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Title: "Smart" Multifunctional Polymers for Enhanced Oil Recovery

Abstract

Recent recommendations made by the Department of Energy, in conjunction with ongoing research at the University of Southern Mississippi, have signified a need for the development of 'smart' multi-functional polymers (SMFPs) for Enhanced Oil Recovery (EOR) processes. Herein we summarize research from the period of September 2003 through March 2007 focusing on both Type I and Type II SMFPs. We have demonstrated the synthesis and behavior of materials that can respond in situ to stimuli (ionic strength, pH, temperature, and shear stress). In particular, Type I SMFPs reversibly form micelles in water and have the potential to be utilized in applications that serve to lower interfacial tension at the oil/water interface, resulting in emulsification of oil. Type II SMFPs, which consist of high molecular weight polymers, have been synthesized and have prospective applications related to the modification of fluid viscosity during the recovery process. Through the utilization of these advanced 'smart' polymers, the ability to recover more of the original oil in place and a larger portion of that by-passed or deemed 'unrecoverable' by conventional chemical flooding should be possible.

Authors:
;
Publication Date:
Research Org.:
University of Southern Mississippi
Sponsoring Org.:
USDOE
OSTI Identifier:
924164
DOE Contract Number:
FC26-03NT15407
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
02 PETROLEUM; PETROLEUM; ENHANCED RECOVERY; EMULSIFICATION; MOLECULAR WEIGHT; POLYMERS; RESEARCH PROGRAMS; FLUID INJECTION

Citation Formats

Charles McCormick, and Andrew Lowe. "Smart" Multifunctional Polymers for Enhanced Oil Recovery. United States: N. p., 2007. Web. doi:10.2172/924164.
Charles McCormick, & Andrew Lowe. "Smart" Multifunctional Polymers for Enhanced Oil Recovery. United States. doi:10.2172/924164.
Charles McCormick, and Andrew Lowe. Tue . ""Smart" Multifunctional Polymers for Enhanced Oil Recovery". United States. doi:10.2172/924164. https://www.osti.gov/servlets/purl/924164.
@article{osti_924164,
title = {"Smart" Multifunctional Polymers for Enhanced Oil Recovery},
author = {Charles McCormick and Andrew Lowe},
abstractNote = {Recent recommendations made by the Department of Energy, in conjunction with ongoing research at the University of Southern Mississippi, have signified a need for the development of 'smart' multi-functional polymers (SMFPs) for Enhanced Oil Recovery (EOR) processes. Herein we summarize research from the period of September 2003 through March 2007 focusing on both Type I and Type II SMFPs. We have demonstrated the synthesis and behavior of materials that can respond in situ to stimuli (ionic strength, pH, temperature, and shear stress). In particular, Type I SMFPs reversibly form micelles in water and have the potential to be utilized in applications that serve to lower interfacial tension at the oil/water interface, resulting in emulsification of oil. Type II SMFPs, which consist of high molecular weight polymers, have been synthesized and have prospective applications related to the modification of fluid viscosity during the recovery process. Through the utilization of these advanced 'smart' polymers, the ability to recover more of the original oil in place and a larger portion of that by-passed or deemed 'unrecoverable' by conventional chemical flooding should be possible.},
doi = {10.2172/924164},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Mar 20 00:00:00 EDT 2007},
month = {Tue Mar 20 00:00:00 EDT 2007}
}

Technical Report:

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  • Herein we report the aqueous polymerization of acrylamide using reversible addition fragmentation chain transfer (RAFT) polymerization to perform a comprehensive study on the polymerization of acrylamide. More specifically, the effect of polymerization conditions on the polymerization kinetics, molecular weight control, and blocking ability were examined. With this in mind, it was necessary to prepare ''A'' block (corona of the micelle) from a hydrophilic monomer. The responsive ''B'' block present in the core will be disclosed in the next two reports.
  • Herein we report the synthesis and solution characterization of a novel series of AB diblock copolymers with neutral, water-soluble A blocks comprised of N,N-dimethylacrylamide (DMA) and pH-responsive B blocks of N,N-dimethylvinylbenzylamine (DMVBA). To our knowledge, this represents the first example of an acrylamido-styrenic block copolymer prepared directly in homogeneous aqueous solution. The best blocking order (using polyDMA as a macro-CTA) was shown to yield well-defined block copolymers with minimal homopolymer impurity. Reversible aggregation of these block copolymers in aqueous media was studied by {sup 1}H NMR spectroscopy and dynamic light scattering. Finally, an example of core-crosslinked micelles was demonstrated bymore » the addition of a difunctional crosslinking agent to a micellar solution of the parent block copolymer. Our ability to form micelles directly in water that are responsive to pH represents an important milestone in developing ''smart'' multifunctional polymers that have potential for oil mobilization in Enhanced Oil Recovery Processes.« less
  • Two homopolyacrylamides, with intrinsic viscosities of 4.85 and 9.48 in water, were synthesized for hydrolysis studies. Samples with degrees of hydrolysis ranging from 29 to 77% have been prepared from these two homopolymers. Additional poly(dextran-g-acrylamide) samples have been prepared via the ceric ion technique. A maximum of 71% acrylamide has been achieved in the copolymers. Additional work on the solution properties of polyacrylamide-type polymers in the low shear rate region (0 to 1000 sec /sup -1/) has been completed. The theoretical models for dilute polymer solutions of Bueche and of Graessley have been utilized to analyze the rheological data frommore » four commercial partially hydrolyzed polyacrylamides. Flow curves of aqueous solutions of Dow's Pusher/sup R/ 500 and Allied Colloid's Alco/sup R/ 800, Alco/sup R/ 1000, and Alco/sup R/ 1200 were measured at 3000, 1500, and 750 ppM in 1.5% Na/sub 2/SO/sub 4/ solution. All flow curves were measured at 30/sup 0/C. The zero shear viscosities and molecular response times were calculated from these data using Bueche's analysis and Graessley's analysis and are summarized. Results from the Bueche analysis give higher values for the zero shear viscosity when compared to results from the Graessley analysis, but lower values for the molecular response time. However, the Bueche parameters are linearly correlated with the Graessleyparameters. More precise data are needed in the very low shear rate range to determine which model, Bueche's or Graessley's, is most reliable in predicting the rheological properties of dilute polymer solutions at very low rates of fluid shear.« less
  • Synthetic polymers have been carefully prepared as models of known composition and measurable molecular weight, molecular weight distribution, ionic charge density, and branching. Major efforts have been centered on random copolymers of acrylamide with sodium acrylate and on graft copolymers of acrylamide with well characterized polysaccharides such as dextran and amylose. Additionally, random copolymers of poly(acrylamide-co-sodium acrylate) have been prepared by controlled hydrolysis of polyacrylamide homopolymer. The synthesized laboratory samples as well as selected commercial samples have been extensively characterized. Solution rheological studies have been initiated to investigate the interrelationships between solution behavior and hydrodynamic volume. For example, relationships betweenmore » molecular structure and solution properties under more ideal conditions have been rather rigorously developed in theory. Intrinsic viscosities of synthesized model polymers and representative commercial samples have been obtained utilizing the Huggins equation, Kraemer equation, and Schulz--Blaschke equation. Effects of mixing conditions and aging effects as well as solvent, electrolyte, pH, and temperature dependence on intrinsic viscosity have been measured. Polymer solution degradation studies during the first year have been directed towarddeveloping quantitative assessments of fluid shear stresses and their effects on primary and secondary bond dissociations during flow of polymer containing fluids through porous media. Laboratory evidence seems to indicate that apparent ''shear degradation'' observed for a number of polymers in aqueous solutions is largely a result of secondary bond dissociation rather than primary bond cleavage. This phenomenon is reversible and highly time and concentration dependent. Mobility control loss, during polymer flooding, may be largely due to adsorption, flocculation, and excluded volume effects.« less
  • This report focuses on the FY-89 results of a fundamental research program underway in the Polymer Science Laboratories at the University of Southern Mississippi to develop novel associative polymers which should be significantly more efficient than those presently used in Enhanced Oil Recovery processes. These new systems rely on cooperative hydrophobic associations to yield appropriate rheological behavior. We hope to ultimately develop, with the help of appropriate rheological behavior. We hope to ultimately develop, with the help of industry, simple copolymer systems which could be easily utilized by independent oil operators in mobility control processes. Research has focused on preparation,more » characterization and rheological study of copolymers possessing intra- or intermolecular associations. Associative copolymers of acrylamide with N-alklacrylamides; terpolymers of acrylamide, N-decylacrylamide, and NaAMPS, NaA, or NaAMB; and copolymers of acrylamide with the zwitterionic AMPDAPS monomer have been shown to possess rheological behavior of potential in EOR processes. The salt-induced conformational responses and resulting association mechanisms are being studied by a number of techniques including rheometry, gel permeation chromatography, quasielastic light scattering, and fluorescence spectroscopy. 114 refs., 50 figs., 18 tabs.« less