Shaohua Gou

A water-soluble antimicrobial acrylamide copolymer containing sulfitobetaine for enhanced oil recovery

Herein, we report a novel acrylamide copolymer with antimicrobial property as an enhanced oil recovery chemical. The copolymer was synthesized from acrylamide (AM), acrylic acid (AA) and 2-((2-(acryloyloxy)ethyl)dimethylammonio)ethyl sulfite (ADMES) using oxidation–reduction initiation system. Subsequently, the copolymer AM/AA/ADMES was evaluated and characterized on several aspects such as IR, 1H NMR, intrinsic viscosity, and dissolubility. The AM/AA/ADMES solution exerted remarkable thickening ability, salt tolerance ability and viscoelasticity. In addition, the rheological properties, temperature resistance ability and long-term stability of AM/AA/ADMES were investigated systematically in the presence of sulfate-reducing bacteria and relatively low viscosity loss could be obtained compared to partially hydrolyzed polyacrylamide. On the basis of core flooding experiments, AM/AA/ADMES was found to be a valuable prospect with 10.5 resistance factor, 4.6 residual resistance factor and up to 11.0% enhanced oil recovery.

A novel water-soluble hydrophobically associating polyacrylamide based on oleic imidazoline and sulfonate for enhanced oil recovery

3-(2-(2-Heptadec-8-enyl-4,5-dihydro-imidazol-1-yl)ethylcarbamoyl)acrylic acid (NIMA), 3-(diallyl-amino)-2-hydroxypropyl sulfonate (NDS), acrylamide (AM) and acrylic acid (AA) were successfully utilized to prepare novel acrylamide-based copolymers (named AM/AA/NIMA and AM/AA/NDS/NIMA) which were functionalized by a combination of imidazoline derivative and/or sulfonate via redox free-radical polymerization. The two copolymers were characterized by infrared (IR) spectroscopy, 1H nuclear magnetic resonance (1H NMR), viscosimetry, pyrene fluorescence probe, thermogravimetry (TG) and differential thermogravimetry (DTG). As expected, the polymers exhibited excellent thickening property, shear stability (viscosity retention rate 5.02% and 7.65% at 1000 s−1) and salt-tolerance (10 000 mg L−1 NaCl: viscosity retention rate up to 17.1% and 10.2%) in comparison with similar concentration partially hydrolyzed polyacrylamide (HPAM). The temperature resistance of the AM/AA/NDS/NIMA solution was also remarkably improved and the viscosity retention rate reached 54.8% under 110 °C. According to the core flooding tests, oil recovery could be enhanced by up to 15.46% by 2000 mg L−1 of the AM/AA/NDS/NIMA brine solution at 80 °C.

Biodegradable polyethylene glycol-based ionic liquids for effective inhibition of shale hydration

A series of ionic liquids based on polyethylene glycol (PEG) with different molecular weights were prepared for inhibiting shale hydration and swelling. The antiswelling ratio was measured to investigate the effect of different PEG-based ionic liquids on bentonite volume expansion, and it has shown that the ionic liquid based PEG200, i.e. PEG with molecular weight of 200, exhibited superior inhibition. The structures of the PEG200-based ionic liquids were characterized by 1H NMR studies. The XRD results indicated that the PEG200-based ionic liquids intercalated into sodium montmorillonite (Na-MMT) reducing the water uptake by the clay. The formation of complexes of Na-MMT and PEG200-based ionic liquids was also verified by FTIR spectroscopy. Thermal degradation analysis suggested that the PEG200-based ionic liquids accessed the interlamellar spaces of Na-MMT and reduced the water content of the complexes obtained. Moreover, no breaks and collapse were observed on the shale samples after immersion in PEG200-based ionic liquid solutions. All the PEG200-based ionic liquids showed biodegradability and potential application in effective inhibition for clay hydration.

A novel α-aminophosphonic acid-modified acrylamide-based hydrophobic associating copolymer with superb water solubility for enhanced oil recovery

As a non-renewable resource, the rational exploitation of oil has attracted a large amount of attention. Among many methods for enhanced oil recovery, polymer flooding is the most suitable method of chemical flooding for non-marine reservoirs and therefore various modified acrylamide-based copolymers have been studied. In this study, a novel α-aminophosphonic acid-modified hydrophobic associating copolymer was successfully synthesized by copolymerization of acrylamide, acrylic acid, N-allyldodecanamide and 1-(dimethylamino)allylphosphonic acid. The copolymer was characterized by FT-IR, 1H NMR and thermogravimetry and exhibited superior water solubility and thickening capability. Subsequently, the shear resistance, temperature resistance and salt tolerance of the copolymer solution were investigated. The value of apparent viscosity retention of a 2000 mg L−1 copolymer solution was as high as 58.55 mPa s at a shear rate of 170 s−1 and remained at 40.20 mPa s at 120 °C. The values of apparent viscosity retention of 55.41 mPa s, 59.95 mPa s and 52.97 mPa s were observed in solutions of 10 000 mg L−1 NaCl, 1200 mg L−1 MgCl2, and 1200 mg L−1 CaCl2, respectively. These were better than those of partially hydrolyzed polyacrylamide under the same conditions. In addition, an increase of up to 14.52% in the oil recovery rate compared with that for water flooding could be achieved in a core flooding test using a 2000 mg L−1 copolymer solution at 65 °C.

Water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration

Here, we report water-soluble complexes of an acrylamide copolymer and ionic liquids for inhibiting shale hydration. The copolymer, denoted as PAAT, was synthesised via copolymerisation of acrylamide (AM), acrylic acid (AA) and N,N-diallyl-4-methylbenzenesulfonamide (TCDAP), and the ionic liquids used were 3-methyl imidazoliumcation-based tetrafluoroborates. X-ray diffraction showed that compared with commonly used KCl, the water-soluble complex of PAAT with 2 wt% ionic liquid 1-methyl-3-H-imidazolium tetrafluoroborate (HmimBF4) could remarkably reduce the d-spacing of sodium montmorillonite in water from 19.24 to 13.16 A and effectively inhibit clay swelling. It was also found that the PAAT–HmimBF4 complex with 2 wt% HmimBF4 could retain 75% of the shale indentation hardness and increase the anti-swelling ratio to 85%. 13C NMR revealed that there existed interactions between PAAT and HmimBF4. Moreover, the thermal stability of the PAAT–HmimBF4 complex is superior to PAAT, suggesting that this water-soluble complex can be used to inhibit clay and shale hydration in high-temperature oil and gas wells.

Thermally stable imidazoline-based sulfonate copolymers for enhanced oil recovery

Novel imidazoline-based sulfonate copolymers (noted PAMDSCM and PAMPSCM) were successfully prepared by copolymerization of acrylamide (AM), acrylic acid (AA), 1-acrylamido ethyl-2-oleic imidazoline (ACEIM) with the sodium salts of 3-(diallyl-amino)-2-hydroxypropyl (NDS) or 2-acrylamido-2-methylpropane sulfonic acid (AMPS), respectively. The copolymers were characterized by infrared (IR) spectroscopy, 1H nuclear magnetic resonance (1H NMR) spectroscopy, pyrene fluorescence probe spectroscopy, viscosimetry and thermogravimetry (TG). Both PAMDSCM and PAMPSCM copolymers had excellent high-temperature tolerance in comparison with the same concentration of HPAM, and the residual viscosities were 32.0 mPa s and 31.3 mPa s (viscosity retention rates were 38.8% and 37.1%) at 140 °C, respectively. The copolymers possessed superior long-term thermal stability and their residual viscosity rates were up to 81.8% and 63.8% (52.9 mPa s and 47.1 mPa s) lasting 1.5 hours at 100 °C and 170 s−1, respectively.

An anti-biodegradable hydrophobic sulfonate-based acrylamide copolymer containing 2,4-dichlorophenoxy for enhanced oil recovery

We report here a novel anti-biodegradable hydrophobic acrylamide copolymer that was prepared from acrylamide, acrylic acid, sodium 3-(allyloxy)-2-hydroxypropane-1-sulfonate and N-allyl-2-(2,4-dichlorophenoxy) acetamide using the 2,2′-azobis(2-methylpropionamide) dihydrochloride initiation system. Subsequently, the copolymer was characterized by FT-IR, 1H NMR, TG-DTG and water-solubility. And the biodegradability test indicated that the copolymer was not deemed to be readily biodegradable via a closed bottle test established by the Organization for Economic Co-operation and Development (OECD 301 D). Meanwhile the copolymer could significantly enhance the viscosity of the aqueous solution in comparison with partially hydrolyzed polyacrylamide. A viscosity retention of 51.9% indicated the result of a dramatic improvement of temperature tolerance. And then the excellent salt resistance, shear resistance, viscoelasticity, long-term stability of the copolymer could be obtained, which provides a good theoretical foundation for the application in enhanced oil recovery. In addition, this copolymer exerted stronger mobility control ability with a resistance factor of 22.1 and a residual resistance factor of 5.0, and superior ability for enhanced oil recovery of 12.9%. Hence, the copolymer has potential application for enhanced oil recovery in high-temperature and high-salinity reservoirs.

Comb-shaped polyzwitterion with surface-activity obtained via N-maleoyl chitosan-modified HPAM for displacement of residual oil

Herein, a novel water-soluble comb-shaped polyzwitterion (PNMASt) was prepared by introducing N-maleoyl chitosan, 2-(dimethyl(5-methyl-4-oxohex-5-en-1-yl)ammonio)ethyl sulfite, and other hydrophilic hydrophobic monomers into HPAM via free-radical copolymerization. Chemical structure determination and heat endurance analysis were accomplished via XRD, FTIR and 1H-NMR spectroscopy, SEM, and TGA. A simulated reservoir environment (shear rates, temperature, and salinity) was used to survey the solution performance and the rheology of the polyzwitterion as a function of the apparent viscosity and changing conditions. PNMASt exhibited excellent thickening efficiency, surface activity, anti-shear behavior, restorable action after shearing, heat tolerance, ageing tolerance, viscoelasticity, and salt tolerance as compared to HPAM under the same simulation environment. Furthermore, a core flooding experiment showed the remarkable flow control capability (Rf = 18.23 and RRf = 6.62), excellent oil production enhancement (13.32%), and remarkable residual oil displacement capacity (6.11%) of PNMASt as compared to those of HPAM.

Amidoxime-modified chitosan for pigment red 224 enrichment through reversible assembly

A new amidoxime-modified material, firstly investigated for the treatment of dye wastewater, was synthesized by the copolymerization of N-(2-methyl-1-oxo-2-propen-1-yl)chitosan (MAc-CTS) and acrylonitrile (AN), and then amidoximation. A regeneration experiment with pigment red 224 showed that the adsorption capacity of the material for pigment red 224 is up to 315.79 mg g−1 at 10 °C with fewer than 10–15 oscillations. Also, the sorbent exhibited good reusability. The amidoxime-based polymer possess a potential application for the treatment of wastewater containing pigment red 224.