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org/EF Review

Thickening CO2 with Direct Thickeners, CO2‑in-Oil Emulsions, or

Nanoparticle Dispersions: Literature Review and Experimental
Validation
P. C. Lemaire,* A. Alenzi, J. J. Lee, E. J. Beckman, and R. M. Enick

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ABSTRACT: High molecular weight associating random copolymers,

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such as poly(fluoroacrylate-styrene) (polyFAST), are direct CO2

thickeners that can dissolve readily in CO2 and significantly increase
viscosity. Although polyfluoroacrylate (PFA) is more CO2-soluble
than polyFAST, PFA induces less thickening because it is non-
associating. High molecular weight poly(dimethylsiloxane) (PDMS)
and poly(vinyl acetate) (PVAc) can increase CO2 viscosity if toluene
cosolvent is introduced. Bis(2-ethylhexyl) sulfosuccinate sodium salt
(AOT) can thicken CO2 modestly if ethanol cosolvent is added. Little
CO2 thickening has been reported for low molecular weight polymers,
including poly(vinyl ethyl ether) (PVEE) and poly-1-decene (P1D).
Associating oligomers of poly(propylene oxide) (PPO) with pendant
aromatic groups showed modest CO2 viscosity enhancement. Cross-
linked phosphate esters can increase the viscosity of CO2 if a very
substantial concentration of a light alkane cosolvent is added. Indirect
thickening of CO2 involves the generation of high apparent viscosity, completely waterless CO2-in-oil (C/O) emulsions that can be
attained when CO2 is mixed with mineral oil containing a silicone-alkyl copolymeric surfactant; similar behavior was observed with a
proprietary blend of oil and surfactants. Only one nanoparticle-based thickening of CO2 involving the dispersal of dilute
concentrations of nanoparticles that are surface-functionalized with highly CO2-philic groups was reported (however, no explanation
was provided to explain how the high molecular weight polymer used in this study could be CO2-soluble). New experimental results
were obtained for some readily available or easily synthesized CO2-thickening candidates. PolyFAST yielded very substantial
viscosity increases. PFA, PDMS-toluene, and PVAC-toluene could appreciably thicken CO2. Very little detectable viscosity
enhancement was achieved with low molecular weight PVEE or P1D. CO2 was thickened slightly with AOT-ethanol. Regarding
future studies, novel, nonfluorous associating CO2-philic oligomers, and highly CO2-philic phosphate esters that remain dissolved in
CO2 after cross-linking are the most obvious candidates for CO2 direct thickeners.

1. INTRODUCTION TO THE NEED FOR THICKENED thickener would not require organic cosolvents or prolonged
CO2 DURING ENHANCED OIL RECOVERY AND stirring and would thicken CO2 at typical wellhead, injection
WATERLESS FRACTURING wellbore, and reservoir conditions.1 The thickener would
increase the viscosity of CO2 to the desired value via
A CO2 thickener could be a transformative technology for two
manipulation of its concentration in CO2. For example, during
distinct petroleum engineering applications. It would suppress
CO2 enhanced oil recovery, one might adjust the viscosity of the
unfavorable mobility ratios during CO2 enhanced oil recovery
CO2 such that a favorable mobility ratio of unity (M = 1) is
(EOR), thereby reducing or eliminating the implementation of
attained. This corresponds to an ∼10−100-fold viscosity
water-alternating-gas (WAG) techniques.1 A CO2 thickener
increase.2 During CO2 hydraulic fracturing operations, one
could also improve the performance of CO2 as a fracturing fluid,
primarily by allowing higher loadings of larger proppant particles
to be blended with the high-pressure liquid CO2. Received: February 5, 2021
The ideal carbon dioxide (CO2) thickener would be an Revised: April 22, 2021
affordable, safe, pumpable, environmentally benign additive that Published: May 12, 2021
could quickly establish a high-viscosity, CO2-rich fluid without
the need for heating the mixture to facilitate dissolution followed
by cooling to promote gelation or thickening. Further, the ideal

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Table 1. Summary of Thickening Technologies Discussed in This Review

could target viscosity values that would facilitate the loadings of

proppant particles comparable to that achieved with aqueous strategies for thickening CO2 will be reviewed: direct thickeners
fluids, which represents at least a ∼100-fold increase. Three that dissolve in CO2,3 indirect thickeners that establish high-
8511 https://doi.org/10.1021/acs.energyfuels.1c00314
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Energy & Fuels
quality CO2 foams or emulsions,4 and dispersed nanoparticle-
based CO2 thickeners.5
The largest body of research has focused on “direct
thickeners” for CO2. The term direct thickener was coined by
John Heller and co-workers at Petroleum Recovery Research
Center of New Mexico Institute of Mining and Technology
during their pioneering work in this area in the early 1980s.6
“Direct thickener” infers that a compound will dissolve in the CO2
and form a thermodynamically stable, transparent, single-phase
solution that is significantly more viscous than pure CO2. The
attainment of a stable single-phase solution is particularly
important for EOR in conventional formations where the fluid
must flow through an interconnected network of micrometer-
scale pores. It would be beneficial if the thickener was water-
insoluble, in order to prevent it from partitioning into brine.
Further, the ideal direct thickener would be unlikely to exhibit
significant adsorption onto sandstone or carbonate surfaces. As a
rule of thumb, it would be desirable for technical, economic, and
logistical to thicken CO2 by a factor of 10−100 at thickener
concentrations of 0.1−1 wt %, preferably closer to the 0.1 wt %
value. Although CO2 is a Newtonian fluid with shear-rate-
independent viscosity, the directly thickened CO2 is likely to
exhibit shear-thinning characteristics.
The secondary emphasis of this review will focus on indirect
thickening via the generation of carbon dioxide-rich foams or
emulsions with a high “apparent viscosity”. The most notable
and common examples of CO2-based foams are high-pressure
CO2-in-water (C/W) (i.e., CO2-discontinuous, water-continu-
ous) emulsions or foams that are stabilized by the presence of
water-soluble surfactants. (The term “emulsion” is typically used
if the system contains subcritical liquid CO2, while “foam” is
used for systems containing supercritical CO2.) Foam formation
requires mixing of CO2 with an aqueous surfactant solution
either on the surface (via mechanical mixing), in the wellhead
(via the collision of the fluids), or within the porous media
(where the rock acts as a static mixer). These foams are typically
designed to contain a large proportion of CO2 in a bubble phase
and a low proportion of continuous films of surfactant-stabilized
water. Although the CO2 contained in the bubbles is not
thickened, the foam aggregate can exhibit a high apparent
viscosity that is significantly greater than either the CO2 or
aqueous phase, especially if the bubbles are small. These two-
phase foams are not thermodynamically stable single-phase
solutions, yet they can exhibit a useful apparent viscosity and
sufficient stability to yield improved performance during EOR or
fracturing. C/W foams can also be generated with surfactants
that are CO2-soluble. In this case, the low-viscosity single-phase
CO2-surfactant solution can be mixed with co-injected brine or
in situ brine to generate a C/W foam, but most of the surfactant
should be transported out of the CO2 bubbles and partition into
the aqueous films in agreement with Bancroft’s rule. There have
been numerous reports and reviews of C/W foams,2 and such
foams have been tested in the field. Therefore, this review will
not include C/W foams. However, it is also possible to generate an
indirect CO2thickener that is a completely anhydrous, high apparent
viscosity, CO2-in-oil (C/O) emulsion or foam (i.e., CO2-
discontinuous, oil-continuous emulsions or foams that are
stabilized by the presence of oil-soluble surfactants). C/O
emulsions have long been a niche area of interest related to
waterless hydraulic fracturing in water-sensitive formations. The
literature related to C/O foams and emulsions will be included
in this review. We recently reported that a novel, mineral oil-
soluble surfactant composed of a poly(dimethylsiloxane)
pubs.acs.org/EF Review
(PDMS) backbone with multiple pendant tricontyl groups
(-C30H61) can stabilize CO2-in-mineral oil (C/O) foams.2 The
PDMS backbone molecular weight was chosen such that it was
more CO2-philic than oil-philic, while the pendant tricontyl
groups were oil-philic and CO2-insoluble. Our group also
replicated numerous earlier attempts to form C/O emulsions
and foams with commercially available surfactants.2 To date, C/
O foams have not been suggested for use in EOR because of the
lower expense and greater ease in making C/W foams. However,
there is a continuing interest in C/O foams for completely
waterless fracturing, especially in water-sensitive formations.
During hydraulic fracturing, the apertures of the flow paths (the
wellbore and the hydraulic fractures) are orders of magnitude
greater than the pore sizes in sandstone and carbonates
encountered during EOR. Therefore, when CO2 is being
considered as a fracturing fluid7 either transparent single-phase
solutions of direct thickeners dissolved in CO2, or indirect
thickeners that stabilize waterless, opaque, two-phase C/O
emulsions may be useful.
The third “thickening” strategy that will be reviewed is related
to a handful of attempts to increase the apparent viscosity of
CO2via the dispersion of nanoparticles (NPs). There have been a
very small number of reports of dispersing nanoparticles in CO2
and an even smaller number of studies in which such particles
were designed to induce a significant increase in CO2 viscosity.
Typically, the nanoparticles are surface-modified to prevent
agglomeration and promote dispersion in CO2, or the
nanoparticles are added in conjunction with a CO2-soluble
polymer.
Table 1 presents a summary of the attributes, advantages, and
disadvantages of direct thickeners, indirect thickeners, and NP-
based thickeners.
1.1. Direct CO2 Thickeners That Dissolve in CO2 and
Form a High-Viscosity, Transparent, Stable, Single-
Phase Solution. Two commonly used classes of direct
thickener candidates for increasing liquid viscosity (whether
water, oil, CO2, or natural gas liquids (NGLs)) include high
molecular weight polymers or associating polymers and low
molecular weight, self-assembling compounds that form supra-
molecular structures. This review will include a review of
attempts to thicken CO2 with either type of compound.
Although it is possible to identify high or ultrahigh molecular
weight polymers that readily dissolve in common liquids (e.g.,
polyacrylamide in water, poly(α-olefins) in hydrocarbon-based
oils) and thicken them, the ability to dissolve high or ultrahigh
molecular weight polymers in dense CO2 at wellbore or reservoir
conditions is extremely challenging because CO2 is a feeble
solvent relative to oils and organic solvents. Heating and/or the
addition of a CO2-soluble organic cosolvent (both of which are
undesirable for field-scale operations) may be required to
facilitate dissolution of the polymers in the solvent.
The fundamental advantage of the small-molecule thickener is
that remarkably high increases in viscosity, including the
formation of transparent rigid gels, can be attained at mass
concentrations in the 0.1−1.0 wt % range.8,9 The apparent
molecular weight of the supramolecular structure formed by
these associating small molecules can exceed the molecular
weight of conventional polymers. However, many (but not all)
small-molecule thickeners require heating and mixing when
combined with a fluid to attain dissolution, followed by cooling
to realize gelation and viscosity enhancement. Further, the
viscosity of a fluid that has been thickened with small molecules
at low temperature typically diminishes dramatically when the
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Table 2. Summary of CO2 Thickener Literature Reviews

polymer small-molecule C/O NP C/W critical exptl comparison
first direct direct indirect dispersion indirect assessment of of many
author thickener thickener thickener thickener thickeners claims candidates type of report year ref
Lee yes yes no no no no no non-peer reviewed 2016, 1, 3
2014
Enick yes yes no no no no no non-peer reviewed 1998 10
Enick yes yes no no yes yes no non-peer reviewed 2011, 2, 11
2012
AlHinai yes yes no no no no no book chapter 2019 12
Zhou yes yes no no no no no peer-reviewed 2021 13
article
Lemaire yes yes yes yes no yes yes peer-reviewed 2021 this
article work

fluid is heated to temperatures great enough to diminish the
intermolecular attractive forces that favor self-assembly. Note
that small self-assembling compounds may “thicken” a solution
via the formation of micrometer- or nanometer-scale fibers
dispersed in the solvent as the liquid−thickener mixture cools.
Although such a mixture may appear to be viscous when assessed
with a conventional viscometer, these fibers may be retained by
the inlet face of a porous medium rather than flowing through
the rock with the solvent. These opaque, two-phase mixtures of
interlocking solid fibers suspended in a liquid are not considered
to be direct thickeners for the purposes of this study. Although it
is relatively easy to identify small-molecule oil thickeners, the
ability to dissolve small molecules in CO2 that form viscosity-
enhancing supramolecular networks that remain dissolved in a
CO2-rich solution is extremely challenging.
There is a long history of attempts to increase the viscosity of
CO2 with either polymers or small molecules, which has been
summarized in several introductory sections of papers or
proceedings, dissertation, or literature reviews reports.1−3,10,11
The prior non-peer-reviewed literature reviews of direct
thickening with polymers or small associating compounds
have been presented in a doctoral dissertation1 and an associated
Society of Petroleum Engineers (SPE) conference proceeding.3
There have been two National Energy Technology Laboratory
(NETL) contract literature reviews that focused on direct CO2
thickeners; the first was published in 1998,10 while the second
was published in 20112 and presented at an SPE conference in
2012.11 There have been no literature reviews (whether peer-
reviewed or not) of direct CO2 thickening, indirect thickening of
CO2 with waterless emulsions, or thickening CO2 with
dispersions of nanoparticles. However, in 2019 a book chapter
on thickening of high-pressure gas was authored by Al Hinai and
colleagues that presented attempts to thicken CO2 with
polymers, oligomers, and small molecules.12 In mid-2021, a
review of direct thickeners was presented by Zhou and
colleagues.13 Both of these reviews presented the results of
direct-thickening studies; however, both of these recent reviews
were not critical in nature and presented no reviews of indirect
thickeners or nanoparticle dispersion thickeners or proprietary
thickeners, and neither provided the reader with specific
suggestions for future research directions or a side-by-side
comparison of a wide array of purported CO2 thickeners.
Therefore, our study was intended to present the first peer-
reviewed critical literature review of polymeric, associating
polymers, low molecular weight polymers, oligomers, and small-
molecule associating thickeners, in addition to reviews of
indirect thickening with waterless emulsions and thickening
with dispersion of nanoparticles. Further, in an attempt to
confirm the thickening capability of some thickeners, or resolve
8513
conflicting reports concerning other thickener performance, this
review provides an experimental assessment of the solubility and
thickening capabilities of many readily obtainable thickeners
that was conducted. Table 2 presents a summary of these
reviews.
1.1.1. Polymeric Direct Thickener Literature Review. Table
3 presents a summary of the attributes, advantages, and
disadvantages of many of the polymeric direct-thickening
candidates.
The initial candidates for direct thickeners were oil thickeners
(rather than water thickeners) because CO2 is miscible with
many light oil components but only slightly miscible with
water.1,3 Nonpolar organic polymers were expected to dissolve
in CO2 more readily than water-soluble polymers. Heller and co-
workers investigated this type of polymer6 and found 18
polymers characterized by CO2-solubility values of 0.22−10 g/L
(0.24−1.1 wt %) at temperatures of 20−58 °C and pressures of
11.7−21.4 MPa (1,700−3,100 psia) (CO2 density values of
∼0.7−0.9 g/mL). None of the candidates thickened CO2
substantially, although several of the polymers caused slight
viscosity increases. They found that an ∼1.1% solution of low
molecular weight (MW 409) atactic poly(methyl oxirane)
(PMO) increased CO2 viscosity by 21−28% at 28−33 °C and
pressures of ∼13.8−19.9 MPa (2,000−2,600 psia). Thereafter
attempts were made to increase the entropy of mixing in order to
enhance polymer solubility. This led to the assessment of
poly(α-olefins), such as poly(α-hexene).14 Although some of
these polymers were slightly soluble in CO2, none were effective
thickeners. Heller’s team found that in order to attain a small
measure of CO2 solubility, the molecular weight of the polymers
had to be very low (MW < 1,000). This low molecular weight,
which is more characteristic of oligomers than ultrahigh
molecular weight polymers, was far below values typically
associated with polymeric oil thickeners. Heller’s team showed
that poly(vinyl ethyl ether) (PVEE) and poly-1-decene (P1D)
were soluble in CO2 to 5.5 and 10.3 g/L (0.57−1.2 wt %,
respectively. However, neither PMO, PVEE, nor P1D, nor any
other commercial polymer tested by their team thickened CO2
to the extent desired (ideally a 10- to 100-fold increase). Heller
concluded that “The viscosity/concentration/molecular-weight
relationships do not seem anomalous for solutions of polymers in
liquid and supercritical CO2. It is expected, therefore, that larger
viscosity increases for smaller concentrations of additive can be
attained with high-molecular-weight polymers, if soluble ones can be
synthesized.” Heller was suggesting that a search for a CO2
thickener should pursue the same path as thickeners for water
and oil: identify the highest molecular weight polymer that
displays at least a small degree of solubility in CO2 because dilute
concentrations of oligomers or low molecular weight polymers
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Table 3. Summary of Commonly Studied Polymeric CO2 Direct Thickener Candidatesa

a
Reference links: 3, 5, 6, 15, 17, 19, 20, 21, 23, 24, 26, 32, 33, 34, 36, 38, 39, 41, 42, 44, 45, 46, 47, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 74, 77,
84.

are unlikely to be efficacious thickeners. It has also been but only at low molecular weights of up to several thousand that
established that poly(propylene oxide) (PPO) is CO2-soluble could be considered oligomeric.15 At higher molecular weight,
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PPO is essentially CO2-insoluble. However, very little viscosity
enhancement occurs when dilute concentrations of PPO are
dissolved in CO2.16
Nonetheless, a study by Zhang and co-workers17 gathered
attention with reports of capillary viscometer measurements
showing an ∼13-fold viscosity increase of CO2 (a 1,200%
increase) using only ∼0.5 wt % of two low molecular weight
polymers that Heller and colleagues had found to be ineffective
thickeners: PVEE (MW 3800) and P1D (MW 910). Outside of
the claims put forward by some recent investigators related to
oligomeric CO2 thickeners, our group has been unable to locate
a single reference for any low molecular non-associating polymer
(MW < 10,000) that is capable of thickening any liquid,
including water, oil, and natural gas liquids. For example, we
have found that conventional oil thickeners and water thickeners
are high molecular weight polymers (100,000−20,000,000),
with the highest reported molecular weights associated with drag
reducing polymers that can thicken light alkanes such as LPG or
propane in concentrations below 1 wt %.18 Hence, the Zhang et
al. results17 should be treated with caution. P1D (MW 910) was
also assessed as a CO2 thickener in the absence of cosolvent,
over the 0.5−10 wt % concentration range by Bashti and co-
workers.19 Remarkably high solubility was reported up to 100
°C; for example, at 25 °C the cloud point pressures at 0.5 and 10
wt % were 7.59 and 18.41 MPa (1,100 and 2,670 psi),
respectively. Remarkable thickening was also reported using a
viscometer described only as a “high temperature-high pressure
falling ball viscometer”. At 0.5 wt % P1D in CO2, the solution
viscosity was 3.5 greater than that of CO2; at 100 °C, a 10-fold
increase in viscosity was reported. No explanation of the
unusually high degree of thickening relative to other studies was
given. Neither was the dramatic increase in thickening with
increasing temperature provided. Therefore, the Bashti results
should also be treated with caution. Our in-house experimental
assessment of these two polymers was similar to the observation
of Heller and co-workers; we found that P1D and PVEE did not
induce an increase in viscosity of more than several percent.3
Further, Schecter’s group20,21 found no appreciable decrease in
mobility when 0.8 wt % low molecular weight PVEE (MW
3800) was used. Our group found that polymers with molecular
weights significantly greater than the P1D or PVEE used by
Zhang and Bashti were ineffective thickeners. For example, 2 wt
% CO2-soluble poly(vinyl acetate) (PVAc; MW 11,000) was
able to induce only a several percent increase in CO2 viscosity at
very high pressure.22 Al Hinai and colleagues examined the CO2-
thickening ability of four low molecular weight polymers (P1D;
MW 900; PVEE, MW 3800; poly(isobutyl vinyl ether) (PIVE),
MW 4000; PDMS, MW 5180),23 some of which Heller had
previously found to be poor thickeners. They23 accurately
portrayed the controversy regarding the viscous changes
associated with these oligomers and low molecular weight
polymers and reported viscosity increases significantly higher
than those reported by Heller, yet much smaller than those
shown in Zhang’s report.17 For example, the Al Hinai team
reported a 70% increase in CO2 viscosity using 1.2 wt % PVEE at
330 K, nearly three times greater than that reported by Heller for
the same mass concentration of a lower molecular weight PMO.
One would expect a greater increase because the PVEE
molecular weight is greater than the PMO molecular weight,
but a 3-fold viscosity increase at the same dilute mass
concentration is unexpectedly high given typical dilute solution
viscosity results. Further, in earlier work23,24 Al Hinai and co-
workers reported that CO2 was thickened by 50% using 1.5 wt %
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P1D oligomer (MW 544). The same group conducted core
studies that demonstrated how the alternating injection of
thickened CO2 with unthickened natural gas gave comparable
results to the continuous injection of thickened natural gas.25
Even if the Al Hinai results are accurate, it appears that, in the
best case, CO2-soluble low molecular weight polymers and
oligomers should be considered as modest thickeners. Rather
than inducing remarkable 5-fold or 10-fold increases in viscosity
at polymer concentrations of about 1 wt %, increases of only to
25−70% may be possible. A very recent paper5 reported CO2
viscosity increases of 20−400% for P1D in CO2 at 2−8 wt %;
however, no details of the falling ball viscometer were reported
and the molecular weight of the P1D was extremely high (MW
600,000). No explanation was offered as to how such a high
molecular weight P1D sample could be solubilized in CO2
without a cosolvent when prior investigators3,6,17,23,24 were only
able to dissolve very low molecular weight (∼500−1,000) P1D
in CO2. Another recent work attempted to shed insight on the
intermolecular interactions responsible for the purported
thickening of CO2 by PVEE (MW 3822) and P1D (MW 910)
using molecular dynamics simulations.26 The authors’ modeling
results indicated that the P1D (which can be considered as
branched because of its comb-like structure) dispersed as
isolated, or non-overlapped, soft spheres in CO2. The PVEE
(which can be considered as a “linear” polymer) forms
entanglements which lead to flow-resisting, viscosity-enhancing
networks. Owing to recent interest and conflicting conclusions
related to these oxygenated hydrocarbon polymers, the same
PVEE and P1D polymers used in the Zhang, Bashti, and Al Hinai
studies are included in the experimental portion of this work,
which enabled us to confirm whether P1D and PVEE are
ineffective, modest, or remarkable thickeners. Fortunately,
samples of low molecular weight P1D and PVEE were readily
available and remain available to any interested reader.
Recently, it has been reported that “phenyl-centered tri-chain
poly(ether-carbonate) (TMA-PEC)”, “phenyl-centered double-
chain poly(ether-carbonate) (TPA-PEC)”, and “phenyl-centered
four-chain poly(ether-carbonate) (TFA-PEC)”, along with
“1,1,1,3,5,5,5-heptamethyl-3-(3-[oxiran-2-ylmethoxy] propyl)-
trisiloxane modified TFA-PEC (TFA-PEC-SAGE)” were capable
of dissolving in CO2 and inducing viscosity increases.27 For
example, at 30 MPa (4350 psi) and 35 °C, TFA-PEC reportedly
thickened CO2 by about a factor of 10. However, the number-
average molecular weight of these polymers was only ∼2100−
2300, and none of the polymers possessed functional groups
recognized to lead to intermolecular interactions that establish
viscosity-enhancing macromolecular structures. Further, no
details of the falling ball viscometer were provided.
A 1987 U.S. patent by Bullen and co-workers28 claimed that a
polycarbonate-ether alternating or random copolymer of
molecular weight 20,000−150,000, derived from CO2 and
propylene oxide monomers was capable of tripling the viscosity
of CO2 at 2.5 wt %, 22 °C, and 10−25 MPa (1,450−3,600 psi),
although no details of the viscometer were provided. Our
group29 synthesized several poly(ether-carbonate) copolymers
derived from propylene oxide and CO2. Subsequent phase
behavior analysis demonstrated that the CO2 solubility of these
copolymers was extremely sensitive to the ratio of monomers,
with CO2 solubility achieved only for a narrow band of co-
monomer ratio. CO2 solubility data for a particular copolymer
(MW ∼ 16,000, 15.4 mol % carbonate) indicated that it could be
dissolved at a concentration of 1 wt % and 22 °C at 14 MPa
(2,030 psi), but no appreciable viscosity change occurred. These
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results29 indicate that the solubility levels for the copolymers (of
unspecified monomer ratio) reported in the Bullen et al.
patent28 appear to be higher than expected, with a level of
viscosity enhancement much greater than that observed in our
study. We were unable to obtain any of these copolymers for
experimental assessment in this study.
An attempt was made by researchers at the University of
Wyoming to polymerize CO2-soluble monomers, including
ethylene, octene, and decene, in dense CO2 in hopes of
generating CO2-soluble polymers.30 Polymers typically exhibit
dramatically lower solubility in solvents than their monomers.
Not surprisingly, the polymers that formed in CO2 precipitated
and no CO2 viscosity enhancement resulted.
In a 1990 patent, it was claimed that CO2 was thickened using
a viscous, substantially anhydrous liquid polymer solution in an
anhydrous solvent, which could be cross-linked by the
introduction of a metal ion source in order to form a viscous
single-phase solution. For example, the proposed treating fluid
was composed of 0−80 vol % CO2 combined with a methanol
solution containing polymers or copolymers based on the
dimethylacrylamide monomer and zirconium ions (e.g.,
zirconium oxychloride, zirconium lactate, and zirconium
acetate).31
Chevron researchers attempted to identify very high
molecular weight polymeric thickeners that exhibited enough
CO2 solubility to induce significant viscosity increases.32−34
Polymers with low-solubility parameters (<7 (cal/cc)0.5) were
chosen because the solubility parameter of CO2 at reservoir
conditions is approximately 5−6 (cal/cc)0.5.35 Further, it was
desired that the polymer exhibits multiple electron donor sites
associated with oxygen, nitrogen, or sulfur atoms that could
interact favorably with the electron acceptor site of the CO2
molecule, which is the carbon atom. Polymer electron donor
functional groups included siloxane, ether, thioether, sulfone,
carbonyl, ester, tertiary amine, dialkylamide, and silylether. The
Chevron researchers concluded that silicone oil (PDMS; MW
197,000; kinematic viscosity = 600,000 cstokes; 7.3 (cal/cc)0.5)
could indeed thicken CO2, but the dissolution of PDMS in CO2
had to be facilitated by the addition of a large proportion of
organic liquid cosolvent (e.g., toluene, 8.9 (cal/cc)0.5). Capillary
viscometry indicated that a 4 wt % PDMS, 20% toluene, 76%
CO2 solution exhibited a viscosity value of 1.2 cP, representing a
30-fold increase relative to pure CO2.34 This solution was
remarkably less mobile during Berea and SACROC core floods
than pure CO2, resulting in delayed CO2 breakthrough and
increased oil recovery. It was not evident if this study also
considered that the reduction of mobility could be partially
attributable to PDMS adsorption and wettability alteration. This
result demonstrated that thickened CO2 could indeed be
expected to exhibit diminished mobility in porous media, but the
level of cosolvent required was not practical for field application.
Although low molecular weight PDMS (MW < 10,000) can
dissolve in neat CO2,36 we observed only a few percent increase
in viscosity upon dissolution of several weight percent of low
molecular weight PDMS in CO2.1 It has been recently reported
by Gandomkar and co-workers that PDMS oligomers (4,800 <
MW < 10,000) are indeed remarkable CO2 thickeners. For
example an “HTHP falling ball viscometer” (no details provided)
was used to detect a 3.5-fold increase in viscosity at 25 °C and
3,400 psi using 2 wt % PDMS, and a 3.7-fold increase at 4 wt %.37
We urge caution when considering the results of Gandomkar
and co-workers because their thickening results for low
molecular weight PDMS are much more dramatic than those
8516
Review
observed by our team. Further, the Gandomkar thickening
results are comparable to the results reported by Chevron even
though Chevron employed significantly higher molecular weight
PDMS.
The Chevron finding that 4 wt % high molecular weight
PDMS (MW = 197,000) could dissolve in CO2 when an organic
cosolvent was employed was consistent with the finding of
Heller and co-workers that ∼0.03 wt % PDMS (MW = 135,000)
could dissolve in CO2 at 25 °C and 2,750 psia.6 Both groups
concluded that high molecular weight PDMS was CO2-philic.
But it was apparent that to dissolve enough PDMS in the CO2 to
thicken the solution, toluene cosolvent had to be added. The
finding that PDMS was indeed more CO2-philic than hydro-
carbon-based polymers38 was reported by others.15,39 Recently a
silicone ter-polymer was synthesized that induced comparable
increases in CO2 viscosity with comparable amounts of
toluene.40 Unfortunately, this work did not cite Bae and Irani’s
work34 or explain why the combinations of three monomers
(octamethylcyclotetrasiloxane, methyl triethoxysilane, and
aminopropyltriethoxysilane) to make a complex silicone
provided a better thickener than PDMS on the basis of a single
monomer. Likewise, Sun and workers41 claimed to have
developed a novel CO2 thickener, which was a toluene−
PDMS mixture, yet the Bae and Irani work34 was again not
mentioned. Li and co-workers42 and Wang and co-workers43
synthesized a modified silicone, an epoxy ether-based PDMS of
MW 21,000, that they claimed yielded viscosity values about 2−
3 times greater than that of linear PDMS in the presence of
toluene as a cosolvent. Viscosity values as great as 1.3 cP at 30 °C
and 18 MPa (2610 psi) were reported using 3 wt % thickener,
9% toluene, and 88% CO2. However, they did not explain how 3
wt % of the epoxy-terminated silicone with a MW of only 21,000
could provide the same viscosity enhancement as 4 wt % of a
linear PDMS with MW 197,000.34,43 A capillary viscometer was
used in a later study to affirm the ability to thicken CO2 with
PMDS if toluene is used as a cosolvent.44 When PDMS (MW
260,000) was dissolved in a solution (4 wt % PDMS, 20%
toluene, 76% CO2), the resultant solution was about 5−10 times
more viscous than the CO2−toluene solution (0.09 cP) or 7−13
more viscous than neat CO2.44 However, upon introduction of
the thickened CO2 to cores it was noted that a portion of the
PDMS was immobilized via adsorption and partitioning in
residual oil; this led to reduced ability to inject the fluid into the
core.44 PDMS terminated with an aromatic group was
synthesized in an attempt to create intermolecular associations
between the toluene and polymer chain ends and reduce the
amount of cosolvent required;42,45 however, the molecular
weight of their polymer was not provided and the reduction in
solvent concentration (9 wt %) was only slightly below previous
reports.34 Due to the ready availability of PDMS with molecular
weights up to 1,000,000, PDMS will be included in the
experimental section of this study as a CO2 thickener using
toluene as a cosolvent. Du and co-workers46 investigated a
PDMS−toluene−CO2 solution for fracturing. Mixtures con-
taining PDMS at concentrations up to 5 wt % and toluene at
concentrations between 5 and 20 wt % were assessed. Solution
viscosity values up to 1.4 cP were reported. More recently, Zhao
and co-workers47 considered several polymers and cosolvents
and ultimately focused on a 5% PDMS, 5% kerosene, 90% CO2
solution that exhibited a 54-fold increase in CO2 viscosity for
hydraulic fracturing due to the thickening potential of PDMS.
Recently, Li and co-workers48 generated a silicone copolymer
by reacting (aminopropyl)triethoxysilane with methyltriethox-
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Energy & Fuels
ysilane in a 2:1 molar ratio. At a concentration of 3 wt % in CO2,
the resultant copolymer appeared to thicken CO2 by an order of
magnitude at 35 °C, 12 MPa (1740 psi), and low shear rates.
Modified silicones containing carbonyl groups have also been
proposed as CO2 thickeners for hydraulic fracturing that can
decrease the CO2 filtration coefficient.49 A novel silicone
polymer was recently developed via the ring opening polymer-
ization of octamethylcyclotetrasiloxane and tetravinyl tetrame-
thylcyclotetrasiloxane in the presence of KOH, followed by
hydrolysis with 2-benzoylbenzoic acid. This strategy incorpo-
rated an associative phenyl group to the silicone polymer. At a
concentration of 3 wt %, the CO2 viscosity increased from 0.04
to 2 cP.50
The extremely low CO2 solubility of high molecular weight
polymers motivated others to add an organic cosolvent
(sometimes referred to as an “entrainer”) to increase polymer
solubility. Cullick claimed that the CO2 solubility of high
molecular weight polymeric thickener candidates could be
enhanced with the addition of alcohol or glycol as a CO2
cosolvent.51 Although Cullick’s patent did not disclose any
viscosity data, he correctly noted that atactic, rubbery polymers
exhibit greater CO2 solubility than isotactic crystalline polymers
at modest temperatures. He also noted that the presence of
oxygen atoms between the backbone and side chain enhanced
solubility, as did the presence of aliphatic side chains. Schecter’s
group20,21 employed organic cosolvents to enhance the
solubility of CO2-philic polymeric thickeners during experi-
ments involving flow through porous media. Improved mobility
was attained using solutions of several weight percent PDMS
(MW 139,000, 260,000, or 600,000) and ∼10−20% toluene
cosolvent in CO2.
A notable breakthrough concerning the design of high
molecular weight polymers capable of dissolving in neat CO2
(i.e., no entrainer required) at conditions similar to those
encountered during CO2 EOR or fracturing was produced by
DeSimone and co-workers.52 This group discovered that
poly(1,1-dihydroperfluorooctyl acrylate) (PFOA; MW =
1,400,000) not only dissolved in neat CO2 but also increased
CO2 viscosity. A falling object viscometer was used to establish
that, at 50 °C and a polymer concentration of 3.4 wt/vol %, the
CO2-rich solution viscosity increased by a factor of 2.5 to a value
of ∼0.25 cP at ∼300 bar (∼4,500 psia). At 6.7 wt/vol %, the
solution viscosity at the same temperature and pressure was 0.45
cP, representative of a 6-fold increase. This pioneering work
proved that high molecular weight fluoroacrylate-based
polymers were CO2-soluble and CO2 thickeners. Polyfluor-
oacrylates (PFAs) remain the most CO2-soluble polymers
known. Nonetheless, it was apparent that the concentration of
the PFOA was too high to be commercialized for CO2 flooding
because fluoroacrylate-based polymers are inherently expensive
(∼$50/pound for the monomer alone).
Our team subsequently developed an associative copolymeric
thickener comprising a fluoroacrylate and a hydrocarbon
monomer in order to reduce the thickener cost and (more
importantly) the concentration of fluoroacrylate-based thick-
ener concentration required to attain a specified viscosity.53−55
The most effective thickener was a random copolymer
containing ∼79 mol % fluoroacrylate monomer (1,1,2,2-
tetrahydroheptadecafluorodecyl acrylate) and 21 mol % styrene,
a slightly CO2-phobic associating monomer.53−55 Lower
concentrations of styrene in the copolymer led to significantly
less viscosity-enhancing intermolecular thickening, whereas
higher styrene concentrations led to increased intramolecular
pubs.acs.org/EF Review
associations and significantly lower copolymer CO2 solubility.
The resultant polyfluoroacrylate styrene random copolymer was
dubbed polyFAST. Other polar or ionic associating groups were
considered, but they rendered the polymer CO2-insoluble. The
aromatic rings of the styrene struck a delicate balance; they were
mildly CO2-soluble, but the styrene pendants still associated
with each other, so the polymer would still dissolve and also
exhibit the intermolecular associations via π−π stacking that
results from a different electron density along the periphery of
the aromatic ring than in the core of the ring. Further, this
copolymer is reasonably soluble in CO2 at temperature and
pressure conditions similar to CO2 EOR conditions.54 At 25 °C
polyFAST is 1.5 wt % soluble in CO2 at 15 MPa (2,175 psia) and
1.0 wt % soluble at 13 MPa (1,885 psia). PolyFAST was capable
of thickening CO2 in both falling cylinder viscometry and
mobility measurements using Berea sandstone cores. In both
cases, the solution was found to be shear-thinning. Other
researchers have recently confirmed the effectiveness of the π−π
stacking mechanism in the design of CO2-soluble vinyl acetate−
heptadecafluorodecyl acrylate copolymeric associative thick-
eners and the need to optimize the ratio of the two monomers to
attain both solubility and thickening.56 In molecular modeling
studies, Goicochea and Firoozabadi26 found that polyFAST had
superior thickening due to the highly CO2-philic fluorinated
branches extending into the CO2 and the π−π intermolecular
stacking associated pendant benzene rings on the styrene units.
Note that the molecular weight of polyFAST typically ranges
from 200,000 to 1,000,000; therefore the polyFAST in their
model26 had the correct ratio of the fluoroacrylate and styrene
monomers, but the polymer molecular weight was about 1,000
times less than the polyFAST used in our experimental studies.
In our short-term core tests, at a concentration of 1.5 wt % in
CO2, polyFAST induced an apparent 19-fold increase in the
viscosity of CO2 as it was displaced through Berea sandstone at a
superficial velocity of 1 ft/day (0.00035 cm/s), a 12-fold
increase was measured at 10 ft/day (0.0035 cm/s), and 3-fold
increase occurred at 50 ft/day (0.018 cm/s). (These factors
were based upon the presumption that the absolute permeability
of the core was unaffected by the flow of CO2−PFA solutions.)
The expense of the fluoroacrylate monomer and concerns over
the persistence of fluoropolymer hydrolysis degradation
products (especially those based on fluoroacrylates with 8
fluorinated carbons in the side chain) has prevented polyFAST
from being considered as a viable CO2 thickener for field
application. Sun and co-workers57 affirmed that polyFAST
thickens CO2 and then showed that a fluoroacrylate-vinyl-
benzene copolymer (polyFAVB) could also thicken CO2.
Recently our team showed that results similar to those of
polyFAST could be obtained with a similar type of polymer, a 20
mol % phenyl acrylate-fluoroacrylate (polyFAPA) copolymer.58
Li and co-workers59 synthesized a fluoroacrylate-styrene
copolymer and used it as a CO2 thickener to control the
filtration velocity of CO2 in sandstone. Recently, Sun and co-
workers56 synthesized copolymers of heptadecafluorodecyl
acrylate (HFDA) and either vinyl n-octanoate, vinyl acetate
(VA), or vinyl pivalate. The FA-VAc copolymer, P(HFDA0.49-
co-VAc0.51), was found to thicken CO2 by a factor of 62 at 5 wt %.
In another study, five fluoroacrylate-hydrocarbon copolymeric
thickeners were synthesized60 The best results, a 96-fold
thickening of CO2, were obtained with 5 wt % copolymer of
HFDA and ethyl acrylate (EA), P(HFDA0.19-EAL0.71. Jyoti and
co-workers61 conjectured that a copolymer of fluoroacrylate and
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Energy & Fuels
3-vinylaniline (as associating group) would possibly yield good
CO2-thickening performance.
Kubala and MacKay’s patent62 claimed that CO2 could be
thickened by many different compounds, including aliphatic
polymers, oxygenated hydrocarbon polymers, hydrofluoropol-
ymers, perfluorinated polymers, low molecular weight fluorous
molecules (MW < 400), perfluoroethers, non-ionic surfactants,
ionic surfactants, zwitterionic surfactants, fatty acid esters, or
viscoelastic surfactants. Although they provided specific
examples (e.g., polymers and block copolymers based on
styrene, α-olefins, terpenoids, PVAc, and PFA), the patent did
not contain data or experimental techniques substantiating their
claims.
Another strategy for enhancing the thickening capability of a
polymer is to put associating functionalities at the ends of the
polymer chain. This type of linear, difunctional, telechelic
ionomers can act as a thickener when dissolved in nonpolar
solvents because the terminal ionic groups can aggregate into
pairs, multiplets, or large-scale clusters. Heller and co-workers
synthesized a relatively low molecular weight sulfonated
polyisobutylene as a CO2-thickening candidate.63 Although
the nonfunctionalized polyisobutylene polymer is about 0.4 wt
% soluble in CO2,6 the sulfonated ionomer was barely CO2-
soluble because CO2 is a very weak solvent for ionic groups.
Subsequently, our team synthesized a fluorinated polyurethane
telechelic ionomer based on more CO2-soluble building blocks;
a relatively low molecular weight perfluoropolyether diol that
was reacted with a fluorinated diisocyanate to yield a fluorinated
polyurethane diol.64 This diol was then transformed into a
fluorinated polyurethane disulfate. This fluorinated telechelic
ionomer (MW = 30,000) dissolved in neat CO2 and increased
CO2 viscosity at 25 °C and 25 MPa (3600 psi) by a factor of 2.7
at a concentration of 4 wt %. Given the expense of the
polyfluoroether oil and the high concentration of the ionomer
required to thicken CO2, this was not considered a viable
thickener.
Our team then began the design of a nonfluorous analog of
polyFAST in an attempt to develop a lower cost thickener that
could be effective at a dilute concentration of 0.1−1.-0 wt %.
Given the great expense of the fluorinated monomers, the
strategy was to either identify or design the most CO2-philic
nonfluorous polymer and to copolymerize its corresponding
monomer with styrene. Rather than simply testing a wide array
of polymers as had already been done in the 1980s, polymers
were designed to include at least one functional group that
exhibited favorable thermodynamic interactions with CO2 or to
exhibit other properties that would tend to favor dissolution in
CO2. For example, rather than using the fluoroacrylate
monomer, Tapriyal selected the vinyl acetate monomer and
subsequently synthesized a random copolymer of vinyl acetate
and benzyl acrylate copolymer.22 Here the fluoroacrylate of
polyFAST was replaced by vinyl acetate to reduce cost, while the
styrene (which has a pendant benzene ring) of polyFAST was
replaced with benzyl acetate (which has a benzene ring) in order
to simplify the synthesis. Although the poly(5% benzyl acrylate−
95% vinyl acetate) associating copolymer (MW 7840) was
several weight percent soluble in CO2, elevated pressure was
required (∼62 MPa, 9,000 psi) for dissolution and the resultant
viscosity increase was only 25% at 2 wt %. More recently, it has
been reported that an oligomer of propylene oxide function-
alized with pendant benzene rings exhibited promise as a CO2
thickener.16 A series of propylene oxide−glycidyl phenyl ether
copolymers with different amounts of pendant aromatic groups
pubs.acs.org/EF Review
was considered. Not surprisingly, CO2 solubility decreased with
increasing phenyl content. Because the CO2-philicity of a low
molecular weight oligomer can be influenced significantly by the
end groups, these researchers replaced the CO2-phobic hydroxyl
terminal group with the CO2-philic acetate moiety. At a
concentration of 0.4 wt %, the copolymer with MW of 940
and 36 mol % phenyl content increased the viscosity of CO2 by a
factor of 2.4−3.4 over the 20−35 MPa (2,900−5,100 psi)
pressure range at 35 °C. Although greater enhancement could be
expected for higher molecular weight copolymers, the
researchers correctly noted that the CO2 solubility of poly-
(propylene oxide) or the propylene oxide-glycidyl phenyl ether
copolymers decreases significantly if high molecular weights are
considered.
Given a practical goal to either identify an existing polymer or
design and synthesize a novel polymer that was comparable in
solubility to PFA or polyFAST, amorphous polymers that were
rich in oxygen atoms found in ether, carbonyl, acetate, sugar
acetate, or vinyl groups were hypothesized to be CO2-
philic.65−75 Not all moieties that contain oxygen atoms are
CO2-philic; oxygen atoms present as hydrogen bonding
hydroxyl groups (-OH) and carboxylic acids (-COOH) typically
rendered the polymer CO2-phobic. The oxygen atoms in
carbonyls, ethers, acetates, and esters are somewhat electro-
positive, while the carbon of CO2 is electronegative, promoting
Lewis acid−Lewis base interactions. Further, the electronegative
oxygen atoms of CO2 were shown by others73 to hydrogen bond
with the protons on the backbone or side chain of the polymer.
With regard to alkyl chains, relatively small, highly branched
alkyl chains were found to be more CO2-philic than longer,
linear alkyl groups.76 Molecular modeling tools were then used
to design a new monomer, (3-acetoxy oxetane) that potentially
would exhibit the greatest possible number of favorable
thermodynamic interactions with CO2, but the oligo(3-acetoxy
oxetane) (OAO) was less CO2-philic than the inexpensive
commodity chemical, PVAc.74 In fact, after years of testing novel
polymers, the most CO2-soluble high molecular weight
polymers composed solely of carbon, hydrogen, and oxygen
were identified to be PVAc, poly[(1-O-(vinyloxy)ethyl-2,3,4,6-
tetra-O-acetyl-β-D-glucopyranoside)] (PAcGIcVE), which is a
polymer with a pendant sugar acetate group in each monomeric
unit, and the amorphous form of polylactic acid (PLA).77
Reduced CO2 mobility had been demonstrated in core
studies,20,21 including with solutions of PVAc (e.g., PVAc,
MW 170,000) that required a large amount of toluene cosolvent
(5% PVAc−10% toluen−85% CO2). As was the case for high
molecular weight PDMS, PVAc was insufficiently soluble in CO2
at field conditions to be a thickener unless an untenable amount
of toluene was introduced. Because all of our novel alternative
oxygenated hydrocarbon polymers, including PAcGIcVE or
amorphous PLA, were less CO2-soluble than PVAc, none were
deemed to be viable thickeners. The thickening capability of
high molecular weight PVAc will be assessed in the experimental
section of this study with CO2−toluene solutions.
Recently, Fu and colleagues78 synthesized two novel silicone-
oxygenated hydrocarbon polymers, liquid polydimethylsilox-
ane-vinyl acetate (PDMS-VAc; MW 76,190; 21 cP) random
copolymer, and a liquid poly(methylsilsesquioxane)-vinyl
acetate (PMSQ-VAc; MW 49,170; 13 cP) graft copolymer.
The PDMS-VAc was determined to be more CO2-soluble and
more effective as a thickener. The authors reported that no
cosolvent was required for dissolution in CO2. For example, at
50 °C and 12 MPa (1,740 psi), a 1.5 wt % solution of PDMS-
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VAc in CO2 exhibited a viscosity of 10 cP at a shear rate of 100
s−1, as determined with pressure drops along 1 cm diameter
pipes at specified flow rates. These are remarkably high viscosity
results at relatively low pressures without the use of a cosolvent;
however, the authors provided no explanation of how only 1.5 wt
% polymer with a viscosity of 21 cP could elevate the viscosity of
a CO2 solution to 10 cP. Nor did the authors explain how dilute
solutions (1.5 wt %) of the relatively low molecular weight
PDMS-VAc (76,190) could be so much more effective as a
thickener (a 227-fold increase of CO2 viscosity to 10 cP) than
the extremely high molecular weight, highly viscous PDMS used
by Chevron researchers (MW 197,000; ∼600,000 cP).
Chevron’s capillary viscometry showed that 4 wt % PDMS
thickened a 21% toluene−79% CO2 solution to 1.2 cP,
representing a 30-fold increase relative to pure CO2. We
would urge caution when considering the viscosity results of Fu
and co-workers78 and encourage further confirmation of
viscosity. In a separate study, Huang and co-workers79 affirmed
the CO2-thickening capabilities of a PDMS-VAc.
Recently, a molecular dynamics study was presented for
solutions of 1.19 or 2.35 wt % of the vinyl acetate-vinyl ethyl
ether copolymer (PVAEE).80 2- to 3-fold viscosity increases
were calculated. However, this work contains no experimental
data, nor any indication of the molecular weight of the
copolymer. This particular copolymer was selected because of
the previous appearance in a modeling study of CO2-philic
polymers, but no experimental viscosity data were presented in
this work either.81
A very recent study by Liu and co-workers82 investigated two
polymers, polyHBD-1 and polyHBD-2. These nonfluorous
polymers did not require a cosolvent to dissolve in CO2. These
polymers were using a hydrosilylation reaction that combined
ethylene glycol dimethacrylate or trimethylolpropane trimetha-
crylate with 2,4,6,8-tetramethylcyclotetrasiloxane (D4H) using
a H2PtCl6·6H2O catalyst. Solutions of 5 wt % of these polymers
exhibited low cloud point pressures and elevated the viscosity of
CO2 to as much as 5 cP, with the greatest increases occurring at
low temperature, low shear, and high pressure.
A recent study83 employed a polymer-based CO2 direct
thickener composed of “a mixture of dif ferent compounds
including copolymers of allenethers, acrylate, acrylic long carbon
chain esters/benzenes, propylene carbonate/allyl ethyl carbonate,
dimethyl carbonate, and white oil/silicon or oil/petroleum ether.”
(We believe that “allenether” may be a typographical error,
perhaps referring to “allyl ether”.) The authors called this
mixture a “direct thickener” and stated that it was soluble in CO2,
formed a stable and homogeneous solution during a 24 h
observation, and resulted in 100−1,200-fold increases in
viscosity at concentrations up to 2 wt % as determined with a
Cambridge viscometer. Although the photographs presented in
their work do show the contents of the windowed cell to be
uniform from the top to the bottom of the window, the contents
of the cell appear to be hazy and translucent rather than
transparent. The vagueness of the description prevented us from
replicating the formulation to test its efficacy. However, the
manufacturer (Beijing AP Polymer Technology Co., Ltd.)
kindly provided us with a sample of their direct thickener in the
form of an emulsion with 35% active ingredients. (As detailed in
the results section, the sample of this compound that was
provided to us was not a direct thickener; rather it was an
indirect thickener that stabilized a carbon dioxide-in-oil
emulsion.)
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Review
Our most recent study84 demonstrated that thickening CO2 is
a necessary, but not sufficient, metric for success as a mobility
control agent during EOR in conventional formations. Further,
it illustrates how assessments of viscosity based on pressure drop
through porous media (rather than high-pressure viscometers)
may yield unrealistically high estimates of CO2 thickening
because polymer adsorption can dramatically alter core
permeability and increase pressure drop to a greater extent
than the increased fluid viscosity. In this study,84 we prepared a
PFA homopolymer from the tridecafluorooctyl acrylate
monomer (PTOA). The possible degradation products
associated with this high molecular weight amorphous polymer
based on the -C6F13 functionality are safer with respect to human
health and more environmentally benign than the degradation
products associated with PFAs based on the -C8F17 function-
ality; degradation products associated with polymers based on
the -C4F9 monomer would likely be even safer and more
benign.85,86 Falling cylinder viscometry results indicated that the
1 wt % PTOA solution was about 3.8 times more viscous than
pure CO2 at low shear rate. Capillary viscometry for the same
solution was conducted at Praxair Inc., and the solution was 3.2
times as viscous as pure CO2 at low shear. This particular sample
was the most effective PFA thickener that we have synthesized to
date. We therefore expected the pressure drop across a core to
increase by no more than 3.2−3.8 times as the CO2−PFA
solution displaced the pure CO2 from the core. Continued
injection of numerous pore volumes (PVs) of the solution into
the cores initially saturated it with CO2; however, we found the
pressure drop increased by a factor of 10−1,000 more than
expected based on increased viscosity. Ultimately, we showed
that there was significant polymer adsorption occurring that
dramatically altered core wettability, which is not surprising
given that PFA is both hydrophobic and oleophobic. In
retrospect, we realized that we made a mistake in our earlier
study involving CO2-polyFAST solutions flowing through
cores.54 In that earlier study the cores were initially saturated
with CO2 to determine pressure drop at a constant flow rate.
However, we used too small of a volume of the subsequent
chaser of thickened CO2. We also erroneously failed to consider
that polymer adsorption could occur and reduce the
permeability of the rock; therefore, we attributed the entire
pressure drop increase of the small slug (∼1.5 PV) of CO2-
polyFAST to thickening.54 Finally, we did not inject a pure CO2
chaser after the thickened CO2 to determine if the baseline
permeability and pressure drop would be attained. Our most
recent study84 corrected all of our earlier errors.54 Large volumes
of thickened CO2 were injected, CO2 chasers were injected after
the thickened CO2, and the rock surfaces were checked for
wettability changes. We demonstrated that PFAs will not work
as CO2 thickeners in porous media even though they effectively
increase CO2 viscosity, because the reductions in permeability
due to PFA adsorption are unacceptably high. To make matters
worse, we found that the low molecular weight hydrocarbons
that are extracted into the CO2-rich front during multiple-
contact miscible displacement act as PFA antisolvents, which is
not surprising in that fluorinated polymers are both hydro- and
oleophobic. Large reductions in permeability also occurred for
cores that were initially brine saturated, especially sandstone.
These permeability reductions were so severe that we concluded
that the CO2−PFA solutions could not be used for in-depth
mobility control despite their proven ability to thicken CO2.
Although some of the permeability was recovered when the
thickened CO2 was injected at a very high rate and/or in the
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Table 4. Summary of Several Commonly Studied Small-Molecule Direct CO2 Thickener Candidatesa

a
Reference links: 18, 64, 87, 88, 89, 90, 91, 92, 93, 95, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 118.

reverse direction, or when a significant amount of pure CO2 was
introduced to the core, PFA adsorption led to a significant
degree of irreversible permeability loss. The only utility of
8520
fluorinated acrylate polymers and copolymers could be as a
CO2-soluble, near-wellbore, conformance control agents to
reduce the permeability of a thief zone.84
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Energy & Fuels
1.1.2. Small Associating Molecule Direct Thickener
Literature Review. Table 4 presents a summary of the attributes,
advantages, and disadvantages of many of the polymeric direct-
thickening candidates.
The second strategy for direct-thickening CO2 involves small
molecules that can associate in solution and form viscosity-
enhancing macromolecular structures.1,3 The molecule contains
at least one CO2-philic group that enhances CO2 solubility. The
small molecule also contains at least one CO2-phobic moiety
that interacts with (the same or a different) moiety on a
neighboring thickener. The most challenging aspect of this
strategy is that the associating groups typically are CO2-phobic;
if one selects a very strong associating functionality then the
thickener may become CO2-insoluble, but if a very weak
associating group is incorporated, the thickener may dissolve in
CO2 but not impart a significant change in viscosity.
A recent dissertation from a member of our team1 noted that
Heller and co-workers made the pioneering efforts in small-
molecule thickener research. They documented that small
amounts of tributyltin fluoride (TBTF) could dramatically
thicken light liquid alkanes such as butane by several orders of
magnitude (OOM) in dilute concentrations of ∼1 wt %. The
electropositive tin associated with the electronegative fluorine of
the neighboring molecule and the butyl arms enhance the
solubility of the molecule in the solvent, do not interfere with the
tin−fluorine associations, and sterically favor the formation of
linear, viscosity-enhancing transient polymers. TBTF was found
to thicken propane and butane.87−89 Although the Heller and
Kovarik of the Petroleum Recovery Research Center (PRRC)
concluded that TBTF could not dissolve in ethane or CO2, we
later showed that TBTF is indeed a remarkable ethane thickener
that dissolves in these light alkanes and forms a transparent
solution and could dissolve in ethane, propane or butane simply
by mixing (i.e., a heating cycle to break the associations and
hasten dissolution, followed by a cooling cycle to establish the
transient polymer was not needed).9 Pressures above 41.4 MPa
(6000 psi) are required for TBTF dissolution in ethane, which is
a pressure range that was not attainable in the PRRC equipment
used by Heller and Kovarik. We also confirmed that TBTF was
CO2-insoluble to 69 MPa (10,000 psi) at 25−100 °C range. The
addition of pentane as a cosolvent did not promote TBTF
dissolution in CO2.90,91 In an attempt to design a more CO2-
soluble tinfluoride, Enick and co-workers replaced the butyl
arms with semifluorinated ligands and synthesized (F-
(CF2)4(CH2)2)3SnF.92 The compound was CO2-soluble but a
very modest thickener; at a concentration of 3 wt % in CO2 at 25
°C and 16.5 MPa (∼2,400 psia), the viscosity of CO2 tripled.
Our team concluded that both the fluorine atoms bound to the
tin and the terminal fluorine atoms at the ends of the three arms
groups were interacting with the tin atoms on the adjacent
molecule, which interrupted the formation of linear transient
polymers.
Perhaps the most well-known hydrocarbon thickener was
initially developed to weaponize gasoline. Hydroxyaluminum
disoaps were used to weaponize gasoline into a sticky viscosity
liquid or gel commonly referred to as Napalm. Initially, the
hydroxyaluminum disoap was based on a mixture of naphthenic
and palmitic acids (hence the designation “Napalm”). It has
since been shown that remarkable viscosity changes can be
achieved with the water-insoluble surfactant hydroxyaluminum
bis(2-ethylhexanoate) (HAD2EH) or hydroxyaluminum bis-
(mixed iso-octanoates). In a manner analogous to tributyltin
fluoride, this aluminum disoap dissolves in the hydrocarbon
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liquid and forms high molecular weight helical micelles. These
micelles are dry, meaning that a small amount of water was not
needed to stabilize the macromolecular structure. The core of
this micelle is composed of the hydroxyaluminum head groups,
with electropositive aluminum atoms associating with electro-
negative oxygen atoms in the hydroxyl group. The branched 2-
ethyl hexanoate chains extend away from the core toward the
solvent, allowing the disoap to dissolve in the oil while also
providing the steric effects required for the micelles to form
cylindrical viscosity-enhancing micelles (rather than spherical
micelles that do not significantly alter viscosity). Even the
slightest changes in the structure of these disoaps can render
them ineffective. For example, the use of linear (rather than
branched) octyl chains, results in a disoap that can still dissolve
in hydrocarbon liquids such as hexane but results in no
thickening.93 Hydroxyaluminum disoaps are CO2-insoluble.
Our team’s attempts to design a CO2-soluble hydroxyaluminum
disoap were unsuccessful. Although we were able to find analogs
that thickened propane, none could even dissolve in CO2.93 Our
unpublished results indicated the even the use of fluorinated
ligands did not help, neither did the inclusion of highly
methylated alkyl chains, such as those that are known to increase
the CO2 solubility of other types of surfactants.76
Our efforts to thicken CO2 in the same manner that oils are
thickened to form grease were also fruitless. For example, when
aluminum tristrearate was added to an oil, the resultant mixture
was heated and stirred. This allowed the aluminum tristrearate
to dissolve in the oil as the intermolecular attractions between
aluminum tristrearate molecules are weakened. Upon cooling of
this solution, tremendous viscosity increases were realized when
aluminum tristrearate molecules associated into macromole-
cules. Metallic stearates could not thicken CO2, however,
because even at high-temperature and -pressure conditions, up
to 120 °C and 60 MPa (10,000 psi), the metallic stearates could
not dissolve in CO2.94
Semifluorinated alkanes were also considered as CO2
thickeners because they have been reported to gel light
alkanes.90,91 Semifluorinated alkanes are small, linear diblocks,
F(CF2)n(CH2)mH, which can be considered as two immiscible
segments forced to join one another through a covalent C−C
bond, can gel organic liquids if they are heated in the solvent, are
allowed to dissolve, and then are permitted to cool. As the
solution cools, the semifluorinated compounds form interdigi-
tated, fibrous, viscosity-enhancing networks. Fibers form
because the fluorinated alkyl groups stack upon fluorinated
segments of neighboring molecules. The hydrocarbon segments
also assemble in a similar manner. These semifluorinated alkanes
did not thicken the CO2 in the desired manner. Rather than
forming a transparent, single-phase, high-viscosity solution, the
semifluorinated alkane−CO2 mixture formed an opaque
dispersion composed of a high-porosity interlocking network
of solid fibers (micrometer-scale diameters) dispersed in dense
CO2.
Another small organic compound, 12-hydroxystearic acid
(12-HSA), was assessed as a CO2 thickener because HSA had
been previously used to thicken hydrocarbon and chlorinated
liquids.95 In solution, the -OH group of one HSA molecule
hydrogen bonds with the electronegative carbonyl (O) atom
of the HSA molecule that it faces. The -OH hydroxyl group on
the 12th carbon in the alkyl chain helps to align the tails of the
HSA molecules above/below it. HSA was essentially insoluble in
CO2 unless 10−15% cosolvent (ethanol) was added. For
example, a solution of 3:15:82 HAS:ethanol:CO2 (%) exhibited
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a slight viscosity increase at 34 °C and 12.4 MPa (1,800 psia).
Capillary viscosity measurements indicated that at a slightly
lower temperature of 27−28 °C a 100-fold increase in viscosity
was detected. The occurrence of microfibers in the CO2-rich gels
indicated that these opaque systems would not be capable of
flowing through porous media during EOR.
Investigators at the National Institute for Petroleum and
Energy Research (NIPER) considered the use of entrainers, or
cosolvents, as CO2 thickeners.96 Although the researchers were
successful in some respects, substantial improvements required
very high concentrations of cosolvent. For example, at 122 °F
and 12.4 MPa (1,800 psia), 13 mol % isooctane increased the
CO2 viscosity by 243%. When 34.3 mol % 2-ethyl hexanol was
added to CO2 at 40 °C and 13.8 MPa (2,000 psi), the solution
viscosity increased by 943%. Although these are impressive
increases, the amount of cosolvent required is extremely high
and hence the system is not economically feasible. Further, there
was no evidence that these entrainers self-assembled into
viscosity-enhancing macromolecules in solution, rather the
increase in viscosity may have been primarily attributable to an
averaging of the viscosities of the constituents in the solution.
Claims were made in a 1989 patent that increases to CO2
viscosity can be caused by dissolving ethylene glycol (EG) in
CO2 at a concentration of 2.3 wt %. The viscosity was reported
to have increased by a factor of ∼3.3−4.0 at 67.2 °C and 14.0
MPa (2025 psi) and at 142.2 °C and 8.5 MPa (1235 psi),
respectively.97 Although there is no literature concerning
ethylene glycol as an associative thickener for any type of
solvent, we decided to include this compound in our
experimental assessment because it is so readily available and
inexpensive.
Low mass organic gelators composed of an aromatic
headgroup and twin n-alkane tails, such as 2,3-bis(dodecyloxy)-
naphthalene,98 were found to be ineffective CO2 thickeners in
unpublished work from our laboratory due to a lack of CO2
solubility. Even when dissolution was facilitated by heating the
mixture and stirring at extremely high temperature and pressure,
the bis(dodecyloxy)naphthalene came out of solution as it was
cooled under pressure.
We were also unsuccessful thickening CO2 with the
triphenoxymethanes (TPMs). TPMs were first made with a
hydrophobic aromatic core for associations and three pendant
poly(ethylene oxide)-based hydrophilic arms to enhance water
solubility. TPM thickened water via the formation of worm-like
micelles,99 but these compounds were CO2-insoluble. Even after
modifying the arms of TPM to enhance CO2 solubility via the
incorporation of multiple propylene oxide groups, no viscosity
increase occurred.
Canadian Fracmaster Ltd. postulated that compounds known
to gel organic liquids (such as diesel fuel) might be effective CO2
thickeners. Their interest was in increasing the viscosity of CO2
for waterless hydraulic fracturing.100 Therefore, relative to CO2
EOR, they considered low temperatures to account for
refrigerated tankers of CO2 being delivered to the well site
and the high pressures that are required to fracture a formation.
Further, the occurrence of micrometer-scale dispersed fibers
would not be problematic because of the large scale of the
wellbore and fracture width compared to the fibers’ diameters.
They assessed a series of compounds known to thicken oils, but
none proved successful in CO2. Caprolactone-based polymers
were CO2-insoluble. The reaction resulting from addition of
CO2-soluble tetraisopropoxy titanate with functionalized
organic substrates (e.g., -OH or -COOH) in the presence of a
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cosolvent yielded a CO2-insoluble macromolecule that
precipitated. The reaction between amine-terminated organics
and CO2 yielded CO2-insoluble ammonium carbamates that
simply precipitated in the solution instead of gelling it.
There has been a strong interest to determine if cross-linked
phosphate esters (CPEs) that are effective alkane thickeners and
gellants could thicken CO2. Formulations of the thickener
system for liquid alkanes are available from several commercial
vendors, composed of two liquids that have low viscosity, are
easily pumped, and can rapidly form viscosity-enhancing
macromolecules when mixed in a solvent (if the macromolecular
structure remains in solution). The two liquid components
include a phosphate ester (PE) blend and an acidic solution that
contains a trivalent ion (e.g., Fe3+ or Al3+). Although it is easy to
dissolve phosphate esters with various alkyl chains in light
alkanes, the alkyl groups of the PE blend must be carefully
designed for the alkane solvent of interest if thickening is
desired. For example, the system designed for gelling propane is
based on very short alkyl chains in the PE, while the PE blends
for higher molecular weight hydrocarbons are based on higher
molecular weight alkyl groups in the PE. For example, we
recently showed that the phosphate esters designed for gelling
hexane and heptane could only induce modest thickening of
liquid propane.18 However, when the PE blend designed for
propane101 subsequently became available to us, we were able to
demonstrate that the resultant propane viscosity increase was
several orders of magnitude greater. PE blends are quite soluble
in high-pressure CO2, ethane, propane, butane, pentane, hexane,
and heptane. When the acidic cross-linking solution is then
mixed into the phosphate ester solution, the cross-linking occurs
quickly, which is another attractive feature for field implementa-
tion. Highly viscous solutions or gels were quickly established
for alkanes such as propane, butane, pentane, hexane, and
heptane (but not CO2 or ethane). These thickened or gelled
light alkanes are typically translucent and light yellow in color.
This appearance is caused by the dispersion of small aqueous
acidic droplets from the cross-linking solution. The cross-linked
phosphates esters form transparent viscous single-phase
solutions in n-alkanes, but small droplets of water from the
acidic cross-linking solution appear to be dispersed in this
thickened liquid alkane phase. Sometimes, however (depending
on the liquid alkane and type and concentration of cross-linker
solution and phosphate ester blend), colorless, transparent,
viscous solutions form. Unfortunately, when the cross-linking
solutions designed for propane or hexane/heptane are blended
with either ethane−phosphate ester or CO2−phosphate ester
solutions, the resultant cross-linked network immediately
precipitates. In order to address this limitation for CO2, Taylor
and colleagues102−104 proposed using a single-phase mixture of
30−80% CO2 and 70−20% blended hydrocarbons (mostly C6−
C11) thickened with a gelling agent at a concentration of 0.1−
2.5 wt % (based on the hydrocarbons) for hydraulic fracturing.
The gelling agent consists of a “ferric iron or aluminum
polyvalent metal complex of an unsymmetrical dialkylphos-
phinic acid or an orthophosphoric acid ester”.102 The claims of
the patent102 imply that at least 20 vol % cosolvent is required to
dissolve the gelling agent in the CO2-rich fluid mixture, although
it is apparent that mixtures with as much as 80 vol % cosolvent
are more readily thickened. An example of a composition
considered for fracturing104 included a small concentration of
the phosphate ester blend and cross-linking solution added to a
single-phase solution of 50 vol % high-pressure CO2, and 50 vol
% of a C7−C11 blend. The laboratory-scale performance of this
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system was excellent compared to other waterless fluids.104 To
date, there are no reports of attempts to optimize the design of
the PE such that the CPE network remains soluble in CO2 upon
introduction of the cross-linking solution.
Urea-based and bis-urea-based small molecules with four
pendant fluorinated arms (two at each end of the molecule) have
also been assessed as CO2 thickeners. Urea groups will interact
with neighboring ureas on nearby molecules via hydrogen
bonding while the fluorinated arms enhance CO2 solubility. This
can provide a means for linear viscosity-enhancing, associating
macromolecular structures to form in CO2.64 Four bis-urea
compounds were dissolved in CO2 and increased CO2 viscosity
by 3−5 times at ∼5 wt %, 25 °C, and 31 MPa (4,500 psi).
Recently, a bis-urea [1,6-bis(1,3-perfluorooctanoic acid biester
2-urea)] hexane (BPFAUH) compound (which is nearly
identical in structure to that previously reported by Shi et
al.64) was synthesized and reported to dissolve in CO2 at a
concentration up to 3 wt % at 40 °C and 10 MPa (1450 psi) and
a 48-fold thickening of CO2 at 2 wt % BPFAUH was reported.105
However, no details of the rheometer or its calibration were
provided, nor were the means used to verify that the BPFAUH
was in solution presented.105 An attempt was made to synthesize
nonfluorous analogs of these urea-based compounds; therefore,
CO2-philic hydrocarbon moieties, including ethers and carbon-
yls, were used rather than fluorinated segments.106 Several of
these oxygenated hydrocarbon-based compounds were CO2-
soluble at 25 °C to ∼1 wt % at elevated pressures of 62−65 MPa
(9,000−9,400 psi), respectively. However, the transparent
solution that was formed upon mixing immediately began to
slowly transform into a dispersion of white thickener fibers
dispersed in CO2. It appeared that the thickener precipitated
during its self-assembly into fibers rather than remaining in
solution. To date, dilute concentrations of bis-ureas have been
shown to dramatically thicken light alkanes such as propane,8
but only very modest success has been realized in CO2.
Our team worked with Bristol University to design CO2-
soluble surfactants that would self-assemble into viscosity-
enhancing rod-like micelles when small amounts of water were
introduced to stabilize the core of the micelle.107 Surfactant
design was drawn from the previously established ability of the
surfactant AOT to stabilize microemulsions in organic liquids.
In these organic liquids, the exchange of the monovalent Na+ ion
with a divalent ion such as Co2+ or Ni2+ can effect a spherical-to-
rod-like change in microemulsion shape. The rods are capable of
enhancing viscosity, and 40-fold increases were realized at 10 wt
% in several organic solvents.108−110 Small-angle neutron
scattering (SANS) results indicated the presence of rigid
micellar rods. Several semifluorinated, CO2-soluble surfactants
were also generated that, in conjunction with small amounts of
water, were intended to stabilize rod-like micelles that could
thicken CO2. The surfactants were soluble in CO2 at 25 °C,
although the requisite pressure was greater than typical
minimum miscibility pressure (MMP) values. Further, high-
pressure small-angle neutron scattering (SANS) and high-
pressure falling cylinder viscometry were used to confirm the
occurrence of rod-shaped micelles. The surfactants responsible
for the greatest viscosity increases were Ni-diHCF4 (nickel bis-
nonofluoropentane sulfosuccinate) and NaF7H4 (sodium
pentadecafluoro-5-dodecyl sulfate), twin-tailed perfluorinated
sulfosuccinate surfactants. At a concentration of ∼6 wt % Ni-
diHCF4, at 25 °C and 350 bar, with 10 mol of water per
surfactant mole (W = 10), a ∼50% increase in viscosity
occurred107 and up to a 100% increase occurred using NaF7H4 at
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a concentration of 4.4 wt % and W = 12.5 mol of water per
surfactant molecule.111 Eastoe and co-workers112 summarized
the literature regarding water-in-CO2 microemulsions, with an
informative look at any surfactant structures aimed at attaining
both CO2 solubility and viscosity enhancement. Although there
have been developments in designing surfactants that form
ellipsoidal micelles in CO2,107,111,113 the extraordinarily long
micelles required to generate the necessary large increases in
viscosity at dilute concentration have not been realized. A recent
review of these attempts affirms that while great advances in the
formulation of spherical and rod-like reverse micelles of water in
CO2 have been made, attempts to exploit the rod-like
geometries for CO2 viscosity enhancement have been
modest.114
In 2016 the University of Pittsburgh and GE Global
Research115 reported that propyltris(trimethylsiloxy)silane-
functionalized benzene tris-urea and tris-ureas functionalized
with varying proportions of propyltris(trimethylsiloxy)silane
and propyl-poly(dimethylsiloxane)-butyl groups could induce
exhibited remarkable viscosity increases (e.g., 3−300-fold at
0.5−2.0 wt %) in CO2. Unfortunately, these compounds cannot
serve as a practical CO2 thickener because extremely high levels
of organic cosolvent (e.g., 18−48 wt % hexanes) had to be added
to enable the thickener to dissolve in CO2. This team also
attempted to functionalize relatively low molecular weight
silicones to enable them to become associative thickeners.116
Neat PDMS oligomers with a benzene group at each end were
liquids rather than solids, indicative of a very weak end-group
interaction and a high probability of poor thickening perform-
ance. Therefore, larger electron-deficient aromatic groups,
including anthraquinone, 4-nitrophenyl, and biphenyl, were
attached to the PDMS oligomers, yielding solid polysiloxanes.
PDMS-based thickeners with anthraquinone-2-carboxamide
(AQCA) terminal functionalities were transparent, rubbery
solids that effectively thickened or gelled hexanes and CO2−
hexanes solutions. Although the AQCA-terminated branched
poly(dimethylsiloxanes) proved to be the best thickeners,
however the CO2-rich solvent required 20−40 wt % hexanes
content to attain dissolution of the thickener.
It has been claimed that the addition of 0.1−5.0 wt % glycerol
and higher fatty acids such as stearic acid or linoleic acid to (0.3−
6.5 wt %) cosolvent mixture of halogenated and hydrocarbon
solvents increased CO2 viscosity by roughly 2 orders of
magnitude to 6−10 cP. This mixture was reported to result in
the in situ generation of triglycerides in CO2. However, when
our team used a windowed close-clearance falling Pyrex ball
viscometer and attempted to thicken CO2 with triglycerides
such as coconut oil, only a 30% increase in viscosity at 5 wt %
coconut oil and 6.5 wt % (cyclohexane:tetrachloromethane at
1:1) was attained at 23 °C and pressures up to 34.5 MPa (5,000
psi). It is uncertain that the dramatic viscosity increases reported
in this patent117 could occur with the addition of triglycerides
and cosolvent. Further, it is not clear that the reaction actually
occurs or that the glycerol is actually CO2-soluble; glycerol is
only sparingly soluble in CO2 and is typically not selected as a
CO2-cosolvent.
Zhang et al.118 reported CO2 thickening with the surfactant
sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and the
addition of ethanol as a cosolvent. For example, they reported
that one could triple the viscosity of CO2 using about 1.5 wt %
AOT dissolved in a mixture of 15−20 wt % ethanol in CO2. The
authors then generated a very high viscosity C/W foam by
mixing the thickened CO2 with water to make a foam. However,
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Table 5. Summary of Indirect CO2-Thickening Candidates for Stabilizing Waterless CO2-in-Oil Emulsions or Foamsa
a
3, 4, 83, 100, 120, 121, 121, 122, 123.
it is possible that the ethanol would interrupt any potential
viscosity-enhancing network formation. Nonetheless AOT was
selected for assessment in this current study.
Sun and co-workers recently suggested that CO2 could be
thickened using silicohydride, but only if toluene was added as a
cosolvent.119 Unfortunately, this work provided no reference for
the use of silicohydride for viscosity enhancement of any solvent
and provided no explanation within the report concerning how
this small molecule could thicken a CO2−toluene solution.
Although wettability alteration results were presented, no high-
pressure viscosity data were presented.
In summary, a few small molecule CO2 thickeners have been
developed, including a tri(semifluorinated alkyl)tin fluoride,
fluorinated urea and fluorinated bis-urea compounds, and a dual,
fluorinated, twin-tailed surfactant with a divalent metal cation.
These fluorous compounds are capable of inducing 50−500%
increases in CO2 viscosity, but these fluorous chemicals are very
expensive and can only work at concentrations of 2−10 wt %.
Cross-linked phosphate esters can certainly thicken CO2-rich
liquids but only if very substantial quantities of n-alkanes are
introduced as cosolvent.
1.2. Indirect Thickeners for the Stabilization of Two-
Phase Waterless CO2-in-Oil Emulsions and Foams. Table
5 provides a summary of indirect CO2-thickening candidates for
stabilizing waterless CO2-in-oil (C/O) emulsions or foams.
A technique for fracturing with an emulsion comprised of 30−
95 vol % dense CO2 in an anhydrous liquid stabilized with a
surfactant was patented in 1985.120 In one example, emulsions
were generated from a mixture of 30−60 vol % CO2 in a mixture
of diesel and ethylene glycol that contained an ammonium salt of
a sulfated normal ethoxylated alcohol containing 12−14
carbons. The emulsion, which was formed within a high-
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pressure viscometer, exhibited viscosities of 170−220 cP at 500
s−1 at 24 °C and 1,000 psi and was stable for less than an hour.
Although not specified in the patent, it appears that the ethylene
glycol was added to enhance the solubility of the ionic surfactant
in the diesel. Other suggested surfactants included betaines,
ethoxylated alcohols, alkyl diethanol amines, and alkyl amine
oxides.120
One of our recent studies3 summarized Canadian Frac-
master’s attempt to formulate cold liquid CO2-in-oil emulsions
containing a high volume fraction of liquid CO2 (i.e., high
quality). Nearly three dozen commercially available surfactants
were assessed. Cold, saturated liquid CO2 is supplied for
fracturing jobs; therefore, the experiments were conducted at
−30 °C. Excellent emulsion stabilization was not attained. Better
performance was associated with ethoxylated resin acids,121 and
it is likely that the poly(ethylene glycol) (i.e., PEG, PEO, or
ethoxylated alcohol) segment of the surfactant was only mildly
CO2-philic.38 Subsequently, a mixture of fatty alcohol, fatty acid,
and sorbitan fatty acid ester was recommended as a stabilizer100
because the emulsions were stable and exhibited viscosity of 10
cP at a shear rate of 1,000 s−1 before they collapsed. The same
company later generated emulsions with ethoxylated resin acids,
sorbitan oleate, and alcohol ethoxysulfates salts.122 In general,
the emulsions were stable for less than an hour.
In a patent, researchers at the Baker Hughes company
suggested the use of C/O foams for gas lift operations,123 rather
than oil recovery or fracking. A recommended surfactant was a
cross-linked siloxane polymer. A commercial silicone cited for
this applicat ion was Do w Corni ng 1250 (poly-
(trimethylhydrosilylsiloxane), MW 5770, MN 3160). This
patent also listed sultaine or hydroxysultaine salts, betaines,
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organic phosphonates, and alkyl sulfonates as plausible
additives.
We recently reported that a novel, mineral oil-soluble
surfactant composed of a PDMS backbone with multiple
pendant tricontyl groups (-C30H61) can stabilize emulsions of
CO2 in mineral oil4 for several days at ambient temperature. The
PDMS backbone molecular weight was chosen to be more CO2-
philic than oil-philic, while the pendant tricontyl groups were
oil-philic and CO2-insoluble. These waterless emulsions can
exhibit high apparent viscosity. For example, a 90% quality (i.e.,
90 vol % liquid CO2 droplets) C/O emulsion stabilized with 2 wt
% of this silicone−alkyl surfactant stabilized an emulsion with
very small CO2 droplets (5−100 μm); the emulsion exhibited an
apparent viscosity of 4.2 cP at 25 °C and 17.2 MPa (2,500 psi),
which is 47 times more viscous than CO2 (0.09 cP) at the same
condition. Foam stability obtained with this surfactant was
clearly superior to that attained with the other conventional
surfactants reported in the literature that we tested, including
poly(trimethylhydrosilylsiloxane).
Quite recently a proprietary direct-thickening product for
CO283 was described. This polymer−solvent mixture (PSM)
consisted of “a mixture of dif ferent compounds including
copolymers of allenethers, acrylate, acrylic long carbon chain
esters/benzenes, propylene carbonate/allyl ethyl carbonate, dimethyl
carbonate, and white oil/silicon or oil/petroleum ether”. PSM was
soluble in CO2 at 25 °C and 2,500 psi, and solution viscosity
values of about 100 cP were reported for 1 wt % mixtures of PSM
with CO2, with viscosity increasing with pressure. Although the
proportions of these components were not provided by the
authors, the authors had the manufacturer provide our team with
a sample for assessment in this current study.
1.3. Increasing the Viscosity of CO2 Using Stable,
Dilute Suspensions of Nanoparticles in CO2. As will be
demonstrated in this section, studies related to suspending
nanoparticles (NPs) in CO2 typically do not involve viscosity
measurements because the primary goal of those studies was to
surface-functionalize NPs with CO2-philic groups and then
monitor the stability of the suspensions in CO2 (e.g., turbidity).
The ability to disperse or suspend NPs in CO2 could find utility
in various engineering applications, such as the formation of
metal or polymer NPs in CO2. Forming stable NP suspensions
in CO2 is much more challenging than dispersing NPs in water
or oil. CO2 is a feeble solvent relative to water relative to polar or
ionic groups. CO2 is also a weaker solvent than organic solvents
for hydrocarbon-based moieties. The very low viscosity of CO2
makes it difficult to disperse or suspend particles. Therefore, the
investigators resorted to grafting highly CO2-philic groups on
the NPs, or using conventional hydrophobic coatings in
conjunction with a substantial amount of cosolvent. Suspensions
that exhibited stability for about 30 min in CO2 were attained by
grafting fluoroalkyl segments onto the surface of nanoscale
silica.124,125 Silica (7 or 12 nm) and alumina (8−14 nm) were
dispersed in CO2 after having fluoroalkyl functional groups
attached to the particle surface.126 Fluoromethacrylate ligands
were used to disperse nanoparticles of silica127 or iron oxide128
in CO2. Hydrophobic (i.e., a proprietary PDMS modification)
silica particles (∼5 μm) were suspended in CO2, as were silica
particles that were surface modified with dispersants containing
fluoroacrylate- and fluoroether-based tails.129 PDMS-function-
alized nanosilica particles were reportedly dispersed in CO2.130
Silver NPs were synthesized and dispersed in CO2 using
isostearic acid as a dispersant and hexane as a cosolvent.131 In
these reports, NP size, shape, and surface functionalization were
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carefully characterized, direct observations of the suspension
were made, and the stability of the suspension was monitored
over a period of time, commonly with turbidity measurements.
A few attempts to explicitly thicken CO2 with stable NP
dispersions have been reported in conference proceedings. One
attempt was made to suspend fumed silica in liquid CO2, with
and without the use of organic cosolvents; these experiments
were unsuccessful because the silica NPs quickly aggregated and
settled to the bottom of the high-pressure windowed vessel.100
Another report of CO2 thickening with suspensions of NPs and
stabilizing agents claimed success, but this report did not include
experimental validations that the cosolvent dissolved in the CO2
nor were there direct observations of a stable NP suspension.132
These investigators reported that the viscosity of pure
supercritical CO2 was 0.016 cP at 50 °C, but the pressure was
unspecified. This CO2 viscosity value of 0.016 cP is attained at
only 100−400 psia,133 but this low-pressure range appears to be
inconsistent with the higher “mixing pressure” of 17.2 MPa
(2500 psi) mentioned elsewhere in the report132 (at 50 °C and
17.2 MPa (2,500 psia); the viscosity of CO2 is 0.062 cP133).
Regardless of this pressure/viscosity inconsistency related to the
pure CO2 control experiment, the viscosity of the NP-thickened
CO2 was then reported to be 2.28 cP due to the addition of 5 wt
% PDMS (MW 139,000; 100,000 cP) and 1 wt % CuO particles
(50 nm cluster size) at 17.2 MPa (2,500 psi). This would
correspond to a 3.7-fold increase in CO2 viscosity from its value
of 0.062 cP. However, there was no validation that 5 wt % PDMS
could even dissolve in CO2 at 50 °C and 2,500 psi without the
addition of a cosolvent. Our group’s CO2−PDMS phase
behavior study, conducted in a windowed vessel, indicates that
only oligomers of PDMS of molecular weight less than ∼4,000
can dissolve in CO2 at these conditions.36 Further, as previously
discussed,34 substantial amounts of toluene cosolvent are
typically required for the dissolution of high molecular weight
PDMS in CO2 at comparable conditions. Neither was there a
visual or optical measurement (e.g., turbidity) to verify that a
stable dispersion of CuO in CO2−PDMS formed in any of the
equipment, including the viscometer.
Subsequently, another group134 cited this prior conference
work132 and reported a stable suspension of 1 wt % NiO NP (60
nm) in CO2 using 2 wt % PDMS (unspecified molecular weight)
at a “mixing pressure” of 2,500 psi (the temperature was not
provided). However, the work did not demonstrate that PDMS
and CO2 were miscible at these conditions nor was the viscosity
of the purported suspension measured.
Very recently, it has been reported that ∼2−8 wt % of a
nanocomposite composed primarily of high molecular weight
(600,000) P1D and graphene oxide (GO) particles (e.g.,
20,000−80,000 ppm nanocomposite containing up to 500 ppm
GO) thickens CO2 (e.g., a 23-fold increases at 60,000 ppm
nanocomposite containing 300 ppm GO).5 However, no details
of the falling ball were provided, and no explanation of how the
P1D of such high molecular weight (600,000) was CO2-soluble
when prior researchers indicated that only very low molecular
weight P1D could dissolve in CO2.
In another study, Zhang and co-workers135 proposed
combining a partially sulfonated fluorinated copolymer that
contained styrene with a nanocomposite fiber formed by
combining nanoparticles in a polyester fiber. The authors
reported that the viscosity of CO2 was increased 100-fold at a 1
wt % concentration of these components along with a
comparable amount of diesel.
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Figure 1. Molecular structures of the purported CO2 thickeners experimentally assessed in this review.
This NP-based method of thickening CO2 remains in its
infancy, with aspirations for success buoyed to some extent by
promising simulation results with nanoparticle-thickened CO2
was injected alternately with neat CO2, or with nanoparticle-
thickened CO2 used in a conventional water-alternating-gas
scheme.136 Modest NP thickening (30−150% increases) of CO2
was also predicted using multiscale computational modeling of 1
vol % CuO NPs dispersed in CO2137
1.4. Unspecified Thickener Compositions. There are
several literature references, both patent and journal, that
describe the thickening of CO2 with compounds or mixtures
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that are not fully specified, and hence not reproducible by other
investigators. These references are described in this section.
Song and co-workers117,138 reported that they had developed
“TNJ”, which is a “new thickener special in structure” that
increased CO2 viscosity by 240−490 times at concentrations of
1.5−2.0%. No other information was provided. In a 2014
Chinese patent, Song claimed that CO2 could be thickened by a
fatty acid-rich mixture described as “the fluid system comprising
the mass percentages of components: 0.1% - 5% viscosifier, 0.3%
−6.5% conditioning agent; the remaining components are super-
critical carbon dioxide. Viscosifier of the higher fatty acid ester, a
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higher fatty acid compounds f rom the glycerol, high fatty acid is
palmitic acid, stearic acid, oleic acid, linoleic acid, eleostearic acid,
linolecic acid, ricinoleic several combinations of acid. The
conditioning agent is a combination of a saturated aliphatic cyclic
hydrocarbon and halogenated alkane of small molecules”. Given the
highly CO2-phobic nature of fatty acids, it is doubtful that this
mixture formed a single-phase solution unless the “conditioning
agent” is a strong CO2-soluble cosolvent. Perhaps this blend
formed an opaque two-phase system composed of an inter-
locking network of fibers in a CO2-rich liquid with high apparent
viscosity, or a C/O emulsion. We could not replicate this
mixture because of a lack of details.
Jian and co-workers139 proposed a CO2 thickener solution
“X”, which is 1/3 copolymer and 2/3 solvent “B” that requires
heating the mixture at elevated pressure until it is one phase,
letting it cool, and pumping it to a mixing point where the
mixture allegedly thickens the CO2. No details were provided.
Lu et al.140 and Cui et al. reported141 a gelled CO2-based
mixture, but presented no details of the alleged “new surfactant”
other than a generic diagram of a cylindrical micelle
accompanied by claims of a 100−500-fold increase in CO2
viscosity.
Jin and Zheng142 found that a “special liquid CO2viscosifier
(Chemical B)” could be dispersed in water, and when the water,
which also contained a “self-crosslinking water viscosif ier
(Chemical A)”, was mixed with CO2, a high apparent viscosity
foam of thickened CO2 droplets within surfactant-stabilized
films of water that was suitable for hydraulic fracturing.
However, there was no description of “Chemical B” nor was
evidence presented that “Chemical B” would thicken CO2
droplets within the C/W foam. Further no description of the
surfactant needed to stabilize the foam was presented.
Unverifiable claims were also made that “Chemical B” and
CO2 could alone make a thickened CO2 fracturing fluid.
Luo and co-workers143 studied a “fluorinated, dual, twin-tailed
surfactant with divalent metal cations, at the same time, it is also a
kind of amphiphilic surfactant.” Small amounts of water were used
to stabilize rod-like micelles. Very significant viscosity increases,
much greater than those presented in well documented
surfactant studies, were reported using several weight percent
of the surfactant in CO2 on the basis of pipe flow measurements.
Yang and co-workers provided an overview of five years of
CO2 fracturing144 in the Jilin oilfield. However, they only
provided vague descriptions of their two thickening strategies,
“small molecule surfactant” and “polymer emulsion thickener system
to promote polymer dissolution with a water-in-oil structure”.
Meng and co-workers145 described their efforts to thicken
CO2 using “(System A) a single amphiphilic f luoropolymer, with a
CO2-philic f luorine-containing group and a polar sulfonic group”
and “other additive system (System B) composed of a main
thickening agent (a CO2-philic double-chained surfactant) and an
assistant agent. These two additives can form viscoelastic micelles in
liquid CO2.”. Meng and co-workers also discussed a case study
involving an “emulsion thickener” for CO2 during waterless
fracturing.146
2. MATERIALS AND EXPERIMENTAL METHODS FOR
ASSESSMENTS OF PURPORTED CO2 THICKENERS
2.1. Experimental Validation of Readily Available CO2-
Thickening Candidates. It was not feasible for our team to assess
every compound that has been proposed as a CO2 thickener, especially
because many of these novel compounds are not available commercially
and must be synthesized, purified, and characterized prior to being
pubs.acs.org/EF Review
evaluated. However, several of the polymeric and small-molecule
compounds that have been reported to be CO2, Figure 1, are either
commercially available or readily synthesized, or were provided to us as
gifts for assessment. The cosolvents required for the dissolution of
many of these thickener candidates are also readily available, and
cosolvent concentrations above 25% were not considered. The
objective of this experimental work was not to optimize the conditions
for CO2 thickening (temperature, pressure, cosolvent concentration,
and thickener concentration). Rather, the objective of this experimental
study was to use a windowed high-pressure falling object viscometer to
validate if the purported thickener dissolved completely in CO2, or
established a foam or emulsion, and also had the ability to thicken CO2
as described in the literature.
2.2. Materials. 2.2.1. High Molecular Weight Polymeric
Thickeners. The following high molecular weight polymers were
assessed in this study.
PolyFAST (MW ∼ 500,000), based on the -C6F13 moiety in the
fluoroacrylate monomer, was synthesized according to our team’s
previously published procedure for bulk copolymerization of a
copolymer containing styrene (29 mol %) and fluoroacrylate (71 mol
%) monomers.55
PFA (MW ∼ 124,000), based on the -C6F13 moiety in the
fluoroacrylate monomer, was synthesized according to our previously
published procedures for bulk homopolymerization of the fluoroacry-
late monomer.84
PDMS, poly(dimethylsiloxane), was obtained from Clearco. Two
samples (MW 500,000+, 20,000,000 cSt, and MW 308,000, 1,000,000
cSt) were used as received without further purification.
PVAc, poly(vinyl acetate) (MW ∼ 500,000), was obtained from
Sigma-Aldrich and used without further purification.
PSM, a “polymer solvent mixture” of allyl ethers, acrylate, acrylic long
carbon chain esters/benzenes, propylene carbonate/allyl ethyl
carbonate, dimethyl carbonate, and white oil/silicon or oil/petroleum
ether, was obtained from the manufacturer (Beijing AP Polymer
Technology Co., Ltd.) in the form of an emulsion with 35% active
ingredients.
2.2.2. Low Molecular Weight Polymeric or Oligomeric Thickeners.
The following low molecular weight polymers or oligomers were
evaluated in this study:
P1D, poly-1-decene (MW ∼ 910), which can be considered as an
oligomer, was obtained from Sigma-Aldrich and used without further
purification.
PVEE, poly(vinyl ethyl ether) (MW ∼ 3800), was obtained from
Sigma-Aldrich and used without further purification.
2.2.3. Small-Molecule Associative Thickeners. The following small
molecules were evaluated in this study.
AOT, bis(2-ethylhexyl) sulfosuccinate sodium salt (97%), was
obtained from Sigma-Aldrich and used without further purification.
EG, anhydrous ethylene glycol (99.8%), was obtained from Sigma-
Aldrich and used without further purification.
TBTF, tributyltin fluoride (97%), was obtained from Sigma-Aldrich
and used without further purification.
12HSA, 12-hydroxystearic acid (99%), was obtained from Sigma-
Aldrich and used without further purification.
HAD2EH, hydroxyaluminum di(2-ethylhexanoate) (96%), was
obtained from TCI and used without further purification.
OG160/XL064 was a two-component mixture: OG160, a phosphate
ester blend designed specifically for gelling butane and propane;102
XL064, a trivalent iron-based acidic cross-linking solution. They were
obtained from one of the inventors and used as received. A preliminary
test verified that 0.5 vol % OG160 + 0.5 vol % XL064 increased the
viscosity of liquid propane and butane by 2−3 orders of magnitude at 25
°C and 5,000 psia. The OG160/XL064 combination was used rather
than a phosphate ester−cross-linker blend designed for hexane; that
product had longer alkyl groups in the OG components and induced
very modest changes in propane viscosity.9
2.2.4. Cosolvents. Ethanol (99.5%), hexanes (98.5%, ∼64% n-
hexane), and toluene (99.8%) were obtained from Sigma-Aldrich and
used without further purification.
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Table 6. Relative Viscosity Results for the CO2-Thickening Candidates

thickener concn CO2concn cosolvent concn Is thickener falling relative viscosity
thickener MW T (°C) P (psig) (wt %) (wt %) cosolvent (wt %) soluble? objecta (±10%)
none 23 0 100 C 1.0
none 23 2−4000 0 76 toluene 24 C 1.1
none 23 3−5000 0 76 ethanol 24 C 1.7
high MW
polymers
polyFAST 5.0 × 105 25 4000 4 96 yes C 138
PFA 1.24 × 106 25 2000 4 96 yes C 2.8
PFA 1.24 × 106 25 3000 4 96 yes C 4.2
PFA 1.24 × 106 25 4000 4 96 yes C 5.4
PDMS 5.0 × 105 23 1500 2 75 toluene 23 yes B 3.6
PDMS 5.0 × 105 23 2000 2 75 toluene 23 yes B 4.1
PDMS 5.0 × 105 23 3000 2 75 toluene 23 yes B 4.7
PDMS 5.0 × 105 23 4000 2 75 toluene 23 yes B 5.6
PDMS 3.1 × 105 23 1500 2 75 toluene 23 yes B 1.9
PDMS 3.1 × 105 23 2000 2 75 toluene 23 yes B 2.1
PDMS 3.1 × 105 23 3000 2 75 toluene 23 yes B 2.0
PDMS 3.1 × 105 23 4000 2 75 toluene 23 yes B 2.0
PVAc 5.0 × 105 23 3000 2 75 toluene 23 yes B 1.7
PVAc 5.0 × 105 23 4000 2 75 toluene 23 yes B 1.7
low MW
polymers
PVEE 3800 100 8000 2 98 yes C 1.0
PVEE 3800 23 1500 2 75 toluene 23 yes B 1.3
PVEE 3800 23 4000 2 75 toluene 23 yes B 1.3
P1D 910 23 5000 2 98 yes B 1.0
P1D 910 100 7000 4 96 yes C 1.0
small
molecules
OG/XL 23 2000 0.34 81 hexane 18.66 no B n/a
EG 62 23 3500 2 98 yes C 1.0
EG 62 23 4000 2 98 yes C 1.0
AOT 445 25 3000 1.5 78.5 ethanol 20 yes C 2.5
TBTFb 309 25 5000 2 75 toluene 23 no
HAD2EHb 331 25 5000 2 75 toluene 23 no
12HSAc 300 23 5000 2 75 toluene 23.00 no
12HSA 300 23 5000 2 75 ethanol 23.00 no
indirect
thickener
PSMd 25 2500 2 98 no C
a
B = falling ball viscometry; C = falling cylinder viscometry. bA heating/cooling cycle was used. cAn opaque 12HSA gel formed. dPSM is a
proprietary composition that formed a C/O emulsion, but undissolved polymer prevented viscosity measurements.

2.3. Methods. The solubility of polymeric and small-molecule
direct thickeners was assessed using a nonsampling, visual technique.
The relative viscosity of the CO2-thickener solution was also
determined using falling object viscometry.
2.3.1. Solubility Measurements. Whether thickener candidates
could dissolve in CO2 was determined using a visual technique that is
detailed in our prior publications.1,9,18,55,65,84,115 Known amounts of the
thickener and liquid CO2 are charged to a fully windowed, agitated,
invertible, variable-volume (10−100 mL), high-pressure view cell
(Schlumberger, 69 MPa (10,000 psi) at 180 °C). This phase behavior
cell is kept within an isothermal air bath with cooling and heating
capabilities (CSZ, −20 to 180 °C). The contents are then compressed
to pressures up to 69 MPa and mixed with a magnetically driven, slotted
fin impeller (2,000 rpm) at the top of the sample volume. After mixing,
the impeller rotation is stopped and the entire cylindrical sample
volume is inspected to verify that a single, transparent fluid phase has
been attained. If so, the single phase is expanded at a very slow rate until
a second phase occurs, typically in the form of a cloud of thickener-rich
droplets or particles. The pressure at which the second phase begins to
appear is the cloud point pressure. Typically, this procedure is repeated
five times and the average value of the cloud points is determined. By
repeating this procedure for various compositions (i.e., different ratios
of CO2 and thickener), a cloud point locus that represents a small
portion of the overall pressure−composition diagram can be
constructed.
If a thickener is insoluble in CO2, as evidenced by the thickener
remaining as a second phase (solid or liquid) after extended mixing,
then the experiment can be repeated using a cosolvent such as ethanol
or toluene.
If, upon mixing, a foam or emulsion is being formed (as evidenced by
dispersed bubbles or droplets of CO2 within a second continuous film
phase), then the mixing is continued until the emulsion is formed to its
fullest extent. In such a case, the additive is not considered as a direct
thickener but rather as a mixture that promotes the formation of a high-
quality (i.e., high volume percent CO2), waterless, CO2-in-oil emulsion.
2.3.2. Falling Object Viscometry. The assessment of the CO2-
thickening capability of each candidate was determined using the same
apparatus that was employed for solubility measurements and has been
detailed in prior publications.9,18,55,65,84,115 A close-clearance Pyrex
sphere (diameter = 3.1587 cm) or an aluminum cylinder (diameter =
3.16179 cm; height = 2.54 cm) is placed in the cylindrical sample
volume with a 3.1750 cm diameter. The mixture is then stirred and

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compressed to a pressure several thousand psi greater than the
previously measured cloud point to ensure the attainment of a single
phase. Mixing is then stopped, and the occurrence of a transparent
single phase is verified. The entire phase cell (which is mounted on a
steel rod and has coiled tubing leading to and from the cell) is then
quickly inverted, and the fall of the object, observed. The foremost
advantage of this visual technique is that it is possible to easily observe
undissolved particles or undissolved viscous droplets of a thickener-rich
phase that can impede the fall of the ball or cylinder. The complete fall
of the ball is observed, and the velocity is determined by measuring the
duration of the fall between two locations separated by a known
distance. The terminal velocity of the ball or cylinder falling within the
confined ∼15 cm column of thickened CO2 is typically attained within
the first third (5 cm) of the fall. The viscometer is also calibrated by
determining the terminal velocity of the same object in pure CO2 at the
same temperature and pressure.
Because the concentrations of the thickeners in CO2 are low, it is
reasonable to assume that the density of the CO2-thickener solution is
approximately the same as the density of pure CO2 at the same
conditions. Therefore, the driving force for the fall (falling object
density − fluid density) is roughly the same for pure CO2 and thickened
CO2. As a result, relative viscosity (the ratio of solution viscosity to pure
CO2 viscosity) can be estimated simply by determining the ratio of the
terminal velocity in CO2 to the terminal velocity in the CO2-thickener
solution. For example, if the ball falls five times slower, then the
thickened CO2 is about five times more viscous than pure CO2.
Viscosity measurements were repeated five times, and in all cases the
five relative viscosity values for each test fell within ±10% of the average
value.
This technique can also be used to assess the apparent viscosity of an
emulsion of foam, but only if the emulsion or foam is stable enough to
fill the entire sample for the duration of the experiment.
3. CO2 THICKENER RELATIVE VISCOSITY RESULTS
Table 6 presents a summary of the relative viscosity results
obtained in this study. The results are presented within the
major groups: polymeric direct thickeners, small-molecule direct
thickeners, and indirect thickeners. No nanoparticle dispersions
were available for evaluation.
3.1. High Molecular Weight Polymeric Direct Thick-
eners. 3.1.1. PolyFAST. PolyFAST exhibited remarkably greater
CO2-thickening (138-fold increase at 4 wt %) than any other
compound and did not require cosolvent addition to attain a
single phase. However, polyFAST requires a greater pressure to
dissolve in CO2 than PFA (a less effective thickener) because
polyFAST contains ∼29 mol % styrene, which is far less CO2-
philic than the fluoroacrylate monomer.
3.1.2. PFA. PFA is capable of thickening CO2, but not as
effectively as polyFAST. The sample of PFA used in this study
was not as effective as the PFA used in our prior study, in which
the CO2 viscosity was increased by a factor of ∼3 at low shear
rate using only 1 wt % PFA.84 The molecular weight of the PFA
in this study was likely less than that of the PFA in our prior
study. The results verify that 3−5-fold increases in CO2 can be
attained using several weight percent PFA.
3.1.3. PDMS. High molecular weight PDMS is essentially
CO2-insoluble; therefore toluene was used to promote
dissolution of enough PDMS in CO2 to attain viscosity
enhancement at pressures below 60 MPa (8,700 psi).6,32−34
Increases in CO2 viscosity of 3−6-fold were realized using 2 wt %
PDMS (MW 500,000+) in the presence of 23 wt % toluene and
75 wt % CO2. When the same mass concentration of a lower
molecular weight PDMS (MW 308,000) was used, the CO2
viscosity increased by a factor of ∼2, representing a 100%
increase. Note that the toluene addition alone to the CO2 (no
pubs.acs.org/EF Review
PDMS) would account for a CO2−toluene solution relative
viscosity of about 1.1.
3.1.4. PVAc. PVAc requires substantial amounts of a
cosolvent, such as toluene, to dissolve in CO2 at pressures
below ∼30 MPa (4,350 psi). A single-phase solution of 23 wt %
toluene, 75 wt % CO2, and 2 wt % of the PVAc was evaluated. At
a concentration of ∼2 wt % of the highest molecular weight
PVAc that was available (MW 500,000), the viscosity of CO2
increased by about 70% to a relative viscosity of 1.7. As was the
case with PDMS, a portion of this increase was attributable to
the presence of the toluene in CO2, which results in a relative
viscosity of 1.1.
3.2. Low Molecular Weight Polymeric Thickeners.
3.2.1. PVEE. No significant increase in solution viscosity was
detected when 2 wt % PVEE was dissolved in CO2 at 100 °C and
8,000 psi. Toluene was then introduced to allow a single phase to
be attained at lower temperature and pressure. For mixtures of 2
wt % PVEE, 23 wt % toluene, and 75 wt % CO2, viscosity
increases of about 30% (relative to pure CO2) were measured at
23 °C and 1,500−4,000 psi. The addition of toluene alone
yielded a relative viscosity of 1.1.
3.2.2. P1D. The addition of 2−4 wt % P1D in CO2 did not
increase the viscosity of CO2 by more than 5% in any of our
measurements.
3.3. Small-Molecule Direct Thickeners. 3.3.1. OG160/
XL064. A 0.5 vol % amount of OG160 and 0.5 vol % XL064 were
mixed with hexane at 23 °C. A thick, viscoelastic solution
formed. This thickened hexane sample was added to the sample
volume of the high pressure phase behavior cell along with liquid
CO2 such that a 50:50 thickened hexane:CO2 (vol %) mixture
formed (0.125:0.125:24.75:75 OG160:XL064:hexane:CO2 (vol
%)) at 22 °C and 17.2 MPa (2,500 psi). Because the density
values of CO2, hexane, OG160, and XL064 at 22 °C and 17.2
MPa (2,500 psi) are 0.91, 0.65, 1.01, and 1.30 g/mL,
respectively, this corresponds to 80.648 wt % CO2, 19.010%
hexane, 0.150 wt % OG160, and 0.192 wt % XL064. Upon
mixing, the cross-linked phosphate ester precipitated and would
not redissolve in the CO2−hexane solution despite a prolonged
mixing at an elevated pressure of 7,000 psi. Apparently, a greater
proportion of cosolvent is needed to attain a stable single phase,
such as the 50:50 CO2:light alkanes (vol %) mixture reported by
Taylor and workers.104
3.3.2. EG. No detectable increase in viscosity was detected
with the addition of 2 wt % EG to CO2.
3.3.3. AOT. AOT is insoluble in CO2. When ethanol was used
as a cosolvent, a single phase of 1.5 wt % AOT was attained in a
mixture containing 20 wt % ethanol and 78.5 wt % CO2. The
relative viscosity was 2.5 times greater than that of pure CO2.
Note that the addition of ethanol alone resulted in a CO2−
ethanol solution relative viscosity of 1.7.
3.3.4. TBTF. A solution that contained 2 g of TBTF and 23 g of
toluene (8 wt % TBTF) was made into a transparent gel by
heating the mixture gently to 40 °C while stirring and letting the
TBTF completely dissolve. The solution was then cooled to 23
°C and a clear, highly viscous solution formed. This viscous
solution was placed in the sample volume of the phase behavior
apparatus in a 2:23:75 TBTF:toluene:CO2 (wt %) ratio. The
high-pressure CO2 acted as an antisolvent at 34.5 MPa (5,000
psi) and 23 °C, dissolving the toluene and leaving fibers and
flakes of TBTF behind. The solution was then heated to ∼75 °C
at 34.5 MPa (5,000 psi) and stirred, at which point only a small
portion of the TBTF had dissolved. This solution was allowed to
cool to 23 °C overnight at 34.5 MPa (5,000 psi). The TBTF
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came out of solution as chunks of gels dispersed in CO2. Gels of
TBTF in toluene were recovered when the CO2 was vented.
Similar results were obtained using hexanes as cosolvent. These
results are consistent with the prior reports,90,91 which indicated
that extremely high concentrations (60+ wt %) of pentane
cosolvent were required for TBTF to dissolve in CO2.
3.3.5. HAD2EH. A mixture of 2 g of HAD2EH and 23 g of
toluene (8 wt % HAD2EH) was heated to 40 °C while being
stirred. The resultant solution was allowed to cool to ambient
temperature and a clear rigid gel formed. This rigid gel was
placed in the sample volume of the phase behavior cell in a
2:23:75 HAD2EH:toluene:CO2 (wt %) ratio. The high-pressure
CO2 acted as an antisolvent at 34.5 MPa (5,000 psi) and 23 °C,
dissolving the toluene and leaving solid fibers and flakes of
HAD2EH behind. The mixture was then heated to 75 °C at 34.5
MPa (5,000 psi) and stirred overnight, at which point only a
portion of the HAD2EH had dissolved. This mixture solution
was allowed to cool to ∼23 °C at 34.5 MPa (5,000 psi). Large
blobs of HAD2EH-gelled toluene formed. We then assessed a
different means of mixing the components. A mixture of 2:23:75
HAD2EH:toluene:liquid CO2 (wt %) ratio was added to the
cell, and then mixing and heating commenced. The high-
pressure CO2 mixed readily with the toluene, leaving clumps of
HAD2EH powder behind. The mixture of CO2 and HAD2EH
was heated to ∼75 °C at 34.5 MPa (5,000 psi) while being
stirred, at which point only a small portion of HAD2EH had
dissolved, while the majority of the HAD2EH remained in
slightly gelled clumps. This mixture was allowed to cool to
ambient T overnight at 5,000 psi, and the HAD2EH came out of
solution as blobs of toluene-rich gels dispersed in CO2.
3.3.6. 12HSA. A mixture of 2 g of 12HSA and 23 g of toluene
(8 wt % 12HSA) was heated to ∼75 °C while stirring. The
resultant solution as allowed to cool to 23 °C, and a single-phase,
transparent, rigid gel formed. This gel was placed in the sample
volume of the high pressure phase behavior cell. Liquid CO2 was
then added such that a 2:23:75 12HSA:toluene:CO2 (wt %)
ratio mixture was present. The high-pressure CO2 acted as an
antisolvent at 34.5 MPa (5,000 psi) and 23 °C, dissolving the
toluene and leaving fibers and flakes of 12HSA behind. The
mixture was heated to 75 °C at 41.4 MPa (6,000 psi) with the
stirrer at 2,000 rpm. Only a small portion of the 12HSA
dissolved. This mixture was allowed to cool to 23 °C at 34.5 MPa
(5,000 psi). The 12HSA precipitated in the form of blobs of
toluene-rich gels dispersed in CO2. A mass of HSA-gelled
toluene was recovered when the CO2 was vented.
We then assessed a different means of mixing the components.
A mixture of 2:23:75 12HSA:toluene:CO2 (wt %) was
introduced to the sample volume of the phase behavior cell.
The CO2 quickly acted as an antisolvent at 34.5 MPa (5,000 psi)
and 23 °C, dissolving some the toluene and clumps of 12HSA
powder left behind. The solution was then heated to 75 °C at
34.5 MPa (5,000 psi) and stirred, at which point some of 12HSA
dissolved, while some of the 12HSA remained suspended in the
fluid as soft translucent gels. This mixture was allowed to cool to
22 °C overnight at 34.5 MPa (5,000 psi). An opaque, light
brown mass of CO2-swollen gel blobs filled the entire sample
volume. Upon subsequent slow expansion of the high-pressure
mixture via lowering the position of the movable piston at the
bottom of the sample volume, the flat bottom of this brown mass
remained flat and stationary in the sample volume as clear CO2
expanded into the volume under the gel and above the sliding
piston. Upon removal of the CO2, a soft monolith of a porous
12HSA:toluene foamed gel remained.
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Following the lead of ref 95, a solution of 2 g of 12HSA and 23
g of ethanol (8 wt % 12HSA) formed a transparent solution (not
a gel) by heating the mixture gently to ∼75 °C while stirring,
thereby allowing the 12HSA to completely dissolve in ethanol.
The solution was then cooled to 23 °C; it remained a low-
viscosity solution. This solution was then transferred to the
sample volume of the windowed phase behavior cell along with
liquid CO2 in a 2:23:75 12HSA:ethanol:CO2 (wt %) ratio. The
high-pressure CO2 acted as an antisolvent at 34.5 MPa (5,000
psi) and 22 °C, dissolving the ethanol and leaving fibers and
flakes of 12HSA behind. The mixture was then heated to ∼75 °C
at 41.4 MPa (6,000 psi) and stirred, at which point only a small
portion of the 12HSA dissolved. This mixture was allowed to
cool to 22 °C at 34.5 MPa (5,000 psi), and a significant amount
of 12HSA precipitated as swollen white flakes.
3.4. Indirect Thickeners. 3.4.1. PSM. When PSM and CO2
were first combined, the polymeric components quickly
precipitated to the bottom of the cell as the lower molecular
solvent components dissolved in CO2. After being mixed
overnight (10 h) at the same conditions reported by the
researchers,83 an opaque, white, C/O waterless emulsion of
millimeter-sized CO2 droplets separated by continuous films of
an oleic phase had filled the entire phase behavior sample with
the exception of two very large (∼5 mm diameter) droplets of
clear CO2 and several small blobs of undissolved polymer. (It is
likely that with improved mixing, the mixture would have been
more homogeneous throughout the entire sample volume.) The
mixture was not a transparent single-phase CO2-rich solution;
therefore, the sample of PSM that we received was not a direct
thickener as described by Al Yousef.83 However, it could be
considered as an indirect thickener that slowly established a
waterless, C/O emulsion with a very high volume fraction
(quality) of liquid CO2. Although not thermodynamically stable,
the emulsion was stable enough to persist without any noticeable
collapse several hours after the cessation of mixing. Unfortu-
nately, a small piece of undissolved polymer became lodged
between our aluminum cylinder and the Pyrex wall of our
windowed viscometer and we were unable to obtain falling
cylinder apparent viscosity values during several attempts.
However, such C/O waterless emulsions can exhibit high
apparent viscosity, and a prior report of high viscosity of CO2
that was “thickened” by PSM83 may have been attributable to
the high apparent viscosity of indirectly thickened CO2 (a C/O
emulsion) such as those we previously reported (Alzobaidi et
al.4). Alternately, the sample of PSM that we received from the
manufacturer may have differed significantly from that used by
Al Yousef and coworkers.83
4. CHALLENGES AND NEW RESEARCH DIRECTIONS
4.1. Understanding the Unique Solvent Nature of CO2
while Designing New CO2-Soluble Compounds. In
retrospect, the unique nature of CO2 was overlooked by many
investigators in the early years of thickener development because
CO2 was simply considered to be like a light alkane. This is not
an inaccurate observation if one is only considering the ability of
CO2 to extract components from a saturated hydrocarbon-based
multicomponent crude oil. In these cases, it would be reasonable
to assume that if the hydrocarbon component was soluble in
pentane, hexane, or isooctane, then the hydrocarbon might be
CO2-soluble. Further, recent studies of high-pressure huff-and-
puff EOR in unconventional liquid reservoirs clearly indicate
that very similar oil recovery is attained using high-pressure
ethane or CO2.147 However, the only saturated hydrocarbon
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thickeners ever proposed for CO2 were high molecular weight
poly(α-olefins), which turned out to be CO2-insoluble. Every
other type of prospective CO2 thickener exhibited striking
dissimilarities in composition with a simple hydrocarbon.
Therefore, the analogy between light alkanes and CO2 was
inappropriate for CO2 thickeners, and continued use of light
alkanes as a screening tool provided poor predictions during
screening. For example, fluoropolymers with oxygenated
hydrocarbon backbones such as PFA and polyFAST are
insoluble in hydrocarbons yet are remarkably soluble in CO2.
PVAc is quite soluble in very high pressure CO2 but insoluble in
alkanes. CO2 is actually a better solvent (not a weaker solvent)
than light alkanes for a wide range of silicone oils. To complicate
matters, light alkanes can also give overly optimistic results for
many thickening candidates. This led to investigators spending a
great deal of resources investigating utterly CO2-insoluble
compounds. For example, TBTF, HAD2EH, 12HSA, and CPE
are remarkable thickeners of light alkanes, yet every one of them
is essentially CO2-insoluble (unless substantial concentrations
of cosolvent are added to the CO2). As it became more apparent
that CO2 was a complex and unique solvent, subsequent
development of novel CO2-soluble compounds (whether
thickeners, surfactants, dispersants, chelating agents, polymers,
or oligomers) was usually conducted with CO2, and only CO2, in
mind and in the laboratory. One of our coauthors encapsulated
these design principles in a journal article dedicated solely to
these design principles148
The solvent attributes of CO2 are probably best understood in
light of what CO2 can, and cannot, dissolve. Regardless of
polymer composition, CO2 is a poor solvent for highly
crystalline, high melting point materials. Anionic and cationic
moieties are inherently CO2-phobic and always tend to diminish
or eliminate CO2 solubility. Highly polar functional groups such
as carboxylic acids, alcohols, and acrylamide are CO2-phobic,
typically because the interactions between these groups are
much stronger than the interactions between these groups and
CO2. As a result, no known high molecular weight water-soluble
polymers (which are typically rich in these functional groups)
exhibit significant CO2 solubility. The CO2-phobicity of highly
polar or ionic groups is also the reason that most conventional
oil-thickening agents are CO2-insoluble. Although CO2 can
solubilize a small hydrocarbon chain, it is not as strong of a
solvent for the hydrocarbon portion of thickeners as mineral oils,
for example. When highly polar or ionic associating groups are
incorporated within the molecule, the thickener may remain
soluble in mineral oil but precipitate in CO2. Therefore, it
appears that “subtle”, nonpolar, non-ionic associating groups
should be considered for CO2 thickeners. For example, benzene
rings have been successfully incorporated into polyFAST, and
the incorporation of aromatic groups into PDMS is under
consideration. This aromatic ring can associate via π−π stacking,
yet this benzene ring is not highly CO2-phobic and its inclusion
in a polymer does not appear to significantly diminish CO2
solubility.
Now the remarkably high solubilities of the PFA, polyFAST,
and perfluoropolyether in CO2, and the CO2-insolubility of
other fluoropolymers such as polytetrafluoroethylene (PTFE,
Teflon) are considered. The design lessons related to these
fluoropolymers148 are (a) fluorine atoms impart a weak self-
interaction attributed to compounds, which may make
miscibility with CO2 possible, (b) the electronegative character
of fluorine atoms may exhibit thermodynamically favorable
interactions with the electron-deficient carbon atom of CO2, (c)
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the fluorine atoms can alter the acidity of neighboring hydrogen
atoms within the polymer backbone, thereby promoting
thermodynamically favorable interactions with the electron-
rich oxygen atoms of CO2, (d) although CO2 is linear and
symmetric and has no dipole moment, the quadrupole moment
of CO2 (associated with its electron-poor carbon and electron-
rich oxygens) is capable of promoting favorable Lewis acid−
Lewis base and weak hydrogen bonding interactions with the
oxygenated hydrocarbon backbone of the fluoropolymer, and
(e) the amorphous nature or low crystallinities and low melting
points of PFA and polyFAST allow CO2 to access the pendant
arms and polymer backbone, while the high melting point PTFE
remains impervious to significant CO2 swelling or dissolution.
Lower molecular weight PDMS is highly soluble in CO2, while
very high molecular weight PDMS requires a substantial amount
of an organic solvent such as toluene to facilitate dissolution in
CO2 at reasonable pressures. When considering high molecular
weight polymers, only polyfluoroacrylate exhibits a greater CO2
solubility than PDMS. CO2 can readily diffuse into these
amorphous, liquid silicones because silicones exhibit weak self-
interactions. This makes it easier for the electron-poor carbon of
CO2 to interact with the electron-rich oxygen atom in the
dimethylsiloxane repeat unit, while the electron-rich oxygen
atoms of CO2 interact with the protons on the methyl groups.
Further, PDMS and high-pressure CO2 exhibit comparable
solubility parameters, which are often an indication of mutual
miscibility of the two components.
The remarkable solubility of some nonfluorous, nonsilicone
polymers in CO2 is now considered. Although not as CO2-
soluble as fluoroacrylates or PDMS, there are a handful of
oxygenated polymers that are demonstrably more CO2-soluble
than others. The best examples include high molecular weight
PVAc, high molecular weight amorphous PLA, and low
molecular weight liquid PEO and PPO, highly oxygenated
hydrocarbon polymers that are not rich in acid or hydroxyl
groups. Further, these polymers are high-flexibility, high free
volume, low softening point compounds. These attributes
facilitate the interactions between CO2 and the polymer chain.
In each case CO2 and the repeat unit of the polymer exhibit
more than one favorable thermodynamic interaction; typically,
the carbon of the CO2 interacts with the oxygen atoms within
the polymer (e.g., carbonyls and ethers), while the oxygens of
CO2 interact with protons in the polymer chain.
4.2. Screening Studies. CO2 is a unique solvent; its
molecular structure and solvent strength are not highly
correlated to any single liquid (in contrast to n-pentane, which
is an obvious screening liquid for high-pressure propane because
both are linear saturated alkanes). However, if one is constrained
to use liquids as screening tools, more than one liquid should be
kept on hand. Although the solvent strength of liquid CO2 is
most similar to liquid ethane when one is considering the ability
the dissolve hydrocarbon compounds or extract oil from rock,147
the use of liquid ethane (like CO2) also requires high-pressure
equipment. Therefore, pentane or hexane can be used at
ambient pressure if the thickener is hydrocarbon-based. If the
thickener cannot dissolve in pentane, it will probably not
dissolve in CO2. If the hydrocarbon compound does dissolve in
pentane, then it might dissolve in CO2. Ethyl acetate should be
used to screen thickeners on the basis of oxygenated
hydrocarbons; if an oxygenated hydrocarbon compound will
not dissolve in ethyl acetate it probably will not dissolve in CO2.
If it does dissolve in ethyl acetate, then it may dissolve in CO2.
Hydrofluoroethers (e.g., nonafluorobutyl methyl ether and
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Novec 7100) and hydrofluorocarbons (e.g., decafluoropentane)
are preferred screening liquids for fluorinated thickeners; if the
fluorinated thickener cannot dissolve in the fluorinated liquid, it
will probably not dissolve in CO2. If the fluorinated compound
does dissolve in the fluorinated liquid solvent, then it might
dissolve in CO2. Numerous other solvents have been suggested
as screening fluids for CO2, including isooctane, perfluorohex-
ane, acetone, and acetonitrile.148 In light of these observations,
the best approach for testing thickening candidates is to use only
CO2 at high pressure and forego screening with liquids.
4.3. Solubility and Viscosity Testing. The vast majority of
CO2 thickeners exhibit little, if any, solubility in CO2. Therefore,
it is recommended that the solubility of thickeners in CO2 be
determined by introducing known amounts of thickener and
CO2 to a windowed, agitated, high-pressure vessel that allows
observations of the entire high-pressure sample volume.
Viscosity testing should then be performed at conditions
known to yield a single-phase solution. The viscometer should
be initially charged with neat CO2, and the CO2-thickener
solution should then be pumped into the viscometer (displacing
CO2) at temperature−pressure conditions known to yield a
single-phase solution. If a small, undissolved portion of the
thickener charged to a viscometer becomes lodged in one of
these small gaps found in various high-pressure viscometer
apparatuses (e.g., falling ball, falling cylinder, capillary tube,
vibrating crystal, or vibrating wire), the device may yield a very
high, but incorrect, viscosity value. Capillary viscometers are
particularly prone to this concern, given the long length and
narrow diameter of the capillary. Windowed viscometers should
be used when possible, in order to verify that the thickener is
actually dissolved. If it is not possible to make a windowed
version of the viscometer (e.g., capillary tube), one should
consider putting small, windowed cells at the entrance and exit
of the tubing to confirm that the mixture flowing in/out of the
viscometer is a single-phase solution. Ideally, thickener perform-
ance should be verified carefully in multiple types of viscometers
and in flow-through-porous-media tests, preferably in multiple
laboratories.
4.4. Thickening CO2 Only the First Step: Necessary but
Not Sufficient. The identification of an affordable, safe,
effective CO2 thickener does not ensure that the compound is
suitable for application in the field. For example, the best CO2
thickeners, polyFAST and PFA, are unsuitable for field
application because of high cost, extremely high viscosity in
neat form, and marked wettability alteration that leads to
excessive permeability reduction. In addition to increasing CO2
viscosity, there must be a sufficient commercial supply of the
thickener for a pilot-scale or field-scale test. The thickener
should be in a pumpable form that can be displaced into a CO2
line. After the CO2 and thickener streams are combined, the
mixture should quickly form a single-phase solution as it passes
through static mixers. A high heating/cooling cycle should not
be required for dissolution or thickening. The thickener should
not exhibit excessive adsorption on the surface of porous media
that would lead to poorer process economics and excessively
large reductions in permeability due to wettability alteration. If
the thickener is brine-soluble (which is unlikely given the low
mutual solubility of CO2 and water), the thickener may partition
into the brine within the porous media. If the thickener is crude-
oil-soluble, a portion of the thickener may ultimately
contaminate the crude oil product and potentially cause
problems in downstream processing equipment within refin-
eries. Therefore, any thickener that yields promising solubility
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and viscosity results must still be thoroughly vetted in core tests
prior to being considered for pilot tests.
4.5. Target Thickeners That Can Induce 10−100-fold
Viscosity Increases at Concentrations as Low as 0.1 wt %
for Economic and Logistical Viability. The literature
indicates that substantial increases (at least several-fold) in
viscosity of dense fluids (water, oil, and NGL) typically require
at least ∼0.1 wt % (1,000 ppm) of a thickener; there is no reason
or evidence in the literature to suspect that significantly lower
concentrations would be required to thicken high-pressure CO2.
Low thickener concentrations also favor process economics and
facilitate the logistics of thickener shipping, receiving, transport
to the field, and mixing with CO2. The least expensive thickeners
noted in this review are PVAc and PDMS, which cost on the
order of $1−10 per pound, with higher prices associated with
higher average molecular weights. These polymers are roughly
2−3 orders of magnitude more expensive than CO2 delivered to
an EOR site. Other thickening candidates described in this
report could cost as much as $10−100 per pound. Therefore, it
is incumbent upon future researchers to design or identify a few
novel thickeners that can be effective at roughly several thousand
parts per million without the need for the additional costs of a
cosolvent for use in EOR or CO2 fracturing.149 This ambitious
goal is preferable to pursuing high concentrations of oligomeric
polymers that may only impart very modest viscosity changes
only because their performance is slightly better than other
thickeners found in the literature.
4.6. High Molecular Weight Polymeric Direct Thick-
eners. Because of the relative simplicity of purchasing off-the-
shelf polymers, a remarkable amount of research has already
been published related to polymeric CO2 thickeners. Although
the literature clearly affirms the ability of PFA and polyFAST to
thicken CO2 at reservoir conditions without the need for a
cosolvent, the inherent expense of fluorous monomers prevents
the use of fluoroacrylate-based polymers for EOR or fracturing.
At this time, neither the literature nor our team can offer insight
into how one can enable inexpensive nonfluorinated high
molecular weight polymers (such as PVAc and PDMS) to
dissolve in CO2 without the addition of untenable amounts of
cosolvent. Even nonfluorous polymers such as PAO that were
designed with molecular modeling tools to maximize favorable
thermodynamic interactions with CO2 have not exhibited more
solubility than PVAc. One must also recognize that nonfluorous
polymers can be incredibly expensive if the monomers are
expensive and/or the polymer synthesis has many steps and/or
low polymer yield. Finally, high and ultrahigh molecular weight
polymers will either be solid or incredibly viscous and slow to
dissolve in CO2. Therefore, one would have to either heat the
polymer to very high temperatures and/or add a solvent to
formulate a pumpable liquid that is rich in the polymer (even if
the cosolvent is not necessary to slowly attain dissolution at
equilibrium conditions). Given these challenges and the
multitude of polymer studies that have been completed, in our
opinion the chances of successfully thickening CO2 with very
dilute amounts (i.e., several tenths of a weight percent) of novel,
inexpensive, nonfluorous, high molecular weight polymers are
slim.
4.7. Low Molecular Weight Polymeric Direct Thick-
eners. The most obvious point of contention in the literature is
the exact nature of the effect of non-associating low molecular
weight polymers or oligomers, such as PEVE or P1D with MW
1,000−4,000, or the effect of PDMS MW 5,000−10,000 on the
viscosity of CO2. Some groups, including ours, find little if any
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detectable viscosity enhancement with these polymers. Further,
there is no evidence in the literature that oligomers or low
molecular weight polymers can thicken other solvents, such as
water or oil; without exception, water and oil thickeners are high
or ultrahigh molecular weight polymers. However, other
researchers have recently presented modest thickening results
for these polymers in CO2. Further studies to resolve this dispute
would be an interesting scientific exercise. However, even if
these polymers are demonstrated to slightly thicken CO2 by 50−
100% at concentrations of several weight percent, these
increases are likely to be too modest at concentrations that are
too high for field application.
4.8. Low Molecular Weight Associating Polymers.
Much less work has been reported for smaller associating
polymers (e.g., telechelic ionomers) as CO2 thickeners. This is
probably because lower molecular weight associative polymeric
thickening candidates are scarce and must be designed,
synthesized, purified, and characterized by the investigators
prior to conducting solubility and viscosity testing. Each of these
steps can be quite challenging. Further, this type of thickener is
likely to be solid or an extremely viscous liquid in pure form and,
therefore, present the same logistical and mixing challenges as
high molecular weight polymers. Nonetheless, there are many
opportunities to explore novel low molecular weight associating
polymers. There are several oligomers that are known to be
soluble in CO2 (e.g., PDMS, PVAc, PVEE, P1D, PEO, PPO, and
oligomers of CTA). These oligomers can be end-functionalized
or functionalized along the polymer backbone with known CO2-
phobic associating groups (e.g., benzene, naphthalene, anthra-
cene, carboxylic acids, and ionic groups). However, there is a
fundamental challenge associated with the molecular design of
functionalized oligomers. If one selects slightly CO2-phobic
associating groups (e.g., naphthalene), the CO2 solubility of the
thickening candidate will increase; however, the intermolecular
interactions between the end groups may be so weak that a
viscosity-enhancing supramolecular structure does not form.
However, if a highly CO2-phobic, strongly associating terminal
group is chosen, the thickener candidate may be CO2-insoluble.
Relatively few studies of nonfluorous associating low molecular
weight polymers have been published,16,150 and there are many
other potential candidates.
4.9. Small-Molecule Associative Thickeners. The most
notable attribute of several small-molecule associative oil
thickeners (e.g., tributyltin fluoride, cross-linked phosphate
esters, hydroxyaluminum di(2-ethylhexanoate), and 12-hydrox-
ystearic acid) is their remarkable ability to increase viscosity
dramatically at very low concentrations. However, each of these
molecules is CO2-insoluble. Further, all of the reported
modifications in their structure intended to enhance CO2
solubility have been shown to not increase solubility and/or
induce steric hindrances that diminish their ability to self-
assemble into viscosity-enhancing structures. Additionally, most
small-molecule associative thickeners are solids that are difficult
to dissolve in a solvent, often requiring extensive mixing and/or
a heating/cooling cycle.
However, novel highly CO2-philic cross-linked phosphate
esters (CPE) appear to be the most promising small-molecule
associative thickening candidates for future studies. CPEs have
been used commercially to thicken various light alkanes for
waterless hydraulic fracturing. CPE is delivered as two, low-
viscosity liquids: a blend of phosphate esters that is highly
soluble in the hydrocarbon and an acidic solution containing a
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trivalent metal ion cross-linker. These two liquids are readily
pumped into the high-pressure liquid hydrocarbon. The
phosphate esters dissolve quickly in the hydrocarbon. The
acidic cross-linking solution can be easily dispersed in the
hydrocarbon−phosphate ester solution. The trivalent metal ions
are rapidly chelated by the phosphate esters in the hydrocarbon
phase, establishing a weblike supramolecular CPE network that
if it remains in solution (which is a big “if”), quickly induces
remarkably high viscosity increases. A CPE-thickened hydro-
carbon liquid may appear transparent, or it may appear to be
hazy if the droplets of acidic solution do not fully dissolve in the
CPE-thickened hydrocarbon. The literature demonstrates that
one can tailor the structure of the phosphate ester structure to
optimize the thickening of specific hydrocarbons. For example,
short alkyl chains (C3−C5) should be used in the synthesis of
the phosphate esters used to gel propane, while longer chain
alkyl groups can be used for the phosphate esters intended to
thicken oils. However, we have found no evidence in the
literature that an attempt has been made to tailor the structure of
the phosphate esters to exhibit high solubility, especially after
cross-linking, in CO2. Instead, several groups (including our
own) have simply tested the commercially available formula-
tions designed for propane, NGL, Y-grade solvent, or mineral oil
in hopes that one of the two-component formulations would
thicken CO2. None do. Although the phosphate esters are highly
CO2-soluble, the addition of the cross-linking solution results in
the immediate precipitation of the CPE network. Therefore,
very high concentrations of cosolvent (e.g., ∼50% hexanes, 50%
CO2) are required to thicken a CO2-rich liquid mixture with a
conventional CPE thickener. Novel phosphate esters could
incorporate highly CO2-philic moieties, such as sugar acetates,
oligomers of propylene oxide, or oligovinyl acetate in the
phosphate ester rather than alkyl groups. However, these
oxygenated hydrocarbon functional groups are bulkier than
short alkyl groups, which may result in steric hindrance to cross-
linking. Further, once the phosphate esters are cross-linked,
there remains a risk that the cross-linked network will still
precipitate even though more CO2-philic tails were used in the
phosphate ester.
Although there has been great success in the design of
surfactants capable of forming viscosity-enhancing wormlike
micelles in water and oil, the only successes in thickening CO2
with elongated micelles have been achieved with high
concentrations of fluorinated ionic surfactants that form
ellipsoidal micelles that induce modest increases in viscosity.
Thickening CO2 with a surfactant(s) is particularly challenging
because the composition of the CO2-phobic heads and CO2-
philic tails must be able to simultaneously induce CO2 solubility
while inducing steric effects that favor the formation of
extremely long wormlike micelles. Slight changes in the structure
that can enhance CO2 solubility, such as the inclusion of highly
CO2-philic tails, may disrupt the formation of long viscosity-
enhancing micelles, but tails that are designed to promote the
formation of long micelles may reduce CO2 solubility. Some
dramatic thickening results have been reported in the literature,
but they are usually associated with vague descriptions (or a
complete lack of description) of the purported surfactant.
4.10. Indirect Thickening with Waterless C/O Emul-
sions and Foams. It is possible to indirectly thicken CO2 by
generating thermodynamically unstable, high-quality, CO2-in-
oil foams or emulsions that have a high apparent viscosity (i.e.,
low mobility) before they collapse. The surfactant is unlikely to
be a commercial product because most commercial surfactants
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(whether oil-soluble or water-soluble) contain an ionic or non-
ionic hydrophile. However, the C/O emulsion stabilizer would
be composed of two hydrophobic segments, one being CO2-
philic and at least slightly oil-phobic (e.g., sugar acetates,
relatively low molecular weight PMDS, or oligomers of vinyl
acetate or propylene oxide), while the other is oil-philic and at
least slightly CO2-phobic (e.g., C30+). The surfactant used to
stabilize C/O emulsions must be more oil-soluble than CO2-
soluble according to Bancroft’s rule, which is fortunate because it
is much easier to design an oil-soluble surfactant than a CO2-
soluble surfactant. Several commercially available compounds,
such as poly(trimethylhydrosilylsiloxane), may provide a
reasonably stable emulsion. Only one highly effective C/O
emulsion stabilizing surfactant has been identified to date: a
novel alkyl(C30)-silicone copolymeric surfactant. The resultant
waterless C/O emulsions and foams can exhibit high apparent
viscosity and prolonged periods of stability. However, because
C/O emulsions contain a large proportion of an oil that is not
CO2-miscible (e.g., mineral oil), they can only serve as CO2-rich
alternative fluids for the niche market of fracturing water-
sensitive formations with a hydrocarbon-based fluid such as
mineral oil, solutions of CO2 in mineral oil, Y-grade, propane, or
NGL. These waterless foams would not be useful or
economically viable for CO2 mobility control in conventional
formations because they would not be able to compete with the
much less expensive CO2-in-water foams.
4.11. Dispersed Nanoparticles as Thickeners. Very few
attempts to increase the apparent viscosity of CO2 using
dispersed, surface-functionalized nanoparticles have been
reported. A relatively high concentration (∼2−8 wt %) of a
nanocomposite composed primarily of high molecular weight
P1D and a small proportion of graphene oxide (GO) particles
was recently reported to thicken CO2.5 However, no details of
the falling ball viscometer were provided and no explanation of
how high molecular weight P1D (600,000) was CO2-soluble
while other researchers indicated that only very low molecular
weight P1D (<1,000) could dissolve in CO2. The first step in
future studies of nanoparticle dispersions in CO2 should be the
design and synthesis of nanoparticles (e.g., silica) that are
surface-functionalized with nonfluorous, highly CO2-philic
groups (e.g., oligovinyl acetate, sugar acetates, and oligomers
of propylene oxide). An attempt should then be made to
disperse these nanoparticles (∼1 wt %) in high-pressure CO2
such that a stable, transparent “solution” is attained, rather than a
turbid unstable dispersion of nanoparticle aggregates. Sub-
sequently, the concentration of the NP should be increased to
determine the “solubility” of these NPs in CO2 at a specified
temperature and pressure. Then the viscosity of the dispersion of
nanoparticles in CO2 should be studied to determine if
substantive increases in viscosity can be realized. If these
dispersions are intended for mobility control, then the apparent
viscosity of the dispersion should be assessed in flow-through-
porous-media experiments to verify that the NPs (and any other
particles that may be introduced such as graphene oxide) can
propagate through the micrometer-scale pores of sandstone or
carbonate rock.
5. CONCLUSIONS
PolyFAST and PFA remain the only verifiable CO2 thickeners
that dissolve in neat CO2 at conditions associated with EOR.
PolyFAST is particularly effective, where high molecular weight
versions that contain the proper proportion of styrene (21 mol
%) are able to induce a 138-fold increase in CO2 viscosity at 4 wt
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%, while PFA addition at the same concentration resulted in only
a 3−5-fold increase. However, it has been recently demonstrated
that these fluoroacrylate-rich polymers are likely to adsorb
significantly onto sandstone or carbonate rock.84 Further, both
materials are inherently expensive and there are concerns about
the toxicity of hydrolysis degradation products associated with
these polymers, particularly if they contain eight fluorinated
carbons in the fluoroacrylate monomer. Although these
environmental concerns can be mitigated by using fluoroacrylate
monomers with short, fluorinated segments (e.g., -C6F13 and
-C4F9), it remains unlikely that either polyFAST or PFA could
be used in a large-scale EOR or hydraulic fracturing operation.
High molecular weight PDMS is also a well substantiated CO2
thickener, although a substantial amount of toluene cosolvent
(e.g., 23 wt %) is required to attain dissolution at EOR
conditions, as has been noted since the first reports on its
evaluation in the early 1990s.32,34 A 4−6-fold increase in CO2
viscosity was realized using 2 wt % PDMS (MW 500,000) and
toluene cosolvent. This degree of thickening is comparable to
that attained with 4 wt % PFA. Although we were not able to
assess them in this study, it would not be surprising that recently
reported variants of silicone oil would also have the potential to
thicken CO2 if a cosolvent was used for polymer dissolution.
High molecular weight PVAc (MW 500,000) remains the
most technically and economically viable oxygenated hydro-
carbon-based polymer capable of thickening CO2. However, like
PDMS, a large amount of cosolvent (e.g., 23 wt % toluene) is
required to permit PVAc to dissolve in CO2 at EOR conditions.
The addition of 2 wt % PVAC and toluene resulted in a 70%
increase in CO2 viscosity.
Although PVEE and P1D have received a good deal of recent
attention, our results are more in line with the earlier results of
Heller and co-workers concerning the efficacy of low molecular
weight oligomers.6 Both PVEE and P1D appear to be very
modest CO2 thickeners. Further, no literature was found in
which low molecular weight, non-associating polymers in dilute
concentration were used to thicken any other fluid, including
water or oil. Although no increase in viscosity was measured
when PVEE was dissolved in CO2 in the absence of a cosolvent, a
30% increase in CO2 viscosity was achieved with PVEE when
toluene was added. This suggests that a portion of the thickening
may be attributable to the presence of the cosolvent and/or the
ability of the cosolvent to cause the P1D to swell more
significantly. No significant increase in viscosity was observed
with the falling object viscometer for P1D, although this material
did not require a cosolvent for dissolution in CO2. These results,
coupled with the absence of any literature verifying that dilute
concentrations of oligomers or low molecular weight can thicken
water or oil, suggest that CO2 thickening using low molecular
weight non-associating oligomers is unlikely to result in a
significant degree of CO2 thickening.
The ionic surfactant AOT was soluble in CO2 only when a
substantial amount of ethanol was introduced as a cosolvent.
The resultant solution was 2.5 times more viscous than CO2, in
good agreement with the claims in the literature.118 However, an
80:20 CO2:ethanol (%) solution at the conditions listed in Table
1 is 1.7 times more viscous than pure CO2. Therefore, the AOT
has apparently self-assembled into micelles that further increase
relative viscosity.
The two low-viscosity liquids (phosphate ester mixture; acidic
trivalent ion solution) that are known to quickly thicken liquid
propane or LPG at very low concentration apparently require a
very substantial amount of alkane cosolvent to dissolve in CO2.
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Energy & Fuels
The 25:75 hexane:CO2 (%) solution used in this work was
incapable of keeping the cross-linked network in solution. It
appears that a CO2−alkane solution containing closer to 50%
alkanes is required104 to thicken CO2.
Ethylene glycol was soluble in CO2; however, it did not yield a
detectable viscosity increase. Hydroxyaluminum di(2-ethyl-
hexanoate), tributyltin fluoride, and 12-hydroxystearic acid
(12HSA) were insoluble in CO2, even in the presence of 23 wt %
cosolvent. The 12HSA−toluene−CO2 mixture did form an
opaque gel that filled the cell; upon the subsequent removal of
CO2 via depressurization at constant volume, a soft, monolithic,
freestanding fibrous foam of 12HSA fibers laden with toluene
remained in the cell.
The sample of PSM mixture that we received, described as a
“mixture of allyl ethers, acrylate, acrylic long carbon chain esters/
benzenes, propylene carbonate/allyl ethyl carbonate, dimethyl
carbonate, and white oil/silicon or oil/petroleum ether”,83 was
insoluble in CO2. However, prolonged mixing with CO2 led to
the establishment of a coarse CO2-in-oil emulsion of millimeter-
sized CO2 droplets that filled most of the sample volume
(although undissolved solid was clearly observed). This
undissolved material prevented the free fall of the cylinder,
and therefore the apparent viscosity of the CO2-in-oil emulsions
could not be determined. On the basis of our recent study of oil-
soluble silicone−alkyl polymeric surfactants capable of quickly
stabilizing CO2-in-mineral oil waterless emulsions, this type of
rarely reported waterless, high-quality (i.e., volume fraction
CO2) emulsion that we observed by mixing PSM with CO2 may
indeed exhibit a high apparent viscosity. Therefore, although the
sample of PSM that we received is not a direct CO2 thickener, it
has the potential to be an indirect CO2 thickener that forms a
completely waterless CO2-in-oil emulsion.
With regard to novel, future research directions, there appear
to be few promising avenues related to CO2−polymer solutions
given the profound amount of work that has been completed in
this area. There is little chance that dilute concentrations of non-
associating oligomers can thicken CO2 (or any other fluid) in
dilute concentration. However, there are many novel designs of
lower molecular weight associating polymers containing two or
more CO2-phobic associating groups that can be explored, such
as benzene-ring-functionalized oligomers of CO2 -philic
oligomers. With regard to small associating molecules, although
phosphate esters with alkyl tails are soluble in CO2, the cross-
linked phosphate ester network is CO2-insoluble. The design of
phosphate esters with highly CO2-philic tails (perhaps sugar
acetates) has not been reported and could lead to a viscosity-
enhancing CO2-soluble cross-linked phosphate ester network.
In our opinion, this is the most promising avenue for CO2
thickener development. High apparent viscosity C/O emulsions
can be stabilized (for many hours to a few days without mixing)
with CO2-soluble nonfluorous, completely, hydrophobic
surfactants. However, this C/O emulsion must contain a high
proportion of an oil that is not miscible with CO2; therefore such
emulsions would be of interest only as alternate fracturing fluids
for highly water-sensitive unconventional formations in which
C/W foams could not be used. There have been a few reports of
stable nanoparticle dispersions in CO2 and a single report of an
apparent increase in CO2 viscosity. However, future research in
this area should begin with a thorough investigation of silica
nanoparticles that are surface-functionalized with nonfluorous
highly CO2-philic ligands. If these nanoparticles can be
dispersed in high-pressure CO2, the apparent viscosity of the
pubs.acs.org/EF Review
dispersion should be measured and the ability of the dispersion
to propagate through porous media should be verified.
■ AUTHOR INFORMATION
Corresponding Author
P. C. Lemaire − Department of Chemical and Petroleum
Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania
15213, United States; orcid.org/0000-0002-8716-0466;
Email: pcl10@pitt.edu
Authors
A. Alenzi − Department of Chemical and Petroleum
Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania
15213, United States; Department of Chemical Engineering
Technology, College of Technological Studies (PAAET),
15460 Dasman, Kuwait
J. J. Lee − Department of Chemical and Petroleum Engineering,
University of Pittsburgh, Pittsburgh, Pennsylvania 15213,
United States
E. J. Beckman − Department of Chemical and Petroleum
Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania
15213, United States; orcid.org/0000-0002-9958-3589
R. M. Enick − Department of Chemical and Petroleum
Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania
15213, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.1c00314
Notes
Disclosure. This report was prepared as an account of work
sponsored by an agency of the United States Government.
Neither the United States Government nor any agency thereof,
nor any of their employees, makes any warranty, express or
implied, or assumes any legal liability or responsibility for the
accuracy, completeness, or usefulness of any information,
apparatus, product, or process disclosed, or represents that its
use would not infringe privately owned rights. Reference herein
to any specific commercial product, process, or service by trade
name, trademark, manufacturer, or otherwise does not
necessarily constitute or imply its endorsement, recommenda-
tion, or favoring by the United States Government or any agency
thereof. The views and opinions of authors expressed herein do
not necessarily state or reflect those of the United States
Government or any agency thereof.
The authors declare no competing financial interest.
Biographies
Peter Lemaire received his B.S. degree in Chemical Engineering from
Carnegie Mellon University in 2016 and is currently pursuing a Ph.D.
degree in Chemical Engineering at the University of Pittsburgh under
Dr. Robert Enick. His research focuses on synthesis and character-
ization of fluorinated polymers for wellbore integrity and CO2
thickening.
Adel Alenzi received his B.Sc. degree in Chemical Engineering from
University of MissouriColumbia in 1996 and his Ph.D. degree in
Chemical Engineering from University of Pittsburgh in 2012. He joined
the Department of Chemical Engineering Technology at the College of
Technological Studies in Kuwait in 2012. Then, he was appointed as the
Department Chair in 2015−2019. His research work focuses on
multiscale, multiphase transport phenomena, and incrustation
phenomena and crystallization in liquid−solid systems.
Jason Lee earned a B.S. in chemical engineering from the University of
Rochester in 2010 and a Ph.D. in chemical engineering from the
8535 https://doi.org/10.1021/acs.energyfuels.1c00314
Energy Fuels 2021, 35, 8510−8540
Energy & Fuels
University of Pittsburgh in 2016. He is currently the lead process design
engineer at Thar Process in Pittsburgh, PA, where he specializes in
large-scale preparative supercritical fluid chromatography equipment
design. Outside of chemical engineering, he also owns and operates
Graduate Audio, a small music electronics design and repair business.
Eric J. Beckman received a B.S. in chemical engineering from
Massachusetts Institute of Technology (MIT) and a Ph.D. in Polymer
Science & Engineering from the University of Massachusetts in 1988.
He joined the University of Pittsburgh in 1989, becoming Associate
Professor in 1994 and Full Professor in 1998. His research interests
include molecular design to address issues in sustainability and
biomedical engineering; his research group has published over 200
papers, and he has received over 40 U.S. patents.
Robert M. Enick received B.S., M.S., and Ph.D. degrees in Chemical
Engineering and an M.S. in Petroleum Engineering from the Chemical
and Petroleum Engineering Department at the University of Pittsburgh,
where he subsequently joined the faculty in 1985. He served as
department chair and is currently Vice Chair for Research. He received
a 2020 SPE IOR Pioneer Award and has served as an ORISE Faculty
Fellow at the U.S. DOE National Energy Technology Laboratory.
■
ACKNOWLEDGMENTS
We express our appreciation to Linde plc and Dr. Richard Kelly,
Energy Applications R&D, Linde Technology Center, for many
useful suggestions and productive discussions related to
molecular design and practical aspects of thickening CO2. We
thank Dr. Frank Adamsky and Shinsuke (Sonny) Ohshita of
Daikin America for the provision of fluoroacrylate monomer
samples, PFA characterization, and many useful discussions
regarding the properties and attributes of PFA. This material is
based upon work supported by the Department of Energy under
Award No. DE-FE0026825.
■
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