Manganese Assisted Waterflooding Processes for Enhanced Oil Recovery in Carbonates

Modifying the wettability of carbonate formations through divalent foreign metal incorporation can become a cost-effective practical method for enhanced oil recovery (EOR) applications. The addition of manganese ions to both high salinity water (HSW) and tailored SmartWater at dilute concentrations is exploited in this study to maximize the interfacial potential and promote water-wet conditions in carbonate reservoirs. In this experimental investigation, the impact of manganese ions on zeta-potentials at calcite/brine and crude oil/brine interfaces is first determined by measuring zeta-potentials in calcite suspensions and oil emulsions. Two different water chemistries representative of HSW (~60,000 ppm TDS) and a low salinity tailored SmartWater (~6,000 ppm TDS) were used. The measurements were then extended to carbonate rocks and reservoir cores by performing contact angle and spontaneous imbibition tests at reservoir conditions. The oil-water interfacial tensions are also measured to understand the interactions of manganese ions at the oil/brine interface. The zeta potential results showed a positive consistent trend, with the addition of 100-1,000 ppm of Mn+2 ions in the form of MnSO4 to the high salinity water, to impact the wetting transition towards water-wet conditions in carbonates. The addition of Mn+2 ions at a concentration of 100-1,000 ppm to HSW enhanced the electrokinetic interactions to favorably alter surface charges at both oil/brine and calcite/brine interfaces. These findings based on eletrokinetic interactions demonstrated good agreement with contact angle data wherein manganese ions in HSW were able to drastically decrease the contact angles from 156 to 88°. Conversely, insignificant changes in oil-water interfacial tensions were observed due to manganese ions. The manganese assisted spontaneous imbibition oil recoveries were increased by about 10% in HSW. Mn+2 ions showed the ability to increase the negative potentials at both calcite/brine and oil/brine interfaces. The obvious trend of such enhanced electrical potential due to Mn+2 addition at the calcite interface supports the claim that Mn+2 selectively gets incorporated into the calcite crystal to modify its surface chemistry. This is expected to increase the surface charges of same polarity at the two opposing interfaces and promote the electrostatic repulsion to inherently change the surface preference towards water-wet conditions. This work for the first time identified the favorable impact of incorporating Mn+2 ions under optimized conditions to enhance the wetting transition in carbonate reservoirs. Such new knowledge gained from this experimental study highlights the practical significance of Mn+2 ions as cheap and sustainable wettability modifiers for EOR applications in carbonate reservoirs.

The inhibitory properties of ion-modified zeolite for priming paint coatings

The anticorrosion environmentally friendly pigments based on synthetic zeolite for paint coatings were obtained by liquid-phase ion exchange method. Zeolite was modified with zinc, calcium and manganese ions. The corrosion resistance of 09G2C steel in 0.1% NaCl solution and in suspensions of modified zeolite was investigated by potentiodynamic polarization method. It was shown that the use of zeolite modified with cations of divalent metals contributes to the reduction of corrosion currents. It was found that the zeolite modified with zinc cations exhibits the most anticorrosion effect relative to 09G2C steel, as indicated by the values of corrosion currents (which are ~2 times smaller than in the non-inhibited solution) and the results of electrochemical impedance spectroscopy. The surface morphology of 09G2S steel after exposure to the inhibited media was determined by scanning electron microscopy. Protection mechanism of the modified zeolite was suggested.

Flexible Diodes/Transistors Based on Tunable p-n-Type Semiconductivity in Graphene/Mn-Co-Ni-O Nanocomposites

We report a novel Mn-Co-Ni-O (MCN) nanocomposite in which the p-type semiconductivity of Mn-Co-Ni-O can be manipulated by addition of graphene. With an increase of graphene content, the semiconductivity of the nanocomposite can be tuned from p-type through electrically neutral to n-type. The very low effective mass of electrons in graphene facilitates electron tunneling into the MCN, neutralizing holes in the MCN nanoparticles. XPS analysis shows that the multivalent manganese ions in the MCN nanoparticles are chemically reduced by the graphene electrons to lower-valent states. Unlike traditional semiconductor devices, electrons are excited from the filled graphite band into the empty band at the Dirac points from where they move freely in the graphene and tunnel into the MCN. The new composite film demonstrates inherent flexibility, high mobility, short carrier lifetime, and high carrier concentration. This work is useful not only in manufacturing flexible transistors, FETs, and thermosensitive and thermoelectric devices with unique properties but also in providing a new method for future development of 2D-based semiconductors.