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Title: Inexpensive CO2 Thickening Agents for Improved Mobility Control of CO2 Floods

Technical Report ·
DOI:https://doi.org/10.2172/968338· OSTI ID:968338

The objective of this research was the design, synthesis and evaluation of inexpensive, non-fluorous carbon dioxide thickening agents. We followed the same strategy employed in the design of fluorinated CO{sub 2} polymeric thickeners. First, a highly CO{sub 2}-philic, hydrocarbon-based monomer was to be identified. Polymers or oligomers of this monomer were then synthesized. The second step was to design a CO{sub 2}-thickener based on these CO{sub 2}-philic polymers. Two types of thickeners were considered. The first was a copolymer in which the CO{sub 2}-philic monomer was combined with a small proportion of CO{sub 2}-phobic associating groups that could cause viscosity-enhancing intermolecular interactions to occur. The second was a small hydrogen-bonding compound with urea groups in the core to promote intermolecular interactions that would cause the molecules to 'stack' in solution while the arms were composed of the CO{sub 2}-philic oligomers. Although we were not able to develop a viable thickener that exhibited high enough CO{sub 2} solubility at EOR MMP conditions to induce a viscosity increase, we made significant progress in our understanding of CO{sub 2}-soluble compounds that can be used in subsequent studies to design CO{sub 2}-soluble thickeners or CO{sub 2}-soluble surfactant-based foaming agents. These findings are detailed in this final report. In summary, we assessed many polymers and verified that the most CO{sub 2}-soluble oxygenated hydrocarbon polymer is poly(vinyl acetate), PVAc. This is primarily due to the presence of both ether and carbonyl oxygens associated with acetate-rich compounds. In addition to polymers, we also made small acetate-rich molecules that were also capable of associating in solution via the inclusion of hydrogen-bonding groups in hopes of forming viscosity-enhancing macromolecules. Despite the presence of multiple acetate groups in these compounds, which can impart incredible CO{sub 2}-solubility to many compounds, our attempts to make acetate-rich high molecular weight polymers and small hydrogen-bonding compounds did not yield a highly CO{sub 2}-soluble polymer or hydrogen-bonding associative thickener. The conclusions of our molecular modeling calculations confirmed that although acetates are indeed 'CO{sub 2}-philic', nitrogen-containing amines also interact favorably with CO{sub 2} and should also be examined. Therefore we obtained and synthesized many N-rich (e.g. amine-containing) polymers. Unfortunately, we found that the intermolecular polymer-polymer interactions between the amines were so strong that the polymers were essentially insoluble in CO{sub 2}. For the convenience of the reader, a table of all of the polymers evaluated during this research is provided.

Research Organization:
Univ. of Pittsburgh, PA (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
FC26-01BC15315
OSTI ID:
968338
Country of Publication:
United States
Language:
English