Amphiphilic Thiol Polymer Nanogel Removes Environmentally Relevant Mercury Species from Both Produced Water and Hydrocarbons.

Technologies for removal of mercury from produced water and hydrocarbon phases are desired by oil and gas production facilities, oil refineries, and petrochemical plants. Herein, we synthesize and demonstrate the efficacy of an amphiphilic, thiol-abundant (11.8 wt % S, as thiol) polymer nanogel that can remove environmentally relevant mercury species from both produced water and the liquid hydrocarbon. The nanogel disperses in both aqueous and hydrocarbon phases. It has a high sorption affinity for dissolved Hg(II) complexes and Hg-dissolved organic matter complexes found in produced water and elemental (Hg0) and soluble Hg-alkyl thiol species found in hydrocarbons. X-ray absorption spectroscopy analysis indicates that the sorbed mercury is transformed to a surface-bound Hg(SR)2 species in both water and hydrocarbon regardless of its initial speciation. The nanogel had high affinity to native mercury species present in real produced water (>99.5% removal) and in natural gas condensate (>85% removal) samples, removing majority of the mercury species using only a 50 mg L-1 applied dose. This thiolated amphiphilic polymeric nanogel has significant potential to remove environmentally relevant mercury species from both water and hydrocarbon at low applied doses, outperforming reported sorbents like sulfur-impregnated activated carbons because of the mass of accessible thiol groups in the nanogel.

Impact of mercury speciation on its removal from water by activated carbon and organoclay.

Mercury (Hg) speciation can affect its removal efficiency by adsorbents. This study assessed the removal of dissolved inorganic Hg(II) species (Hg(II)*), ß-HgS nanoparticles (HgS NP), and Hg complexed with dissolved organic matter (Hg-DOM) by three sorbents: activated carbon (AC), sulfur-impregnated activated carbon (SAC), and organoclay (OC). The effect of ionic composition, solution ionic strength, and natural organic matter (NOM) concentration on the removal of each Hg species was also evaluated. The three adsorbents were all effective in removing Hg(II)*, Hg-DOM, and HgS NPs. Increasing ionic strength decreased the removal of Hg(II)* species due to the formation of ionic Hg species with lower affinity for the sorbents. Added NOM decreased the removal of Hg(II)* and HgS NPs by all sorbents with the OC sorbent being most susceptible to NOM fouling. On a surface area-normalized basis, the OC removed all types of Hg species better than the AC and SAC samples. Moreover, adsorbed Hg-DOM transformed to a ß-HgS phase on the OC, but not for AC and SAC. These studies indicate that both Hg speciation and the water quality parameters need to be considered when designing sorbent-based emission controls to meet Hg removal targets.

Elemental Analysis of Asphaltenes Using Simultaneous Laser-Induced Breakdown Spectroscopy (LIBS)-Laser Ablation Inductively Coupled Plasma Optical Emission Spectrometry (LA-ICP-OES).

Laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma optical emission spectrometry (LA-ICP-OES) were used simultaneously for the elemental analysis of asphaltene samples using minimum sample pretreatment in combination with low laser energy to reduce the amount of removed particles and avoid carbon deposits in the ablation cell. Quantitative analyses of S, Ni, and V were accomplished with LA-ICP-OES using external calibration with the C line as internal standard. The aromatic/paraffinic nature of the asphaltenes was also obtained throughout the H/C ratio using LIBS and partial least square regression model. The results showed very good agreement (±10%) between the concentration obtained by LA-ICP-OES and microwave-assisted acid digestion values.

Influence of the dielectric medium on the carbonyl infrared absorption peak of acetylferrocene.

The solvent effect on the position of the carbonyl vibrational stretching of acetylferrocene in aprotic media was studied in this work. The solvent-induced shifts in this organometallic compound were interpreted in terms of the alternative reaction field model(SCRF-MO) proposed by Kolling. In contrast to the established trends for carbonyl groups in organic systems, the results suggest that the continuum models for the reaction field are not adequate and that the influence of dipolarity-polarizability described by an inhomogeneous coupling function theta(epsilon )L(n(2)) that assumes optical dielectric saturation is responsible for the carbonyl band shift and, there is empirical evidence that the effect of field-induced intermolecular interaction on band shift, interpreted in terms of the van der Waals forces from the solvent, have a important contribution to this phenomena.