This report represents completion of milestone deliverable M2SF-21SN010309012 “Annual Status Update for OWL and Waste Form Characteristics” that provides an annual update on status of fiscal year (FY 2020) activities for the work package SF-20SN01030901 and is due on January 29, 2021. The Online Waste Library (OWL) has been designed to contain information regarding United States (U.S.) Department of Energy (DOE)-managed (as) high-level waste (DHLW), spent nuclear fuel (SNF), and other wastes that are likely candidates for deep geologic disposal, with links to the current supporting documents for the data (when possible; note that no classified or official-use-only (OUO) data are planned to be included in OWL). There may be up to several hundred different DOE-managed wastes that are likely to require deep geologic disposal. This draft report contains versions of the OWL model architecture for vessel information (Appendix A) and an excerpt from the OWL User’s Guide (Appendix B and SNL 2020), which are for the current OWL Version 2.0 on the Sandia External Collaboration Network (ECN).
Sandia National Laboratories (SNL) is developing a cooling technology concept the Sandia National Laboratories Natural Circulation Cooler (SNLNCC) that has potential to greatly improve the economic viability of hybrid cooling for power plants. The SNLNCC is a patented technology that holds promise for improved dry heat rejection capabilities when compared to currently available technologies. The cooler itself is a dry heat rejection device, but is conceptualized here as a heat exchanger used in conjunction with a wet cooling tower, creating a hybrid cooling system for a thermoelectric power plant. The SNLNCC seeks to improve on currently available technologies by replacing the two-phase refrigerant currently used with either a supercritical fluid such as supercritical CO2 (sCO2) or a zeotropic mixture of refrigerants. In both cases, the heat being rejected by the water to the SNLNCC would be transferred over a range of temperatures, instead of at a single temperature as it is in a thermosyphon. This has the potential to improve the economics of dry heat rejection performance in three ways: decreasing the minimum temperature to which the water can be cooled, increasing the temperature to which air can be heated, and increasing the fraction of the year during which dry cooling is economically viable. This paper describes the experimental basis and the current state of the SNLNCC.
Water management has become critical for thermoelectric power generation in the US. Increasing demand for scarce water resources for domestic, agricultural, and industrial use affects water availability for power plants. In particular, the population in the Southwestern part of the US is growing and water resources are over-stressed. The engineering and management teams at the Palo Verde Generating Station (PV) in the Sonoran Desert have long understood this problem and began a partnership with Sandia National Laboratories in 2017 to develop a long-Term water strategy for PV. As part of this program, Sandia and Palo Verde staff have developed a comprehensive software tool that models all aspects of the PV (plant cooling) water cycle. The software tool the Palo Verde Water Cycle Model (PVWCM) tracks water operations from influent to the plant through evaporation in one of the nine cooling towers or one of the eight evaporation ponds. The PVWCM has been developed using a process called System Dynamics. The PVWCM is developed to allow scenario comparison for various plant operating strategies.
One of the objectives of the United States (U.S.) Department of Energy's (DOE) Office of Nuclear Energy's Spent Fuel and Waste Science and Technology Campaign is to better understand the technical basis, risks, and uncertainty associated with the safe and secure disposition of spent nuclear fuel (SNF) and high-level radioactive waste. Commercial nuclear power generation in the U.S. has resulted in thousands of metric tons of SNF, the disposal of which is the responsibility of the DOE (Nuclear Waste Policy Act 1982). Any repository licensed to dispose the SNF must meet requirements regarding the longterm performance of that repository. For an evaluation of the long-term performance of the repository, one of the events that may need to be considered is the SNF achieving a critical configuration. Of particular interest is the potential behavior of SNF in dual-purpose canisters (DPCs), which are currently being used to store and transport SNF but were not designed for permanent geologic disposal. A two-phase study has been initiated to begin examining the potential consequences, with respect to longterm repository performance, of criticality events that might occur during the postclosure period in a hypothetical repository containing DPCs. Phase I, a scoping phase, consisted of developing an approach intended to be a starting point for the development of the modeling tools and techniques that may eventually be required either to exclude criticality from or to include criticality in a performance assessment (PA) as appropriate; Phase I is documented in Price et al. (2019). The Phase I approach guided the analyses and simulations done in Phase II to further the development of these modeling tools and techniques as well as the overall knowledge base. The purpose of this report is to document the results of the analyses conducted during Phase II. The remainder of Section 1 presents the background, objective, and scope of this report, as well as the relevant key assumptions used in the Phase II analyses and simulations. Subsequent sections discuss the analyses that were conducted (Section 2), the results of those analyses (Section 3), and the summary and conclusions (Section 4). This report fulfills the Spent Fuel and Waste Science and Technology Campaign deliverable M2SF-20SN010305061.
This report provides an analysis of the clad barrier function associated with the direct disposal of dual purpose canisters (DPCs) under hypothetical conditions in a shale repository and in an alluvial repository, including the effect of a postulated criticality event inside a disposed DPC. Should a postulated criticality event occur in a hypothetical shale repository, cladding will primarily degrade by general corrosion. Stress corrosion cracking, hydride cracking, creep failure, pitting and crevice corrosion, rod pressurization, and clad unzipping are calculated to have little impact on cladding persistence. At the higher temperature expected during a postulated criticality event in a saturated shale repository, general corrosion of cladding would be rapid - on the order of 0.034 microns/yr. A few hundred years after onset of a postulated criticality event in a shale repository complete general corrosion of fuel assembly grid spacer walls and guide tubes will likely result in settling of fuel rods upon each other. This rod consolidation should displace the water moderator and possibly terminate a postulated criticality. The primary potential degradation pathway for cladding in a hypothetical alluvial repository is localized corrosion by fluoride, which cannot occur in a shale repository. Fluoride-enhanced corrosion of cladding would be accelerated under the slightly higher (< 100°C) temperatures associated with a postulated criticality event. The impact of criticality in both cases (shale and alluvial) would be to increase the amount of failed cladding. But it would require very specialized transport pathways.
This review analyses the fundamental thermodynamic theory of the crude oil-brine-rock (COBR) interface and the underlying rock-brine and oil-brine interactions. The available data are then reviewed to outline potential mechanisms responsible for increased oil recovery from low salinity waterflooding (LSWF). We propose an approach to studying LSWF and identify the key missing links that are needed to explain observations at multiple length scales. The synergistic effect of LSWF on other chemical enhanced oil recovery methods such as surfactant, alkaline, nanoparticle and polymer flooding are also outlined. We specifically highlight key uncertainties that must be overcome to fully implement the technique in the field.
Sandia National Laboratories has built and successfully tested a dynamic simulation technoeconomic model of the Palo Verde Generating Station that is now being updated to help other US power plants improve operations. Palo Verde, located west of Phoenix, Arizona, is the largest electricity generator in the US at 4 GW. Palo Verde uses — 60 million gallons per day of treated wastewater from Phoenix to cool reactors, and disposes of blowdown in evaporation ponds. The model built for Palo Verde numerically evaluates the economic impact of changing, for example, alternative cooling technologies, water usage and treatment, and influent water chemistry, and is based on detailed accounting of mass, energy, and cash flows.
Low-salinity waterflooding (LSWF) has proven to improve oil recovery in carbonate formations through rock wettability alteration, although the underlying mechanism remains elusive. Multivalent ionic exchange and calcite dissolution have usually been investigated using geochemical analysis in secondary coreflooding. In this work, coreflooding, in tertiary mode, coupled with a surface reactivity analysis approach was employed to investigate the interplay of wettability alteration mechanisms such as mineral dissolution, electrostatic bond attraction, and the effect of pH at in situ conditions. Improved oil recovery (IOR) in tertiary mode observed by coreflooding in Indiana limestone rocks showed an ionic strength dependence, that is, reducing brine ionic strength resulted in an increase in oil recovery. Coreflooding results showed that the seawater and low-salinity brines deprived of Mg2+ ions resulted in the lowest IOR in tertiary mode, indicating the significance of Mg2+ on IOR in limestone rocks. Similar results were observed through the contact angle measurement showing the limestone rock wettability state dependence on ionic strength and the effect of Mg2+ ions. Surface reactivity analysis showed an increase in solution pH, Ca2+ and Mg2+ ions concentration in the effluent solution from the coreflooding in tertiary mode using low salinity brines (about 40 and 20% increase in the effluent composition for Ca2+ and Mg2+, respectively). These changes in solution composition were used to calculate the in situ oil-brine and rock-brine zeta potential using a validated surface complexation model, showing the changes of zeta potential as brine is injected into limestone rocks. The results show that using seawater-like brine in tertiary mode resulted in no mineral dissolution or ionic exchange. However, improved oil recovery (IOR) using such seawater-like brine was due to wettability alteration caused by reduced electrostatic bond attraction associated with Mg2+ ions [from 2.6 × 10-13 (mol/m2)2 for formation water salinity to 1.5 × 10-13 (mol/m2)2 for seawater salinity]. Using low-salinity brines in tertiary mode improved oil recovery by mineral dissolution, resulting in oil desorption and an increase in solution pH. The increase in solution pH also resulted in reduced electrostatic bond attraction which lead to rock wettability alteration using low-salinity brines.
This report represents completion of milestone deliverable M2SF-19SNO10309013 "Online Waste Library (OWL) and Waste Forms Characteristics Annual Report" that reports annual status on fiscal year (FY) 2019 activities for the work package SF-19SN01030901 and is due on August 2, 2019. The online waste library (OWL) has been designed to contain information regarding United States (U.S.) Department of Energy (DOE)-managed (as) high-level waste (DHLW), spent nuclear fuel (SNF), and other wastes that are likely candidates for deep geologic disposal, with links to the current supporting documents for the data (when possible; note that no classified or official-use-only (OUO) data are planned to be included in OWL). There may be up to several hundred different DOE-managed wastes that are likely to require deep geologic disposal. This annual report on FY2019 activities includes evaluations of waste form characteristics and waste form performance models, updates to the OWL development, and descriptions of the management processes for the OWL. Updates to the OWL include an updated user's guide, additions to the OWL database content for wastes and waste forms, results of the beta testing and changes implemented from it. Also added are descriptions of the management/control processes for the OWL development, version control, and archiving. These processes have been implemented as part of the full production release of OWL (i.e., OWL Version 1.0), which has been developed on, and will be hosted and managed on, Sandia National Laboratories (SNL) systems. The version control/update processes will be implemented for updates to the OWL in the future. Additionally, another process covering methods for interfacing with the DOE SNF Database (DOE 2007) at Idaho National Laboratory on the numerous entries for DOE-managed SNF (DSNF) has been pushed forward by defining data exchanges and is planned to be implemented sometime in FY2020. The INL database is also sometimes referred to as the Spent Fuel Database or the SFDB, which is the acronym that will be used in this report. Once fully implemented, this integration effort will serve as a template for interfacing with additional databases throughout the DOE complex.
The safety case for deep borehole disposal of nuclear wastes contains a safety strategy, an assessment basis, and a safety assessment. The safety strategy includes strategies for management, siting and design, and assessment. The assessment basis considers site selection, pre-closure, and post-closure, which includes waste and engineered barriers, the geosphere/natural barriers, and the biosphere and surface environment. The safety assessment entails a pre-closure safety analysis, a post-closure performance assessment, and confidence enhancement analyses. This paper outlines the assessment basis and safety assessment aspects of a deep borehole disposal safety case. The safety case presented here is specific to deep borehole disposal of Cs and Sr capsules, but is generally applicable to other waste forms, such as spent nuclear fuel. The safety assessments for pre-closure and post-closure are briefly summarized from other sources; key issues for confidence enhancement are described in greater detail. These confidence enhancement analyses require building the technical basis for geologically old, reducing, highly saline brines at the depth of waste emplacement, and using reactive-transport codes to predict their movement in post-closure. The development and emplacement of borehole seals above the waste emplacement zone is also important to confidence enhancement.
Commercial generation of energy via nuclear power plants in the United States (U.S.) has generated thousands of metric tons of spent nuclear fuel (SNF), the disposal of which is the responsibility of the U.S. Department of Energy (DOE) (Nuclear Waste Policy Act of 1982). Any repository licensed to dispose of the SNF must meet requirements regarding the long-term performance of the repository. In evaluating the long-term performance of the repository, one of the events that may need to be considered is the SNF achieving a critical configuration. Of particular interest is the potential behavior of SNF in dual-purpose canisters (DPCs), which are currently being used to store the SNF but were not designed for permanent disposal. As part of a multiyear plan that is currently being developed for the DOE, a two-phase study has been initiated to examine the potential consequences, with respect to long-term repository performance, of criticality events that might occur during the postclosure period in a hypothetical repository containing DPCs. Phase I, a scoping phase, consists of generating an approach intended to be a starting point for the development of the modeling tools and techniques that may eventually be required either to exclude criticality from or include criticality in a performance assessment (PA) as appropriate. The Phase I approach will be used to guide the analyses and simulations done in Phase II to further the development of these modeling tools and techniques as well as the overall knowledge base. The purpose of this report is to document the approach created during Phase I. The study discussed herein focuses on the consequences of criticality in a DPC; it does not address the probability of occurrence of a criticality event. This approach examines two types of criticality events for SNF disposed of in a single type of DPC: a steady-state criticality and a transient criticality. The steady-state critical event is characterized by a relatively low constant power output over 10,000 years, while the transient critical event is characterized by a power spike that lasts on the order of seconds. Possible effects of the criticality are an increase in the radionuclide inventory; an increase in temperature; and a change in the chemistry inside the waste package, along with a change in radionuclide solubilities, fuel degradation rates, and steel corrosion rates. Additionally, for transient criticality the possibility of mechanical damage to the engineered and natural barriers also exists.
This report describes the current status of the safety case for the deep borehole disposal (DBD) concept. It builds on the safety case presented in Freeze et al. (2016), presenting new information and identifying additional information needs for specific safety case elements. At this preliminary phase of development, the DBD safety case focuses on the generic feasibility of the DBD concept. It is based on potential system designs, waste forms, engineering, and geologic conditions; however, no specific site or regulatory framework exists. Updated information is provided for the following safety case elements: (1) pre-closure basis and safety analysis, (2) post-closure basis and performance assessment, and (3) confidence enhancement. This research was performed as part of the deep borehole field test (DBFT). Based on revised U.S. Department of Energy (DOE) priorities in mid-2017, the DBFT and other research related to a DBD option was discontinued; ongoing work and documentation were closed out by the end of fiscal year (FY) 2017. This report was initiated as part of the DBFT and documented as an incomplete draft at the end of FY 2017. The report was finalized by Sandia National Laboratories in FY2018 without DOE funding, subsequent to the termination of the DBFT, and published in FY2019.
Various versions of deep borehole nuclear waste disposal have been proposed in the past in which effective sealing of a borehole after waste emplacement is generally required. In a high temperature disposal mode, the sealing function will be fulfilled by melting the ambient granitic rock with waste decay heat or an external heating source, creating a melt that will encapsulate waste containers or plug a portion of the borehole above a stack of the containers. However, there are certain drawbacks associated with natural materials, such as high melting temperatures, inefficient consolidation, slow crystallization kinetics, the resulting sealing materials generally being porous with low mechanical strength, insufficient adhesion to waste container surface, and lack of flexibility for engineering controls. In this study, we showed that natural granitic materials can be purposefully engineered through chemical modifications to enhance the sealing capability of the materials for deep borehole disposal. The present work systematically explores the effect of chemical modification and crystallinity (amorphous vs. crystalline) on the melting and crystallization processes of a granitic rock system. The approach can be applied to modify granites excavated from different geological sites. Several engineered granitic materials have been explored which possess significantly lower processing and densification temperatures than natural granites. Those new materials consolidate more efficiently by viscous flow and accelerated recrystallization without compromising their mechanical integrity and properties.
Post-closure performance assessment (PA) calculations suggest that deep borehole disposal of cesium (Cs)/strontium (Sr) capsules, a U.S. Department of Energy (DOE) waste form (WF), is safe, resulting in no releases to the biosphere over 10,000,000 years when the waste is placed in a 3-5 km deep waste disposal zone. The same is true when a hypothetical breach of a stuck waste package (WP) is assumed to occur at much shallower depths penetrated by through-going fractures. Cs and Sr retardation in the host rock is a key control over movement. Calculated borehole performance would be even stronger if credit was taken for the presence of the WP.
This report represents completion of milestone deliverable M2SF-18SNO10309013 "Inventory and Waste Characterization Status Report and OWL Update that reports on FY2018 activities for the work package (WP) SF-18SNO1030901. This report provides the detailed final information for completed FY2018 work activities for WP SF-18SN01030901, and a summary of priorities for FY2019. This status report on FY2018 activities includes evaluations of waste form characteristics and waste form performance models, updates to the OWL development, and descriptions of the two planned management processes for the OWL. Updates to the OWL include an updated user's guide, additions to the OWL database content for wastes and waste forms, results of the Beta testing and changes implemented from it. There are two processes being planned in FY2018, which will be implemented in FY2019. One process covers methods for interfacing with the DOE SNF DB (DOE 2007) at INL on the numerous entries for DOE managed SNF, and the other process covers the management of updates to, and version control/archiving of, the OWL database. In FY2018, we have pursued three studies to evaluate/redefine waste form characteristics and/or performance models. First characteristic isotopic ratios for various waste forms included in postclosure performance studies are being evaluated to delineate isotope ratio tags that quantitatively identify each particular waste form. This evaluation arose due to questions regarding the relative contributions of radionuclides from disparate waste forms in GDSA results, particularly, radionuclide contributions of DOE-managed SNF vs HLW glass. In our second study we are evaluating the bases of glass waste degradation rate models to the HIP calcine waste form. The HIP calcine may likely be a ceramic matrix material, with multiple ceramic phases with/without a glass phase. The ceramic phases are likely to have different degradation performance from the glass portion. The distribution of radionuclides among those various phases may also be a factor in the radionuclide release rates. Additionally, we have an ongoing investigation of the performance behavior of TRISO particle fuels and are developing a stochastic model for the degradation of those fuels that accounts for simultaneous corrosion of the silicon carbide (SiC) layer and radionuclide diffusion through it. The detailed model of the TRISO particles themselves, will be merged with models of the degradation behavior(s) of the graphite matrix (either prismatic compacts or spherical "pebbles") containing the particles and the hexagonal graphite elements holding the compacts.
Mwangi, Paulina; Brady, Patrick V.; Radonjic, Mileva; Thyne, Geoffrey
This paper examines the role of crude oil's organic acid surface active compounds (SAC) in determining the reservoir wettability over a range of salinities and temperatures. To isolate the effects of individual SACs, this project used model oil mixtures of pure decane and single SACs to represent the oleic phase. Due to the large number of experiments in this study, we used wettability measurement method by the modified flotation technique (MFT) to produce fast, reliable, and quantitative results. The results showed that oil wetting by decane increased with temperature for carbonate rocks. Sandstones oil wetting showed little temperature dependency. The presence of long-chained acids in decane increased oil wetting in sandstone and carbonate rocks as salinity was lowered, while the short-chained acid increased water wetting under the same conditions. The effect of organic acids on wettability was slightly enhanced with increasing temperature for all rock types.
This report supplements Joint Workplan on Filler Investigations for DPCs (SNL 2017) providing new and some corrected information for use in planning Phase 1 laboratory testing of slurry cements as possible DPC fillers. The scope description is to "Describe a complete laboratory testing program for filler composition, delivery, emplacement in surrogate canisters, and post-test examination. To the extent possible specify filler material and equipment sources." This report includes results from an independent expert review (Dr. Arun Wagh, retired from Argonne National Laboratory and contracted by Sandia) that helped to narrow the range of cement types for consideration, and to provide further guidance on mix variations to optimize injectability, durability, and other aspects of filler performance.
Chen, Yongqiang; Xie, Quan; Sari, Ahmad; Brady, Patrick V.; Saeedi, Ali
Wettability of the oil/brine/rock system is an essential petro-physical parameter which governs subsurface multiphase flow behaviour and the distribution of fluids, thus directly affecting oil recovery. Recent studies [1–3] show that manipulation of injected brine composition can enhance oil recovery by shifting wettability from oil-wet to water-wet. However, what factor(s) control system wettability has not been completely elucidated due to incomplete understanding of the geochemical system. To isolate and identify the key factors at play we used SO42—free solutions to examine the effect of salinity (formation brine/FB, 10 times diluted formation brine/10 dFB, and 100 times diluted formation brine/100 dFB) on the contact angle of oil droplets at the surface of calcite. We then compared contact angle results with predictions of surface complexation by low salinity water using PHREEQC software. We demonstrate that the conventional dilution approach likely triggers an oil-wet system at low pH, which may explain why the low salinity water EOR-effect is not always observed by injecting low salinity water in carbonated reservoirs. pH plays a fundamental role in the surface chemistry of oil/brine interfaces, and wettability. Our contact angle results show that formation brine triggered a strong water-wet system (35°) at pH 2.55, yet 100 times diluted formation brine led to a strongly oil-wet system (contact angle = 175°) at pH 5.68. Surface complexation modelling correctly predicted the wettability trend with salinity; the bond product sum ([>CaOH2+][–COO−] + [>CO3−][–NH+] + [>CO3−][–COOCa+]) increased with decreasing salinity. At pH < 6 dilution likely makes the calcite surface oil-wet, particularly for crude oils with high base number. Yet, dilution probably causes water wetness at pH > 7 for crude oils with high acid number.
Society of Petroleum Engineers - SPE EOR Conference at Oil and Gas West Asia 2018
Al-Saedi, Hasan N.; Alhuraishawy, Ali K.; Flori, R.E.; Brady, Patrick V.; Heidari, P.
Numerous quantitative and qualitative methods have been presented to measure wettability. The most well-known methods are Amott-Harvey and U.S. Bureau of Mines. The Amott method describes how the wetting phase displaces the nonwetting phase spontaneously; the main problem with this method insensitivity near neutral wettability. Another problem with this method is that imbibition can take several hours to more than two months to complete. The most important benefit of USBM that differs from the Amott method is the sensitivity close to neutral wettability, but the disadvantage is that USBM cannot recognize if the reservoir has mixed wettability or not, though Amott can. We come up with a method to measure sandstone wettability only by Ca2+ and Br− chromatographic separation according to the method described by Strand et al. (2006) on a chalk core. Three sister cores were pre-aged in formation water without Ca2+ and Br−, and the cores were then aged in oil for three weeks at 95°C. The cores were then flooded with the same formation water until Sor was established. Core#1 was flooded with high salinity water (~117,000 ppm) containing identical concentrations of Ca2+ and Br− (89 μmole). Core#2 was flooded with low salinity water d30HSW. Core#3 was sequentially flooded with HS and LS water to investigate the wettability alteration in the same core. All experiments were conducted at 25 and 70°C to examine the effect of temperature on wettability alteration by the new method. The effluents were collected by a fraction collector for chemical analysis for Ca2+ and Br−, divided by the inlet concentration of Ca2+ and Br−, and then plotted with injected pore volume (PV). The area between the Ca2+ and Br− curves was calculated (Ao). Core#4 was pre-aged in heptane in order to establish water-wet sandstone. The heptane was displaced from the core by the same formation water until residual heptane saturation was reached. The same HS water was injected into Core#3. The effluents were analyzed using the same method as for Core#1, 2. The area between the two curves was also determined using the same method as for Core#1, 2 (AH). The wettability index was then calculated by dividing Ao by AH. The wettability index ranged from 0 for strongly oil-wet to 1 for strongly water-wet and 0.5 for intermediate wettability. Another core was sequentially flooded by HS and LS water to further investigate the wettability alteration by LS water and to verify our new method. The divalent cation Ca2+ was considered as the most potential ion towards sandstone when injecting low salinity water to sandstone. An ion exchange occurred between Ca2+ and H+ during flooding which is the key point for wettability alteration, and in turn, increases oil recovery. Bromine is a tracer that has no potential to the sandstone surface area. Thus, the area between Ca2+ and Br− is proportional directly to the water-wet surface site in sandstone (i.e., both Ca2+ and Br− contact the same water-wet surface area).
Proceedings - SPE Symposium on Improved Oil Recovery
Al-Saedi, Hasan N.; Brady, Patrick V.; Flori, Ralph; Heidari, Peyman
The ever-growing global energy demand and natural decline in oil production from mature oil fields over the last several decades have been the main incentives to search for methods to increase recovery efficiency. This paper quantifies the clay role and the important role of pH in the water flooding of low salinity water in sandstone with and without clays as a function of temperature. Four chromatography columns containing different amounts of sand, illite, and kaolinite (100% sand; 5% Illite, 95% sand; 5% kaolinite, 95% sand; 2.5% Illite, 2.5% kaolinite, 95% sand) were water flooded with various salinities at four different temperatures 25, 70, 90 and 120 °C. Effluent concentrations of Ca2+ and CH3COO−, and pH were measured. The system was pre-aged for a week at 70 °C with 0.01 molar (M) sodium acetate to simulate the bonding of oil-bound carboxylic acids with the reservoir. Desorption of carboxylic groups from reservoir clay surfaces is thought to be an important control over low salinity EOR water injection and its extent should depend on pH. To quantify the impact of the presence of the clay, a clay-free sample was also used, the acetate release and Ca2+ desorption were in some cases higher than those observed in non-clay free samples. Typically, cores with higher clay content saw a great rise in pH, but the clay-free samples also saw a rise in pH, as great as that of the clay-containing cores.
The removal of silica, ubiquitous in produced and industrial waters, by novel mixed oxides is investigated in this present study. We have combined the advantage of high selectivity hydrotalcite (HTC, (Mg6Al2(OH)16(CO3)·4H2O)), with large surface area of active alumina (AA, (Al2O3)) for effective removing of the dissolved silica from cooling tower water. The batch test results indicated the combined HTC/AA is a more effective method for removing silica from CTW than using each of HTC or AA separately. The silica uptake was confirmed by Fourier transform infrared (FTIR), and Energy dispersive spectroscopy (EDS). Results indicate HTC/AA effectively removes silica from cooling tower water (CTW), even in the presence of large concentrations of competing anions, such as Cl−, NO3− HCO3−, CO32− and SO42−. The Single Path Flow Through (SPFT) tests confirmed to rapid uptake of silica by combined HTC/AA during column filtration. The experimental data of silica adsorption fit best to Freundlich isotherm model.
This workplan addresses filler attributes (i.e., possible requirements), assumptions needed for analysis, selection of filler materials, testing needs, and a long-range perspective on R&D activities leading to filler demonstration and a safety basis for implementation.
Saeedi, Ali; Delle Piane, Claudio; Esteban, Lionel; Brady, Patrick V.
The South West Hub project is one of the Australian Flagship Carbon Capture and Storage projects located in the south-west of Western Australia. To evaluate the injectivity potential during the forthcoming full-scale CO2 injection, we conducted three core-flooding experiments using reservoir core plugs from the well Harvey-1. We aimed to investigate whether the injection of CO2 leads to fines migration and permeability reduction due to the relatively high kaolinite content (up to 13%) in the injection interval of the target formation (i.e. the Wonnerup Member of the Lesueur Formation). We imaged the core samples before flooding to verify the presence of kaolinite at the pore-scale using scanning electron microscopy (SEM). We also examined the pore network of the core plugs before and after the core-flooding experiments using Nuclear Magnetic Resonance (NMR). Moreover, to gain a better understanding of any kaolinite fines migration, we delineated surface force using two models based on Derjaguin−Landau−Verwey−Overbeek (denoted by DLVO) theory coupled hydrodynamic force: (1) sphere/flat model representing interaction between kaolinite/quartz, and (2) flat/flat model representing interaction between kaolinite/kaolinite. Our core-flooding experimental results showed that CO2/brine injection triggered moderate to significant reduction in the permeability of the core samples with a negligible porosity change. NMR measurements supported the core-flooding results, suggesting that the relatively large pores disappeared in favour of a higher proportion of the medium to small pores after flooding. The DLVO calculations showed that some kaolinite particles probably lifted off and detached from neighbouring kaolinite particles rather than quartz grains. Moreover, the modelling results showed that the kaolinite fines migration would not occur under normal reservoir multiphase flow conditions. This is not because of the low hydrodynamic force. It is rather because the geometries of the particles dominate their interplay. Overall, both of the experimental and analytical modelling results point to the fines migration to be the most likely cause of the permeability impairment observed during core-flooding experiments.
Significant quantities of water are produced during enhanced oil recovery making these “produced water” streams attractive candidates for treatment and reuse. However, high concentrations of dissolved silica raise the propensity for fouling. In this paper, we report the design and economic analysis for a new ion exchange process using calcined hydrotalcite (HTC) to remove silica from water. This process improves upon known technologies by minimizing sludge product, reducing process fouling, and lowering energy use. Process modeling outputs included raw material requirements, energy use, and the minimum water treatment price (MWTP). Monte Carlo simulations quantified the impact of uncertainty and variability in process inputs on MWTP. These analyses showed that cost can be significantly reduced if the HTC materials are optimized. Specifically, R&D improving HTC reusability, silica binding capacity, and raw material price can reduce MWTP by 40%, 13%, and 20%, respectively. Optimizing geographic deployment further improves cost competitiveness.
Water shortages are a growing global problem. Reclamation of industrial and municipal wastewater will be necessary in order to mitigate water scarcity. However, many operational challenges, such as silica scaling, prevent large scale water reuse. Previously, our team at Sandia has demonstrated the use of selective ion exchange materials, such as calcinated hydrotalcite (HTC, (Mg 6 Al 2 (OH) 16 (CO 3 )*4H 2 O)), for the low cost removal of silica from synthetic cooling tower water. However, it is not currently know if calcinated HTC has similar capabilities in realistic applications. The purpose of this study was to investigate the ability of calcinated HTC to remove silica from real cooling tower water. This was investigated under both batch and continuous conditions, and in the presence of competing ions. It was determined that calcinated HTC behaved similarly in real and synthetic cooling tower water; the HTC is highly selective for the silica even in the presence of competing cations. Therefore, the data concludes that calcinated HTC is a viable anti-scaling pretreatment for the reuse of industrial wastewaters.
Silica is ubiquitous in produced and industrial waters, and plays a major disruptive role in water recycle. Herein we have investigated the use of mixed oxides for the removal of silica from these waters, and their incorporation into a low cost and low energy water purification process. High selectivity hydrotalcite (HTC, (Mg6Al2(OH)16(CO3)•4H2O)), is combined in series with high surface area active alumina (AA, (Al2O3)) as the dissolved silica removal media. Batch test results indicated that combined HTC/AA is a more effective method for removing silica from industrial cooling tower wasters (CTW) than using HTC or AA separately. The silica uptake via ion exchange on the mixed oxides was confirmed by Fourier transform infrared (FTIR), and Energy dispersive spectroscopy (EDS). Furthermore, HTC/AA effectively removes silica from CTW even in the presence of large concentrations of competing anions, such as Cl-, NO3- HCO3-, CO32- and SO42-. Similar to batch tests, Single Path Flow Through (SPFT) tests with sequential HTC/AA column filtration has very high silica removal too. Technoeconomic Analysis (TEA) was simultaneously performed for cost comparisons to existing silica removal technologies.
ANS IHLRWM 2017 - 16th International High-Level Radioactive Waste Management Conference: Creating a Safe and Secure Energy Future for Generations to Come - Driving Toward Long-Term Storage and Disposal
The Deep Borehole Field Test (DBFT) is a planned multi-year project led by the US Department of Energy's Office of Nuclear Energy to drill two boreholes to 5 km total depth into crystalline basement in the continental US. The purpose of the first characterization borehole is to demonstrate the ability to characterize in situ formation fluids through sampling and perform downhole hydraulic testing to demonstrate groundwater from 3 to 5 km depth is old and isolated from the atmosphere. The purpose of the second larger-diameter borehole is to demonstrate safe surface and downhole handling procedures. This paper details many of the drilling, testing, and characterization activities planned in the first smaller-diameter characterization borehole.
Fresh water scarcity is going to be a global great challenge in the near future because of the increasing population. Our water resources are limited and, hence, water treatment and recycling methods are the only alternatives for fresh water procurement in the upcoming decades. Water treatment and recycling methods serve to remove harmful or problematic constituents from ground, surface and waste waters prior to its consumption, industrial supply, or other uses. Scale formation in industrial and domestic installations is still an important problem during water treatment. In water treatment, silica scaling is a real and constant concern for plant operations. The focus of this study is on the viability of using a combination of catechol and active carbon to remove dissolved silica from concentrated cooling tower water (CCTW). Various analytical methods, such as ICP-MS and UV-vis, were used to understand the structure-property relationship between the material and the silica removal results. UV-Vis indicates that catechol can react with silica ions and form a silica-catecholate complex. The speciation calculation of catechol and silica shows that catechol and silica bind in the pH range of 8 – 10; there is no evidence of linkage between them in neutral and acidic pHs. The silica removal results indicate that using ~4g/L of catechol and 10g/L active carbon removes up to 50% of the dissolved silica from the CCTW.
ANS IHLRWM 2017 - 16th International High-Level Radioactive Waste Management Conference: Creating a Safe and Secure Energy Future for Generations to Come - Driving Toward Long-Term Storage and Disposal
Disposal of used nuclear fuel and vitrified high-level radioactive waste (UNF and HLW) in a mined geologic repository is the preferred alternative for the countries with the largest inventories of UNF and HLW. However, deep borehole disposal (DBD) may be especially well suited for countries with small nuclear power programs because DBD is relatively inexpensive and scalable; whereas the threshold costs to develop a mined geologic repository are high and do not scale with the inventory. Historically, options for countries with small nuclear power programs (programs that individually generate only a few percent of the world total mass of UNF and/or HLW) have been: (1) to return the UNF to the supplier, (2) to have the SNF reprocessed, with return and incountry disposal of the resulting vitrified HLW in a mined geologic repository, (3) to develop in-country, direct disposal of the UNF in a mined geologic repository or (4) to send the UNF to a hypothetical multi-national mined geologic repository for disposal. However, in-country DBD is likely to be least expensive, and technically achievable with existing technology. In-country DBD could also be a viable alternative for disposal of used fuel assemblies from decommissioned research reactors in developing countries.
Xie, Quan; Brady, Patrick V.; Pooryousefy, Ehsan; Zhou, Daiyu; Liu, Yongbing; Saeedi, Ali
The mechanism(s) of low salinity water flooding (LSWF) must be better understood at high temperatures and pressures if the method is to be applied in high T/P kaolinite-bearing sandstone reservoirs. We measured contact angles between a sandstone and an oil (acid number, AN = 3.98 mg KOH/g, base number, BN = 1.3 mg KOH/g) from a reservoir in the Tarim Field in western China in the presence of various water chemistries. We examined the effect of aqueous ionic solutions (formation brine, 100X diluted formation brine, and softened water), temperature (60, 100 and 140 °C) and pressure (20, 30, 40, and 50 MPa) on the contact angle. We also measured the zeta potential of the oil/water and water/rock interfaces to calculate oil/brine/rock disjoining pressures. A surface complexation model was developed to interpret contact angle measurements and compared with DLVO theory predictions. Contact angles were greatest in formation water, followed by the softened water, and low salinity water at the same pressure and temperature. Contact angles increased slightly with temperature, whereas pressure had little effect. DLVO and surface complexation modelling predicted similar wettability trends and allow reasonably accurate interpretation of core-flood results. Water chemistry has a much larger impact on LSWF than reservoir temperature and pressure. Low salinity water flooding should work in high temperature and high pressure kaolinite-bearing sandstone reservoirs.
Determination of in situ formation water chemistry is an essential component of reservoir management. This paper details the use of thermodynamic computer models to calculate reservoir pH and restore produced water analyses for prediction of scale formation. Bakken produced water samples were restored to formation conditions and calculations of scale formation performed. In situ pH is controlled by feldspar-clay equilibria. Calcite scale is readily formed due to changes in pH during pressure drop from in situ to surface conditions. The formation of anhydrite and halite scale, which has been observed, was predicted only for the most saline samples. In addition, the formation of anhydrite and/or halite may be related to the localized conditions of increased salinity as water is partitioned into the gas phase during production.
A growing body of research supports widespread future reliance on apatite for radioactive waste cleanup. Apatite is a multi-functional radionuclide sorbent that lowers dissolved radionuclide concentrations by surface sorption, ion exchange, surface precipitation, and by providing phosphate to precipitate low-solubility radionuclide-containing minerals. Natural apatites are rich in trace elements, and apatite's stability in the geologic record suggest that radionuclides incorporated into apatite, whether in a permeable reactive barrier or a waste form, are likely to remain isolated from the biosphere for long periods of time. Here we outline the mineralogic and surface origins of apatite-radionuclide reactivity and show how apatites might be used to environmental advantage in the future.
Oil adsorbs to carbonate reservoirs indirectly through a relatively thick separating water layer, and directly to the surface through a relatively thin intervening water layer. Whereas directly sorbed oil desorbs slowly and incompletely in response to changes in reservoir conditions, indirectly sorbed oil can be rapidly desorbed by changing the chemistry of the separating water layer. The additional recovery might be as much as 30% original oil in place (OOIP) above the ∼30% OOIP recovered from carbonates through reservoir depressurization (primary production) and viscous displacement (waterflooding). Electrostatic adhesive forces are the dominant control over carbonate reservoir wettability. A surface complexation model that quantifies electrostatic adhesion accurately predicts oil recovery trends for carbonates. The approach should therefore be useful for estimating initial wettability and designing fluids that improve oil recovery.
The sorption of selenite, SeO32−, by carbonate substituted hydroxylapatite was investigated using batch kinetic and equilibrium experiments. The carbonate substituted hydroxylapatite was prepared by a precipitation method and characterized by SEM, XRD, FT-IR, TGA, BET and solubility measurements. The material is poorly crystalline, contains approximately 9.4% carbonate by weight and has a surface area of 210.2 m2/g. Uptake of selenite by the carbonated hydroxylapatite was approximately an order of magnitude higher than the uptake by uncarbonated hydroxylapatite reported in the literature. Distribution coefficients, Kd, determined for the carbonated apatite in this work ranged from approximately 4200 to over 14,000 L/kg. A comparison of the results from kinetic experiments performed in this work and literature kinetic data indicates the carbonated apatite synthesized in this study sorbed selenite 23 times faster than uncarbonated hydroxylapatite based on values normalized to the surface area of each material. The results indicate carbonated apatite is a potential candidate for use as a sorbent for pump-and-treat technologies, soil amendments or for use in permeable reactive barriers for the remediation of selenium contaminated sediments and groundwaters.
Water is the backbone of our economy - safe and adequate supplies of water are vital for agriculture, industry, recreation, and human consumption. While our supply of water today is largely safe and adequate, we as a nation face increasing water supply challenges in the form of extended droughts, demand growth due to population increase, more stringent health-based regulation, and competing demands from a variety of users. To meet these challenges in the coming decades, water treatment technologies, including desalination, will contribute substantially to ensuring a safe, sustainable, affordable, and adequate water supply for the United States. This overview documents Sandia National Laboratories' (SNL, or Sandia) Water Treatment Program which focused on the development and demonstration of advanced water purification technologies as part of the larger Sandia Water Initiative. Projects under the Water Treatment Program include: (1) the development of desalination research roadmaps (2) our efforts to accelerate the commercialization of new desalination and water treatment technologies (known as the 'Jump-Start Program),' (3) long range (high risk, early stage) desalination research (known as the 'Long Range Research Program'), (4) treatment research projects under the Joint Water Reuse & Desalination Task Force, (5) the Arsenic Water Technology Partnership Program, (6) water treatment projects funded under the New Mexico Small Business Administration, (7) water treatment projects for the National Energy Technology Laboratory (NETL) and the National Renewable Energy Laboratory (NREL), (8) Sandia- developed contaminant-selective treatment technologies, and finally (9) current Laboratory Directed Research and Development (LDRD) funded desalination projects.
Deep Borehole Disposal (DBD) of high-level radioactive wastes has been considered an option for geological isolation for many years (Hess et al. 1957). Recent advances in drilling technology have decreased costs and increased reliability for large-diameter (i.e., ≥50 cm [19.7”]) boreholes to depths of several kilometers (Beswick 2008; Beswick et al. 2014). These advances have therefore also increased the feasibility of the DBD concept (Brady et al. 2009; Cornwall 2015), and the current field test design will demonstrate the DBD concept and these advances. The US Department of Energy (DOE) Strategy for the Management and Disposal of Used Nuclear Fuel and High-Level Radioactive Waste (DOE 2013) specifically recommended developing a research and development plan for DBD. DOE sought input or expression of interest from States, local communities, individuals, private groups, academia, or any other stakeholders willing to host a Deep Borehole Field Test (DBFT). The DBFT includes drilling two boreholes nominally 200m [656’] apart to approximately 5 km [16,400’] total depth, in a region where crystalline basement is expected to begin at less than 2 km depth [6,560’]. The characterization borehole (CB) is the smaller-diameter borehole (i.e., 21.6 cm [8.5”] diameter at total depth), and will be drilled first. The geologic, hydrogeologic, geochemical, geomechanical and thermal testing will take place in the CB. The field test borehole (FTB) is the larger-diameter borehole (i.e., 43.2 cm [17”] diameter at total depth). Surface handling and borehole emplacement of test package will be demonstrated using the FTB to evaluate engineering feasibility and safety of disposal operations (SNL 2016).
We describe here a method for modifying the bulk composition (pH, salinity, hardness) of fracturing fluids and overflushes to modify wettability and increase oil recovery from tight formations. Oil wetting of tight formations is usually controlled by adhesion to illite, kerogen, or both; adhesion to carbonate minerals may also play a role when clays are minor. Oil-illite adhesion is sensitive to salinity, dissolved divalent cation content, and pH. We measure adhesion between middle Bakken formation oil and core to verify a surface complexation model of reservoir wettability. The agreement between the model and experiments suggests that wettability trends in tight formations can be quantitatively predicted and that the bulk compositions of fracturing fluid and overflush compositions might be individually tailored to increase oil recovery.
The subject report from High Bridge Associates (HBA) was issued on March 2, 2016, in reaction to a U.S. Department of Energy (DOE) program decision to pursue down-blending of surplus Pu and geologic disposal at the Waste Isolation Pilot Plant (WIPP). Sandia National Laboratories was requested by the DOE to review the technical arguments presented in the HBA report. Specifically, this review is organized around three technical topics: criticality safety, radiological release limits, and thermal impacts. Questions raised by the report pertaining to legal and regulatory requirements, safeguards and security, international agreements, and costing of alternatives, are beyond the scope of this review.
The U.S. Department of Energy (DOE) has embarked on the Deep Borehole Field Test (DBFT), which will investigate whether conditions suitable for disposal of radioactive waste can be found at a depth of up to 5 km in the earth’s crust. As planned, the DBFT will demonstrate drilling and construction of two boreholes, one for initial scientific characterization, and the other at a larger diameter such as could be appropriate for waste disposal (the DBFT will not involve radioactive waste). A wide range of geoscience activities is planned for the Characterization Borehole, and an engineering demonstration of test package emplacement and retrieval is planned for the larger Field Test Borehole. Characterization activities will focus on measurements and samples that are important for evaluating the long-term isolation capability of the Deep Borehole Disposal (DBD) concept. Engineering demonstration activities will focus on providing data to evaluate the concept’s operational safety and practicality. Procurement of a scientifically acceptable DBFT site and a site management contractor is now underway. The concept of deep borehole disposal (DBD) for radioactive wastes is not new. It was considered by the National Academy of Science (NAS 1957) for liquid waste, studied in the 1980’s in the U.S. (Woodward–Clyde 1983), and has been evaluated by European waste disposal R&D programs in the past few decades (for example, Grundfelt and Crawford 2014; Grundfelt 2010). Deep injection of wastewater including hazardous wastes is ongoing in the U.S. and regulated by the Environmental Protection Agency (EPA 2001). The DBFT is being conducted with a view to use the DBD concept for future disposal of smaller-quantity, DOE-managed wastes from nuclear weapons production (i.e., Cs/Sr capsules and granular solid wastes). However, the concept may also have broader applicability for nations that have a need to dispose of limited amounts of spent fuel from nuclear power reactors. For such nations the cost for disposing of volumetrically limited waste streams could be lower than mined geologic repositories.