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Around 1960, a private company entered into a research agreement to analyze for dissolved solids in water produced from >800 fields in the U.S. and Canada.. The elemental compositions provided were measured spectrochemically by Rittenhouse et al. The information has been made available to the public as a public service, but the names off of the companies and exact well locations have been removed. The samples are now located at the University of Texas in Austin. More details can be found in the following reference: Gordon Rittenhouse, Robert B. Fulton, Robert J. Grabowski, Joseph L. Bernard, Minor elements in oil-field waters, Chemical Geology, Volume 4, Issues 1–2, 1969, Pages 189-209, ISSN 0009-2541, https://doi.org/10.1016/0009-2541(69)90045-X.

This is a standalone release of PARETO UI using the previously released PARETO version 0.9.0 for the backend.. New features in this version of PARETO UI are: - Added functionality to upload GIS map network visualizations and auto generate input templates - Added map visualizations based on GIS data

This research investigated a novel electrochemical process for producing a ferric iron coagulant for use in treating flowback and produced water (FPW) from hydraulic fracturing and oil production operations. The electrolytic coagulant generation (ECG) system uses an electrochemical cell to produce acid and base from oilfield brine solutions. The acid is used to dissolve scrap iron to provide a Fe³⁺ coagulating agent, and the base is used to neutralize the treated water. The costs for generating the ferric iron coagulant were determined as a function of current density and feed water salinity. The process was shown to be effective for removing colloidal bentonite particles from brine solutions. Here, the process has several advantages over conventional electrocoagulation using iron anodes, including: the ability to treat anoxic waters, elimination of electrode fouling, lower cost for the coagulant, and the ability to deliver Fe³⁺ doses greater than 1 mM, since it is not limited by the amount of dissolved oxygen required to oxidize ferrous to ferric iron.

PARETO 0.9.0 Release. Highlights: New Features - Initial beneficial reuse implementation - Post-optimization timing for infrastructure buildout Bug Fixes - Address Pyomo solver bug for UI Gurobi solve - Update Toy Case Study to feasible data for hydraulics post_process - Update Jupyter notebook for fall release UI Updates - Added functionality to optimize with hydraulics options - Added new plots to KPI dashboard for water quality and hydraulics timelines

Executive Summary This Final Report is composed of two major sections. The first section presents experimental results obtained in the laboratory during Budget Period 1. The second section presents results from the field test conducted during Budget Period 2. Laboratory Results This research investigated a novel electrochemical process for producing a ferric iron coagulant for use in treating flowback and produced water from hydraulic fracturing and oil production operations. The treatment system improves the effectiveness and lowers the cost of coagulation processes using Fe3+ as the coagulant. The electrolytic coagulant generation (ECG) system uses an electrochemical cell to produce acid and base from oilfield brine solutions. The acid is used to dissolve scrap iron to provide a Fe3+ coagulating agent. The base is used to neutralize the treated water. Compared to conventional electrocoagulation (EC), the main advantage of the ECG system is an order of magnitude lower cost for the source of iron. The second advantage over conventional EC is that it can deliver Fe3+ doses greater than 1 mM, since it is not limited by the amount of dissolved oxygen in the water required to oxidize ferrous to ferric iron. The capital costs for conventional EC and the ECG system are similar, but the operational costs for the ECG system are an order of magnitude lower than conventional EC. The combined costs for iron and electrical energy for treating 1 m3 of FPW with 1 mM Fe3+ is estimated to be $0.87 for conventional EC, and $0.087 for the ECG system. The estimated all-in cost for treating FPW with a 2 mM Fe3+ dose is $0.73/m3 ($0.12/bbl). Field Test Results The field test was conducted at the Paul Foster Central Tank Battery (CTB) in Lea County, New Mexico from November 10, 2022 through December 15, 2022. The feed water to the system was produced water from the Tatanka 1H formation. After approximately two weeks of testing, the initial batch of produced water had been treated and no untreated produced water was available. Thus, after this time, the feed water to the system consisted of previously treated water (i.e., recycled water). The recycled water had nearly all colloidal particles removed, and had a much lower alkalinity due to precipitation of carbonate minerals during the first pass through the system. Although the recycled water was not an ideal test solution due to its low particulate concentrations, its lower alkalinity did allow us to identify the main problem with the treatment system. The main problem with the treatment system was caused by the high alkalinity of the initial feed water (5.4 meq/L) that consumed a significant fraction of the electrochemically generated acid. This resulted in pH values exiting the iron contact tank that were too high to dissolve enough iron to effectively treat the produced water. Tests performed with recycled water with lower alkalinity did not have this issue, and dissolved iron concentrations greater than 20 mM could be achieved. One consistent observation was that effluent water from the iron contact tank was always free of particulates, even when fed with circumneutral solutions. This suggests that there is no need to dissolve high concentrations of iron if all the water to be treated is passed through the scrap iron canister. In this case, dissolved O2 and hypochlorous acid can promote sufficient iron corrosion to provide an effective coagulating agent – even in neutral pH water. This solves the problem resulting from highly alkaline produced water. Modifications to the design of the treatment system were made based on the field test results. These modifications will add minimal additional cost, and were tested in bench-scale laboratory experiments. In short-term testing, the modified treatment process was able to remove colloidal FeS particulates to levels below detection. Long-term, steady state testing will be required to determine whether the modified process is suitable for commercial treatment systems.

PARETO 0.8.0 Release. Highlights: Model Updates - Applied unified sets for pipeline and trucking arcs in strategic model - Apply unified sets for pipeline and trucking arcs in operational model - Added new config argument for removal efficiency calculation method - Standardized bidirectional capacity constraint - Added dependencies removed in IDAES 2.1 - Created bounding functions & utilities - Added Hydraulics module to the strategic model - Add additional arc types to strategic model Documentation and Tutorial Updates - Improved PARETO treatment document - Introduced general tutorial and treatment module Jupyter notebooks for Strategic Model - Update docs with correct support email list address - Consolidate and deduplicate Getting Started and resources for developers - Enable Black formatting for Jupyter notebooks - Add Binder configuration files and README Bug Fixes - Fix strategic model documentation typos - Removed duplicated units from output file header UI Updates - Added view for comparing different scenarios - Added functionality for manually overriding PARETO decisions

The objective of this work was to optimize the operation of a zeolite nanofiltration membrane (Zebrex, manufactured by Mitsubishi Chemical) to remove the organic compounds from produced water (PW) that cause fouling of the RO membranes. TDA Research worked to develop a new treatment process and carried out proof-of-concept demonstrations at bench-scale and in a 1 bpd prototype using simulated and actual PW received from different fields. The TRL was elevated to 6 at the successful completion of the project. The performance of the Zebrex membranes for separating target impurities (e.g. volatiles organics, polyaromatics, ketones, phenols, amides, phosphate esters, methanol, glycol, and organic acids) was evaluated. Various versions of the Zebrex membranes with different pore sizes and surface properties were tested to determine the best combinations to reject the widest possible range of hydrocarbons. Bench-scale experiments were conducted to assess the impact of temperature and salinity on performance, and we discovered that when operated in pervaporation mode, the ceramic nanofiltration membrane can reject both hydrocarbons and salts in a single process step, altogether eliminating the need for an RO membrane. Pervaporation mode requires heating of the inlet feed water and transport of the water across the membrane in the vapor phase. The pore size of the membrane selectively rejects all molecules larger than water, and the lack of a liquid concentration gradient prevents mass transfer of ions (salts) across the membrane. Produced water is filtered for total suspended solids using a mechanical filter, heated to 120-150°C, and delivered to the membrane shell at moderate pressure < 50 psig. Water is transported through each tubular membrane element in the vapor phase and collected under vacuum in a clean permeate plenum. The clean water is cooled, condensed, and collected for use. The retentate stream is recycled back to the inlet of the membrane to conserve sensible heat and further concentrate the rejected contaminates in a waste stream. The water recovery is dependent on the solubility of salts in the produced water. TDA demonstrated the performance of the proposed PW purification system, showing that the treated water was free of both salt and soluble organic compounds. A techno-economic analysis (TEA) was developed and a prototype system capable of processing 1 bpd of PW to fit-for-purpose water was designed. In BP2, the prototype was fabricated and reclamation of fit-for-purpose water at 1 bpd scale was demonstrated. The membrane life was evaluated for over 8,000 hours. Proof-of-concept tests were carried out using actual PW samples received from multiple basins in collaboration with operators from those regions. A design of the full-scale system with all auxiliary units was conducted. Finally, the overall process was optimized and the TEA was updated based on the prototype performance demonstrating economic viability with a treatment cost less than the target of $3/bbl.

Membrane distillation (MD) is a promising technique for desalinating hypersaline brine, such as produced water (PW). To date, fouling and scaling have remained as major challenges for MD implementation. In this study, chlorine dioxide combined with induced air floatation (ClO₂-IAF) was systematically investigated as a pretreatment prior to MD. First, the ClO₂ generation based on sodium chlorite and hydrochloric acid was optimized to maximize the on-demand ClO₂ production. The maximum production yield of 18.4% was obtained with 4wt.% NaClO₂ and 20wt.% HCl solutions, with a molar ratio of 1:1.25. Then, two real PW samples were pretreated, and removal efficiencies for total suspended solids (TSS), turbidity, iron, and total organic carbon (TOC) were comprehensively studied by varying the ClO₂ dosage between 6 and 91 mg/L. The ClO₂-IAF pretreatment displayed TSS and turbidity removals above 90% and TOC removal close to 55%. Further, the PW constituents such as benzene, toluene, ethylbenzene, xylene (BTEX), and total petroleum hydrocarbons (TPH) were analyzed and quantified throughout the cascade of the treatments. The volatiles like BTEX were mainly removed by air floatation, while saturated hydrocarbons such as TPH were retained by the hydrophobic membrane. The MD long-term stability without any in-place cleaning was evaluated, and the membrane withstood for twenty two days without wetting, suggesting that optimizing oxidation pretreatment is critical for mitigating the fouling in MD. Results suggest that organic fouling in PW could be effectively reduced by the pretreatment, but further treatment is required to mitigate the scaling, which resulted in MD wetting.

PARETO 0.7.0 Release. Highlights: - Update years for copyright - Correct Core-dev installation instructions - Improve delivery constraint indexing - Incorporate component removal efficiency at treatment sites - Allow model Parameters to be mutable - Address CodeCov failures - Ensure compatibility with IDAES v2

Produced water (PW) is a complex mixture generated during oil and gas extraction. Membrane fouling by hydrocarbon emulsions (sizes < 10 µm) challenges most PW treatment systems. Electrospinning has the possibility of creating microporous membranes that present unique performance properties, though evaluations of these characteristics are largely restricted to unrealistic dead-end configurations. Three different nanofibrous polyacrylonitrile (PAN) membranes were synthesized by electrospinning and their performances contrasted with a commercially available PAN membrane. Feed solutions included synthetic oil and solvent emulsions and a PW from an operating well-site. Two nanoparticles, polyaniline (PANI) and reduced graphene oxide (RGO), were studied for enhancing the oleophobicity and fouling properties of the electrospun PAN membranes. Electrospun membranes showed higher porosities (68 to 80 %) and water permeance values (9,000 to 10,000 LMH/bar) relative to that for the commercially available PAN membrane (44 % and 8,800 LMH/bar). All electrospun membranes provided superior performance characteristics when treating the emulsions and PW relative to the commercial membrane. Furthermore, the PANI integrated membrane demonstrated the greatest resistance to oil/solvent emulsion fouling and comparable performance to the RGO and PAN membrane treating the PW.