Enid J. Sullivan

The cross-scale science of CO2 capture and storage: from pore scale to regional scale

We describe state-of-the-art science and technology related to modeling of CO2 capture and storage (CCS) at four different process scales: pore, reservoir, site, and region scale. We present novel research at each scale to demonstrate why each scale is important for a comprehensive understanding of CCS. Further, we illustrate research linking adjacent process scales, such that critical information is passed from one process scale to the next adjacent scale. We demonstrate this cross-scale approach using real world CO2 capture and storage data, including a scenario managing CO2 emissions from a large U.S. electric utility. At the pore scale, we present a new method for incorporating pore-scale surface tension effects into a relative permeability model of CO2-brine multiphase flow at the reservoir scale. We benchmark a reduced complexity model for site-scale analysis against a rigorous physics-based reservoir simulator, and include new system level considerations including local site-scale pipeline routing analysis (i.e., reservoir to site scale). We also include costs associated with brine production and treatment at the site scale, a significant issue often overlooked in CCS studies. All models that comprise our total system include parameter uncertainty which leads to results that have ranges of probability. Results suggest that research at one scale is able to inform models at adjacent process scales, and that these scale connections can inform policy makers and utility managers of overall system behavior including the impacts of uncertainty.

EFFECTS OF MINERALOGY, EXCHANGE CAPACITY, SURFACE AREA AND GRAIN SIZE ON LITHIUM SORPTION TO ZEOLITIC ALLUVIUM NEAR YUCCA MOUNTAIN, NEVADA

The resistance to acidic and sulfate attack of Portland-pozzolan cement containing 35 wt.% of zeolite was compared with that of unamended Portland cement. Mortar specimens kept in 0.5% and 1.0% HCl solution, 5% Na2SO4 solution, and in reference water for 365 and 720 days were tested using a set of physical-mechanical and chemical techniques. The ability of mortars containing zeolitic cements with 15 to 50 wt.% of zeolite to protect steel against corrosion was verified by a potentiodynamic method. Mortar with zeolitic cement performs better when exposed to 1% HCl solution due to the presence of a finer pore matrix, a hydrate phase poorer in CaO-containing hydration products with lower leachability, and the high resistance of zeolite material itself to acidic attack, compared with Portland cement and siliceous sand. The improved sulfate resistance of the mortar with zeolitic cement is caused by the decreased C3A in the cement blend in comparison with that in Portland cement, a reduction in SO3 binding into the cement paste and decreased amount of CaO-containing hydration products capable of reacting with a sulfate solution forming voluminous reaction products, and consequent crack propagation, large expansion and structural disintegration. Passivation of steel in mortars with blends of Portland cement to zeolite percentage ratios of 85/15, 75/25 and 65/35 by weight is comparable to that of Portland cement mortar. This is particularly important because the mortar with zeolitic cement exhibits late strengths similar to that of Portland cement mortar. This confirms that zeolitic cement can replace Portland cement in many applications with the advantage of higher resistance to acidic and sulfate attack.The Li + ion is used frequently as an environmentally acceptable surrogate for sorbing radionuclides in field tracer tests, and experiments using Li are an important part of assessing the potential transport of radionuclides in saturated alluvium south of Yucca Mountain, Nevada, the site of a proposed nuclear waste repository. Equilibrium partition constants (Li + K d s) were measured using batch studies incorporating a wide range of Li + concentrations and two different grain-size fractions of alluvium samples from multiple depth intervals in two wells. Cation exchange capacity, surface area, bulk mineralogy from quantitative X-ray powder diffraction, and trace Mn- and Fe-oxyhydroxide mineralogy from extractive studies were evaluated as predictors for linearized Li + K d values (K lin ) in the alluvium. Many of the predictor variables are correlated with each other and this was considered in the analysis. Linearized K d values were consistently higher for fine particle-size fractions than for coarse fractions. Single and multivariate linear regression analyses indicated that the clinoptilolite + smectite content, taken together as a combined variable, was the best predictor for Li + sorption in the alluvium, although clinoptilolite content was clearly a better predictor when the two variables were considered separately in simple linear regressions. Even so, Li + K lin predictions based on clinoptilolite and smectite abundance were accurate only to within about ±100%. This uncertainty suggests that there is either a high inherent variability in Li + K lin values or that additional alluvium characteristics not measured or evaluated here may play an important role in simple Li + cation exchange in the alluvium.

Transport of a reactive tracer in saturated alluvium described using a three-component cation-exchange model

A weakly sorbing cation, lithium, will be used as a reactive tracer in upcoming field tracer tests in the saturated alluvium south of Yucca Mountain, Nevada. One objective of the field tests is to determine how well field-scale reactive transport can be predicted using transport parameters derived from laboratory experiments. This paper describes several laboratory lithium batch sorption and column transport experiments that were conducted using ground water and alluvium obtained from the site of the planned field tests. In the batch experiments, isotherms were determined over 2.5 orders of magnitude of lithium concentrations, corresponding to the range expected in the field tests. In addition to measuring equilibrium lithium concentrations, concentrations of other cations, namely Na(+), K(+), and Ca(2+), were measured in the batch tests to determine Li(+)-exchangeable equilibria. This information was used in conjunction with alluvium cation exchange capacity measurements to parameterize a three-component cation-exchange model (EQUIL) that describes lithium sorption in the alluvium system. This model was then applied to interpret the transport behavior of lithium ion in saturated alluvium column tests conducted at three different lithium bromide injection concentrations. The concentrations were selected such that lithium ion either dominated, accounted for a little over half, or accounted for only a small fraction of the total cation equivalents in the injection solution. Although tracer breakthrough curves differed significantly under each of these conditions, with highly asymmetric responses occurring at the highest injection concentrations, the three-component cation-exchange model reproduced the observed transport behavior of lithium and the other cations in each case with a similar set of model parameters. In contrast, a linear K(d)-type sorption model could only match the lithium responses at the lowest injection concentration. The three-component model will be used to interpret the field tests, with the expectation that it will help refine estimates of effective flow porosity, particularly if the lithium response curves are asymmetric.

A CO2-PENS model of methods and costs for treatment of water extracted during geologic carbon sequestration

Abstract Extraction of water during subsurface carbon sequestration may be useful for the control of CO2 placement, reducing pressure risks, and mitigating environmental risks. Desalination of this water may be possible if costs are kept low, in order to minimize the quantity that must be reinjected or otherwise disposed. Added value may be recovered in the form of treated water that can be reused by carbon capture, sequestration, and other industrial processes. Total dissolved solids will range from 10,000 mg/L up to over 100,000 mg/L, and temperatures may range up to 120°C, once the water is brought to the surface. We have developed a system-level, mesoscale analysis module for the CO2-Predicting engineered natural system model to analyze the feasibility of treatment, the costs of treatment, the value of energy recovery, and the costs of concentrate disposal. Costs are derived from a database of reported literature values. The model allows the user to select the most economic options for treatment, to c...

Treatment of Produced Oil and Gas Waters With Surfactant-Modified Zeolite

Whereas most water produced from onshore oil and gas operations is disposed via reinjection, some waters, such as those from offshore production platforms, coastal production, and some onshore wells, must be treated to remove organic constituents before the water is discharged. Current methods for reducing residual free phases and dissolved organic carbon are not always fully effective in meeting regulatory limits. In addition, cost, space requirements, and ease of use are important factors in any treatment system. Surfactant-modified zeolite (SMZ) has been used successfully to treat contaminated ground water for organic and inorganic constituents. This research will use laboratory batch and column studies to design a field system that will be used to treat produced waters to reduce dissolved and free-phase organic constituents. The system will be designed to operate simply and to have low operating costs. Methods for regeneration of the spent zeolite will also be tested, as will the treatment system at a field production site in the final project task. Research over the past six months has focused on the selection and characterization of the surfactant modified zeolite and the produced waters. The zeolite to be used in this work has been obtained from St. Cloud Mine near Winston, New Mexico. The primary surfactant to be used to modify the zeolite is hexadecyltrimethylammonium (HDTMA).

Long Term Field Development of a Surfactant Modified Zeolite/Vapor Phase Bioreactor System for Treatment of Produced Waters for Power Generation

The main goal of this research was to investigate the feasibility of using a combined physicochemical/biological treatment system to remove the organic constituents present in saline produced water. In order to meet this objective, a physical/chemical adsorption process was developed and two separate biological treatment techniques were investigated. Two previous research projects focused on the development of the surfactant modified zeolite adsorption process (DE-AC26-99BC15221) and development of a vapor phase biofilter (VPB) to treat the regeneration off-gas from the surfactant modified zeolite (SMZ) adsorption system (DE-FC26-02NT15461). In this research, the SMZ/VPB was modified to more effectively attenuate peak loads and to maintain stable biodegradation of the BTEX constituents from the produced water. Specifically, a load equalization system was incorporated into the regeneration flow stream. In addition, a membrane bioreactor (MBR) system was tested for its ability to simultaneously remove the aromatic hydrocarbon and carboxylate components from produced water. The specific objectives related to these efforts included the following: (1) Optimize the performance VPBs treating the transient loading expected during SMZ regeneration: (a) Evaluate the impact of biofilter operating parameters on process performance under stable operating conditions. (b) Investigate how transient loads affect biofilter performance, and identify an appropriate technology to improve biological treatment performance during the transient regeneration period of an SMZ adsorption system. (c) Examine the merits of a load equalization technology to attenuate peak VOC loads prior to a VPB system. (d) Evaluate the capability of an SMZ/VPB to remove BTEX from produced water in a field trial. (2) Investigate the feasibility of MBR treatment of produced water: (a) Evaluate the biodegradation of carboxylates and BTEX constituents from synthetic produced water in a laboratory-scale MBR. (b) Evaluate the capability of an SMZ/MBR system to remove carboxylates and BTEX from produced water in a field trial. Laboratory experiments were conducted to provide a better understanding of each component of the SMZ/VPB and SMZ/MBR process. Laboratory VPB studies were designed to address the issue of influent variability and periodic operation (see DE-FC26-02NT15461). These experiments examined multiple influent loading cycles and variable concentration loadings that simulate air sparging as the regeneration option for the SMZ system. Two pilot studies were conducted at a produced water processing facility near Farmington, New Mexico. The first field test evaluated SMZ adsorption, SMZ regeneration, VPB buffering, and VPB performance, and the second test focused on MBR and SMZ/MBR operation. The design of the field studies were based on the results from the previous field tests and laboratory studies. Both of the biological treatment systems were capable of removing the BTEX constituents in the laboratory and in the field over a range of operating conditions. For the VPB, separation of the BTEX constituents from the saline aqueous phase yielded high removal efficiencies. However, carboxylates remained in the aqueous phase and were not removed in the combined VPB/SMZ system. In contrast, the MBR was capable of directly treating the saline produced water and simultaneously removing the BTEX and carboxylate constituents. The major limitation of the MBR system is the potential for membrane fouling, particularly when the system is treating produced water under field conditions. The combined process was able to effectively pretreat water for reverse osmosis treatment and subsequent downstream reuse options including utilization in power generation facilities. The specific conclusions that can be drawn from this study are summarized.