Exploration and Production Technologies
 
Development of Nanoparticle-Stabilized Foams To Improve Performance of Water-less Hydraulic Fracturing Last Reviewed 12/9/2014

DE-FE0013723

Goal
The overall objective of this project is to develop a new method of stabilizing foams for frac fluids, namely, the addition of surface-treated nanoparticles to the liquid phase. The research will be conducted using fluids already employed in hydraulic fracturing (carbon dioxide [CO2], nitogen [N2], water, liquefied petroleum gas [LPG]) and commercially available nanoparticles.

Performer
The University of Texas at Austin, Austin, TX, 78712-0228

Background
The vast majority of hydraulic fracturing jobs are formulated with fresh water, and the use of water resources introduced by the rapidly growing development of unconventional oil and gas reservoirs is high. Foamed fluids for hydraulic fracturing have been used for more than forty years to improve flowback and cleanup after treatment, to improve stimulation performance by reducing leakoff rates, and to reduce fluid blocking of hydrocarbon production from the reservoir. A decisive advantage of foamed fluids is that they use substantially less water, thus making them easier to use for hydraulic fracturing would help reduce the demand for fresh water. Nanoparticles with suitable surface coatings have several advantages specific to the application of foamed frac fluids: they can stabilize foams very effectively and for long periods of time; they are small enough to stabilize small bubbles and hence enable large foam viscosities (needed for carrying proppant); they are much smaller than fracture widths and pores in proppant packs allowing them to be transported out of the reservoir during flowback; and their coating and concentration can be tuned to different fluid/fluid systems. Crucially, the mechanism by which nanoparticles stabilize foam differs from the mechanism for current technologies (i.e., surfactants and emulsifiers). This enables a potentially significant advance: foams can be generated that will carry proppant into a fracture but will break at a tunable threshold pressure after the stage is pumped and will not re-form in the proppant pack during flowback. These advantages would simplify the design and reliability of foamed frac jobs, thus reducing one of the obstacles to using less water for hydraulic fracturing.

Impact
This project seeks to demonstrate that suitably coated nanoparticles can stabilize foams of fluids useful for hydraulic fracturing (CO2 and water; N2 and water; N2 and LPG) at elevated pressures and at temperatures between ambient and reservoir. The water-based foams require four to five times less water per barrel of fluid than conventional water-based frac fluids. The LPG foam would require no water and three to five times less LPG than current water-less fluids. Thus this research would have a significant impact on the development of unconventional oil and gas resources in areas where water use and/or disposal is constrained.

The results of this research will expand the options available to operators for hydraulic fracturing and can simplify the design and field implementation of foamed frac fluids. This technology, when developed, will make it easier for operators to switch to reduced-water or zero-water hydraulic fracturing campaigns, thereby alleviating one of the most sensitive challenges for domestic hydrocarbon production.

Accomplishments (most recent listed first)

  • Nanoparticle/surfactant/polymer synergy was explored in order to increase the foam viscosity. C/W foams of 70 centipoise (cP) at 0.95 quality were stabilized by using 0.15 % HPAM, 1% Nissan EOR-5XS nanoparticles and 0.08 % LAPB surfactants, which is comparable to typical viscosities of fracturing fluids reported in literature.
  • Phase behavior studies of mixtures of a series of different polymers, surface modified NPs and surfactants have been further investigated to show that the formulations were stable in CO2 saturated 2% potassium chloride brine at pressures and temperatures relevant to field operation conditions (1000–5000 pounds per square inch, 50 degrees Celsius).
  • A simulator for nanoparticle-stabilized foam flowback after hydraulic fracturing has been developed in order to study the effect of depressurization on nanoparticle-stabilized foams. A preliminary comparison of fracture propagation with slick water, viscous fracpad, and 0.9-quality foam shows that foams leave a much cleaner proppant bed after fracturing, which can subsequently improve producibility from the formation.
  • Stable CO2-in-water foams were produced in a beadpack using mixtures of surface-modified, commercially available silica nanoparticles and three carboxybetaine surfactants. These foams have much higher viscosity than foams generated with the either the nanoparticles or surfactant alone. This synergy is a remarkable property and, to our knowledge, not previously demonstrated.
  • Building on this synergy between nanoparticles and a very low concentration of betaine surfactant, the project team was able to generate stable 90 percent quality CO2-in-water foams—with apparent viscosities as high as 50 cP—with addition of 0.1 percent of partially hydrolyzed polyacrylamide polymer.  The polymer provides a second, distinct synergistic effect: foam cannot be generated until a threshold polymer concentration is reached. 
  • Conceptual models have been developed to predict stability of bulk foams and foams in porous media under different operating and synthesis conditions with particular attention to the influence of pressure, which is the proposed mechanism for controlling foam destabilization for flowback after fracture stimulation.

Current Status (December 2014)
Foam generation experiments are being conducted to explain the basis for the nanoparticle, surfactant, and polymer synergy in foam stabilization. Of particular interest is keeping the  CO2:water ratio high, while maintaining this synergy and determining the role of operating conditions (temperature and pressure). 

A detailed literature review on particle-surfactant interactions and their influence on foam (as well as emulsion) stability under different conditions has provided some insight on how to tune the interactions to reservoir conditions. A more detailed study of like-charged particles and surfactants for foams, as well as of the interactions between surfactants and surface-modified particles (e.g., Nissan EOR-series and PEG-coated particles) is being conducted because this information does not  appear to be available in the literature.

The ability to control pressure on stable, static foam and observe whether collapse occurs at a threshold pressure is being developed. An apparatus to test N2/NGL (Natural Gas to Liquid) foams is currently being designed and constructed.  

Numerical simulation software has been written for the propagation of CO2-water bulk foams stabilized by nanoparticles. Fracture geometry was obtained using commercial software. The project team is focusing on simulating fracture clean-up. A population balance model was coupled with a pressure, mass, and colloid filtration model to simulate foam flow inside a fracture. Preliminary simulations show that foam lowers water saturation compared to conventional fluids. The project team continues to test the software under multiple scenarios and improve models of foam formulations (with or without surfactant or polymer) provided by experimental work.

Project Start: October 1, 2013
Project End: September 30, 2016

DOE Contribution: $1,089,660
Performer Contribution: $272,995

Contact Information:
NETL – Gary Covatch (gary.covatch@netl.doe.gov or 304-285-4589)
UT– Masa Prodanovic (masha@utexas.edu or 512-471-0839)

Additional Information:

Quarterly Project Performance Report [PDF-983KB] January - March, 2014

Quarterly Project Performance Report [PDF-784KB] October - March, 2013 

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