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Beckman, Eric

Publications and source records attributed to Beckman, Eric.

Using high pressure solutions of polyfluoroacrylate and CO 2 to Seal cement cracks for improved wellbore integrity

Polyfluoroacrylate (PFA) is a hydrophobic and oleophobic polymer that is soluble in high pressure carbon dioxide (CO 2 ). In this study, the ability of PFA-CO 2 solutions to greatly reduce the apparent permeability of split or cracked Portland cement cylindrical samples is assessed. The apparent permeability values of confined samples were determined before and after treatment with PFA-CO 2 solutions. In four tests, PFA-CO 2 solutions were continuously displacing pure CO 2 from the cracked cement and the decrease in apparent permeability due to PFA adsorption and wettability alteration was monitored. The lowest apparent permeability cracked cement sample (81 nD) was completely sealed with a very small amount of solution. Samples with initial apparent permeabilities of 89 μD and 29.4 mD exhibited 92% and 99% reductions in permeability, respectively, before the experiments had to be stopped because of the excessively large increase in pressure drop. A 50% reduction in apparent permeability was observed with a 3.80 mD sample. Four other split cement samples (bound together with tape) with an initial apparent permeability in the 9.0–70 mD range were removed from the core holder and immersed in a PFA-CO 2 solution for 24 h to allow for PFA adsorption. Then the PFA-CO 2 solution was depressurized, allowing for the deposition of additional PFA from the solution within the crack as the pressure fell below the cloud point pressure of the PFA-CO 2 solution. These four samples were then confined again in a core holder and apparent permeability reductions of 29–93% were observed. Finally, results from these eight experiments indicates that the more substantial reductions in the nD – mD apparent permeability of the cracked cement correlated to lower initial crack permeability, higher PFA concentration, and slower injection rate of the PFA-CO 2 solution into the crack.

58 GEOSCIENCES↗

Mixtures of CO 2 and poly(fluoroacrylate) based on monomers containing only six or four fluorinated carbons: Phase behavior and solution viscosity

In this study, homopolymerization of fluoroacrylate monomers containing a segment with eight fluorinated carbons, (CH 2 CHCOO(CH 2 ) 2 (CF 2 ) 7 CF 3 ), yield poly(fluoroacrylate) (PFA) with remarkably high solubility in CO 2 , but the corresponding ultimate PFA degradation product perfluorooctanoic acid (PFOA) is bio-accumulative. Based on cloud point loci in the 1–4 wt% PFA in CO 2 concentration range at temperatures of 25, 50, 75, 100 and 125°C, it is shown that C 6 F 13 -based and C 4 F 9 -based PFA, with relatively benign degradation products perfluorohexanoic acid (PFHxA) and perfluorobutanoic acid (PFBA), respectively, retain the same level of CO 2 -solubility as that of C 8 F 17 -based PFA. Further, both C 6 F 13 -based and C 4 F 9 -based PFA can increase the viscosity of single-phase CO 2 -PFA solutions (i.e. thicken CO 2 ) as much as C 8 F 17 -based PFA in the 25–125°C range. Therefore, the design of CO 2 -soluble PFA need not be constrained to monomers containing the C 8 F 17 moiety; fluoroacrylate monomers containing shorter fluoroalkyl segments with only four or six fluorocarbons can be utilized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Method of fracking using silicone surfactants

Methods for fracking, particularly dry fracking, comprising the use of surfactants for preparation of substantially water-free carbon dioxide in oil foams are presented.

02 PETROLEUM↗

Carbon dioxide-in-oil emulsions stabilized with silicone-alkyl surfactants for waterless hydraulic fracturing

The design of surfactants for CO 2 /oil emulsions has been elusive given the low CO 2 -oil interfacial tension, and consequently, low driving force for surfactant adsorption. Here our hypothesis is that waterless, high pressure CO 2 /oil emulsions can be stabilized by hydrophobic comb polymer surfactants that adsorb at the interface and sterically stabilize the CO 2 droplets. The emulsions were formed by mixing with an impeller or by co-injecting CO 2 and oil through a beadpack (CO 2 volume fractions (φ) of 0.50–0.90). Emulsions were generated with comb polymer surfactants with a polydimethylsiloxane (PDMS) backbone and pendant linear alkyl chains. The C 30 alkyl chains are CO 2 -insoluble but oil soluble (oleophilic), whereas PDMS with more than 50 repeat units is CO 2 -philic but only partially oleophilic. The adsorbed surfactants sterically stabilized CO 2 droplets against Ostwald ripening and coalescence. The optimum surfactant adsorption was obtained with a PDMS degree of polymerization of ~88 and seven C 30 side chains. The emulsion apparent viscosity reached 18 cP at a φ of 0.70, several orders of magnitude higher than the viscosity of pure CO 2 , with CO 2 droplets in the 10–150 µm range. These environmentally benign waterless emulsions are of interest for hydraulic fracturing, especially in water-sensitive formations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regenerable solid imine sorbents

Two new classes of amine-based sorbents are disclosed. The first class comprises new polymer-immobilized tertiary amine sorbents; the second class new polymer-bound amine sorbents. Both classes are tailored to facilitate removal of acid anhydrides, especially carbon dioxide (CO.sub.2), from effluent gases. The amines adsorb acid anhydrides in a 1:1 molar ratio. Both classes of amine sorbents adsorb in the temperature range from about 20.degree. C. upwards to 90.degree. C. and can be regenerated by heating upwards to 100.degree. C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗