparticles into the fracturing fluid was observed to significantly improve the fluid- loss prevention effect. The spurt-loss coefficient values were also determined to cause lower filtrate volume than those with crosslinked base solutions. The PEI-DS complex bridging effects revealed a denser, colored filter cake indicating a relatively homogenous dispersion and properly sized particles in the filter cake.