Doe/netl-2012/1540 Mobility And Conformance Control For Carbon Dioxide Enhanced Oil Recovery (Co2-Eor) Via Thickeners, Foams, And Gels - U.s. Department Of Energy Page 57

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Figure 4.7. PolyBOVA [Tapriyal, 2009]; Mw = 12,000; this copolymer was slightly soluble in
o
CO
at pressures far above MMP and induced a 40% increase in CO2 viscosity at 1wt%, 25
C,
2
10,000 psia
Although ~40% and ~80% increases in viscosity were realized at 1 and 2wt% concentrations of
polyBOVA, the pressure required to dissolve only 0.5wt% of a vinyl acetate-styrene random
o
polymer (Mw = 12,000) in CO
was 64 MPa (~ 10,000 psia) at 25
C [Tapriyal, 2009].
2
In conclusion, several polymer-based thickeners have been identified.
These include a
fluorinated polyurethane disulfate telechelic ionomer and a homopolymer of fluoroacrylate. In
both of these cases the compound is highly fluorinated and roughly 3%–5wt% of the compound
is required to achieve a two-to four fold increase in CO
viscosity. An effective CO
thickener,
2
2
polyFAST, has been identified that can significantly increase the viscosity of CO
(~10-fold) at
2
reservoir conditions in dilute concentrations (~1wt%), but the cost of the fluoroacrylate
monomer is prohibitive. A non-fluorous analog of polyFAST, referred to as polyBOVA, was
only slightly CO
soluble at a pressure far beyond the MMP and induced small changes in CO
2
2
viscosity. Therefore, at the time of this report, an affordable, non-fluorous, polymeric or co-
polymer or associative polymeric CO
thickener capable of dissolving in CO
in dilute
2
2
concentrations (0.1 – 1.0 wt.%) at typical EOR conditions and increasing the CO
viscosity by a
2
factor of 2–20 at low superficial velocities has yet to be identified.
Small molecule CO
thickeners
2
The second strategy that has been explored for CO
thickeners has been the design of small
2
molecules that have the capability to associate and form viscosity-enhancing macromolecular
structures. Therefore, in each case, the molecule contains a segment that is CO
-philic enough to
2
promote dissolution of the compound in CO
. The compound also contains one or more CO
-
2
2
phobic moieties that are intended to be attracted to/associate with the CO
-phobic moieties of
2
neighboring molecules, thereby establishing a viscosity-enhancing, associating, non-covalently
bound, macromolecular network.
Trialkyltin fluorides and semi-fluorinated trialkyltin fluorides
Heller and co-workers recognized the remarkable ability of tributyltin fluoride (Figure 4.8) to
induce incredibly large viscosity increases in light alkanes at dilute concentration (e.g., ~ three
26

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