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At least 109 records · Page 6

Effect of exposure temperature on the corrosion behavior of a FeNiCrCuAl high entropy alloy in supercritical water

The corrosion behavior of a FeNiCrCuAl high entropy alloy exposed to supercritical water at 380–650 °C and 25 MPa was investigated. The weight gain exhibited a nearly parabolic kinetics. At 380 °C, Al 2 O 3 precipitated on Fe 3 O 4 particles in FeCr-rich regions and intensified as the temperature increased to 650 °C, eventually resulting in an Al 2 O 3 particle. A mixed Fe 3 O 4 and NiAl 2 O 4 outer layer developed on NiAl-rich regions at 380 °C, whereas an Al 2 O 3 layer formed at 650 °C. Cu 2 O formed along the boundaries of NiAl-rich regions, regardless of exposure temperatures. In conclusion, the corrosion mechanism at different temperatures was elucidated.

36 MATERIALS SCIENCE↗

Temperature dependence of corrosion behavior of a dual-phase Fe 50 Mn 30 Co 10 Cr 10 high entropy alloy in supercritical water at 380–650 °C

Corrosion behavior of a dual-phase Fe 50 Mn 30 Co 10 Cr 10 HEA subjected to supercritical water at different temperatures was investigated. Both weight gain and oxide film thickness increased with increasing temperatures. An outer layer with polyhedral MnFe 2 O 4 particles and an inner layer containing a mixture of CrMn 1.5 O 4 and Fe 3 O 4 were formed at 380 °C. Mn 2 O 3 outer and CrMn 1.5 O 4 inner layers developed at 550 and 650 °C, but the loose granular Mn 2 O 3 particles at 550 °C transformed into a compact oxide film at 650 °C. Besides, Cr 2 O 3 oxide particles were observed along the grain boundaries. Finally, the corrosion mechanism at different temperatures was also discussed.

36 MATERIALS SCIENCE↗

Sulfate Promotes Compact CaCO 3 Formation and Protects Portland Cement from Supercritical CO 2 Attack

Supercritical (sc) CO 2 in geologic carbon sequestration (GCS) can chemically and mechanically deteriorate wellbore cement, raising concerns for long-term operations. In contrast to the conventional view of “sulfate attack” on cement, we found that adding 0.15 M sulfate to the acidic brine can significantly reduce the impact of scCO 2 attack on Portland cement, resulting in stronger cement than that found in a sulfate-free system. Scanning electron microscopy revealed a decreased total attack depth in reacted cement in the presence of sulfate. With a newly defined minimum porosity term in reactive transport modeling, our model suggests that sulfate caused CaCO 3 to fill more nanopore spaces in the cement. Small angle X-ray scattering experiments also showed that sulfate can decrease the pore sizes of the carbonate layer. The results suggest that the interactions between sulfate and cement can generate a less porous CaCO 3 layer, which better resists acidic brine. Using this mechanism as a proof-of-concept, we tested the incorporation of sodium sulfate into Portland cement and synthesized new cement composites that show stronger resistance against scCO 2 attacks. Finally, these newly discovered interfacial interactions between CaCO 3 and sulfate provide new insights into engineering mechanically strong and green materials for safer GCS.

54 ENVIRONMENTAL SCIENCES↗

High-temperature seals for supercritical carbon-dioxide (sCO 2 ) turbines (Final Report)

This is the final report for project DE-FE0031924 titled “High-temperature seals for supercritical carbon-dioxide (sCO 2 ) turbines.” The report provides a summary of the entire project efforts from October 2020 through December 2024 including the high-temperature commercial dry gas seal (DGS) tests and thermal modeling of Task 2, as well as the high-temperature, large-diameter seal design and high-temperature tests of large-diameter seals in Task 3. A key outcome of Task 2 was the testing completion of specially instrumented commercial DGS in the GE-SwRI Apollo sCO 2 compressor (27,000 rpm). Test data from the DGS showed elevated temperatures upwards of 350 o F, which are close to the higher operating temperature limit of the DGS. The temperature measurements provide insight into the expected thermal loads on DGS operating in high-speed sCO 2 compressor and provided test data for validation of an in-house thermal model of the compressor/seal. Under Task 2.0, this report also presents the development of a steady-state conjugate heat-transfer model of the DGS operating in the sCO 2 compressor – a first of its kind model for modeling heat transfer of sCO 2 in an actual operating compressor. The findings of the thermal model show a reasonable match between temperature predictions of the model and the measured temperature data, also pointing out the validity of the approach and assumptions made in modeling the flows, heat transfer coefficients and windage modeling in the rig. Under Task 3.0, this report presents the preliminary design of a large-diameter hybrid face seal (14 inch and 26-inch diameter) for field testing in a land-based GE turbine. The preliminary seal design effort presented in this report under project DE-FE0031924 builds on the development and successful laboratory testing for such large diameter hybrid face seal under the prior DE-FE0024007 project. Key aspects of seal fluid analyses with CFD, mechanical design considerations and assembly considerations in a land-based turbine are presented. Finally, under Task 3.0, this report also presents the continued high-temperature testing of the 14-inch diameter hybrid face seal developed previously under the DE-FE0024007 program. Specifically, test data demonstrating successful non-contact seal operation and seal effective leakage of 0.001-inch with seal inlet temperatures above 700 o F are presented in this report. Successful hybrid seal operation in a laboratory environment for a large diameter (14-inch) seal at temperatures above 700 o F is a major technological milestone for this technology.

01 COAL, LIGNITE, AND PEAT↗

Hydrothermal catalysis of waste greases into green gasoline, jet, and diesel biofuels in continuous flow supercritical water

Production of green gasoline, jet, and diesel biofuels from waste greases was achieved using a novel hydrothermal, continuous-flow catalytic process operating under supercritical water conditions, with recycled water the only added chemical. Thermally and chemically stable catalysts were explored to optimize yields of liquid biofuels and to minimize production of gases and acidic compounds. A 50:50 mixture of brown and yellow waste greases converted into 76.6 wt% liquid biocrude (BC); the remainder converted to water and gases. Less than 0.2% of the FS formed carbon char (mainly amongst catalyst particles). Various tubular reactors (Inconel, ® Hastelloy®, titanium, stainless) showed no interior defects, erosion, or mass loss after runs. Here, the titanium catalyst was fully recovered and regenerated back to its original potency. The BC was further refined into 28%, 48%, 20%, and 4 wt%, respectively for green gasoline, jet, diesel, and bunker. Biofuels were analyzed for compound class compositions and reaction mechanisms were proposed. The hundreds of identified fuel products (C3-C35) from processing oleic acid as a pure model compound were identified. The neat green gasoline and diesel biofuels along with a 50% green jet blend (with petroleum Jet A) were tested in appropriate spark ignition, turbine, and diesel engines at University of MN Engine Labs. Biofuels achieved 107.7%, 97.2%, and 101.3% engine power performance levels relative to petroleum fuels (91-Octane, Jet A, #2 Diesel) along with lower CO and pollutant emissions. Biofuels passed ASTM fuel specifications (D4814, D7566, D975) including mandated corrosion and low sulfur limits of all three biofuels.

09 BIOMASS FUELS↗

Effect of annealing and supercritical CO 2 exposure at 750°C on the tensile properties of stainless steel and Ni-based structural alloys

Subsize dogbone tensile specimens of alloys 304H, 310HCbN, and 740H were exposed to 30 MPa supercritical CO 2 (sCO 2 ) for up to 4000 h at 750°C. Similar exposures in laboratory air were used to assess the specific role of sCO 2 exposure on the alloy tensile properties. Type 304H specimens were only embrittled by exposure in sCO 2 due to the formation of a thick Fe-rich oxide and C ingress in the bulk of the alloy. For 310HCbN and 740H, no effect of the sCO 2 environment was observed and a decrease of the alloy's ductility was associated with previously observed microstructure evolutions, for example, grain boundary carbide formation. The 740H was tested in the solution annealed condition and self-aging took place during 750°C exposures in sCO 2 and air with the formation of fine gamma prime precipitates leading to significant tensile strength increase. It was found that both 740H and 310HCbN have adequate sCO 2 compatibility for high-temperature commercial applications.

36 MATERIALS SCIENCE↗

Evaluation of coated steels in supercritical CO 2

The carburizing supercritical CO 2 (sCO 2 ) environment limits the use of lower cost steels in the lower temperature (450–650°C) portions of the sCO 2 Brayton cycle because of concerns about internal carburization and embrittlement. Results on a ferritic–martensitic steel and conventional and advanced austenitic steels at 450–650°C in 30 MPa sCO 2 with and without 1% O 2 and 0.1% H 2 O additions have indicated that sCO 2 environments will have lower maximum operating temperatures compared to steam plants. Pack Al and Cr coatings were evaluated at 650°C on T91 and 316H substrates and showed some benefit for up to 2000 h at 650°C, especially without impurities. However, characterization indicated Al 2 O 3 was not formed and Cr-rich carbides formed in the Cr coatings. With the addition of impurities in the sCO 2 , the coatings were less protective at 650°C. Subsequent exposures at 600°C in sCO 2 showed similar behavior. Postexposure evaluations included measuring the bulk C content and room temperature tensile properties. Finally, improvements were indicated but the tensile results were complicated by the high temperature pack coating process affecting the substrate properties.

36 MATERIALS SCIENCE↗

Mechanical and Corrosion Response of 316SS in Supercritical CO 2

The supercritical carbon dioxide (s-CO 2 ) Brayton cycle is currently being explored as a replacement for the steam Rankine cycle due to its potential for higher efficiency and lower cycle cost. 316 stainless steel is a candidate alloy for use in s-CO 2 up to roughly 600 °C, but the mechanical effects of prolonged exposure of base and welded material in s-CO 2 have not been analyzed. The potential for carburization makes this an important concern for the implementation of 316 and similar austenitic stainless steels in the s-CO 2 environment. In this study, welded and base material of two types of 316–316L and 316H–were exposed in either s-CO 2 or argon at 550 °C or 750 °C for 1000 h. 550 °C s-CO 2 exposure yielded a thin (< 1 µm) Cr oxide with occasional nodules of duplex Fe oxide and Fe–Cr spinel that were up to 5 microns thick. However, tensile results from s-CO –2 exposure matched those of 550 °C thermal aging in Ar, indicating that no mechanically detrimental carburization occurred in either 316 variant after 1000 h exposure. Conversely, 750 °C s-CO 2 exposure produced roughly 10 × the oxide thickness, with a more substantial Fe oxide (3–5 µm) on the majority of the surface and nodules of up to 40 µm thick. In comparison to aged samples, tensile testing of 750 °C CO 2 -exposed samples revealed ductility loss attributed to carburization. As a result, projections of 316L performance in s-CO 2 indicate that mechanically detrimental carburization—equal to that shown here for 750 °C, 1000 h—will likely be present after 7–14 years of service at 550 °C.

316 stainless steel↗

Oxidation Behavior of Welded Fe-Based and Ni-Based Alloys in Supercritical CO 2

Next-generation supercritical CO 2 (sCO 2 ) power cycles will require different classes of alloy throughout the operational temperatures to optimize tradeoff of creep strength, oxidation performance and cost. This will necessitate joining methods such as welding, which might pose compatibility concerns at the joined interfaces. In this study, similar and dissimilar metal welds were generated from a variety of candidate alloys for sCO 2 systems including ferritic/martensitic steels, austenitic steels, and Ni-based superalloys. Samples were extracted from different regions of the welds and exposed to sCO 2 at 550 °C and 20 MPa for 2500 h, then characterized to understand their behavior in this environment. Unsurprisingly, the local oxidation behavior was largely dictated by the Cr content in the underlying metal. High-Cr austenitic steels and Ni alloys formed slow-growing Cr-rich oxide scales with minimal carburization of the underlying metal, while low-Cr ferritic/martensitic steels formed fast-growing Fe-rich oxide scales with significant carburization. Most welds did not show any unusual oxidation behavior at the interfaces, considering the local Cr content. The one exception was the 347H similar metal weld, where a larger grain size and complex grain structure in the fusion zone led to a significantly higher rate of Fe-rich oxide nodule formation compared to the base metal. This suggests that microstructural changes at joined interfaces can play an important role on the oxidation-limited lifetimes in future sCO 2 systems. The composition changes across the interfaces enabled study of the effect of Fe on the growth rate of Cr-rich oxides and of the origins of the sub-surface recrystallization zone that forms beneath them.

36 MATERIALS SCIENCE↗

Rapid determination of supercritical CO 2 and brine relative permeability using an unsteady-state flow method

In this study, relative permeability of supercritical CO 2 (scCO 2 ) and brine was determined in reactive and non-reactive rock cores using a combination of unsteady-state methodology and computed tomography. Experiments were conducted using a medical grade CT scanner to determine saturation using a custom Python script. The saturation and differential pressure across the core were then used to derive four empirical constants to calculate relative permeability. This methodology increases temporal efficiency while reducing experimental complexity. Additionally, we show that the method can be used to determine scCO 2 relative permeability in a wide range of lithologies and flow rates, and with the ability to account for matrix dissolution during scCO 2 flooding.

54 ENVIRONMENTAL SCIENCES↗

Control methods for mitigating flow oscillations in a supercritical CO 2 recompression closed Brayton cycle

A dynamic model of a 10 MWe supercritical CO 2 (sCO 2 ) recompression closed Brayton power generation cycle is used to investigate control methods for mitigating oscillations in flow conditions and power demand load, especially as the load ramp rate is increased and the load setpoint is more closely tracked. The focus is on control of the main compressor inlet temperature (MCIT) since oscillations are prompted by the strong nonlinearities in sCO 2 fluid properties near the critical point and by changes in system inventory for efficient load management. In this study, the oscillatory behavior during load ramping is first shown and then two potential control solutions for substantially reducing oscillations are given: 1) the use of the main compressor inlet guide vanes (IGV) and 2) bypassing a portion of the sCO 2 around the cooler to maintain the MCIT. These control methods reduce the effect of cycle feedback from interactions between the MCIT and load. When implementing either control method, a load setpoint ramp of 7.5%/min was maintainable while achieving closer load setpoint tracking with limited oscillations. Finally, the impact of sensor noise on the control was examined since derivative action was used in the IGV and cooler sCO 2 bypass control. Finally, while some effect was evident, signal noise was not problematic to the control.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Scaling considerations for supercritical carbon dioxide cycles including turbomachinery loss models

A modeling framework for the supercritical carbon dioxide recompressed closed Brayton cycle was developed. Unlike typical models, this effort incorporated generalized empirical turbomachinery loss models. Aerodynamic, windage, and leakage losses were considered in order to address the limitations of conventional constant-efficiency turbomachinery assumptions without relying on machine-specific or computationally expensive simulations. The model enables system-level exploration of optimal cycle design across a range of power scales, including smaller scales that are relevant to microreactors and extraterrestrial power applications. Parametric studies and multi-objective optimizations are used to evaluate the trade-offs between thermal efficiency and system compactness based on an analytical heat exchanger scaling model, yielding Pareto-optimal fronts across a range of operating pressures. Results reveal that at small power scales, the Pareto-optimal compressor inlet pressure becomes subcritical due to the increasing influence of density-dependent turbomachinery losses. Here, the relative contributions of each loss mechanism are quantified, and design recommendations are provided for key parameters such as recompression split ratio and generator cavity pressure across varying power scales.

Multi-objective optimization↗

Carburization resistance of cu-coated stainless steel in supercritical carbon dioxide environments

This study investigates the effectiveness of Cu as a corrosion barrier in supercritical carbon dioxide (s-CO 2 ) by coating 316 stainless steel (316) with various thicknesses of Cu. In this work, 316 exposed to s-CO 2 with 50 ppm CO showed a reduction in oxidation corresponding to the thickness of its Cu barrier coating. Additionally, a continuous Cu layer between the environment and the alloy was found to correlate to an elimination of carburization and corrosion-related mechanical degradation. This Cu coating technique could be applied over a variety of temperatures to improve the corrosion resistance of alloys that are susceptible to carburization.

36 MATERIALS SCIENCE↗

Effect of thickness on degradation of austenitic 347H steel by direct-fired supercritical CO 2 power cycle environment

Austenitic 347H steel of two thicknesses (2.54 and 0.6 mm) was exposed to a simulated direct-fired supercritical CO 2 (sCO 2 ) power cycle environment at 650°C and 1 atm for 1000 h then tensile stressed at room temperature to study the deformation behavior. The thicker 347H formed a protective chromia scale over most of the surface, which minimized carburization of the underlying steel and resulted in no change in mechanical performance. In stark contrast, the thinner 347H formed non-protective Fe-rich oxides over the entire surface, resulting in extensive carburization of the underlying steel. Finally, this led to increased strength but significantly reduced ductility, resulting in partially brittle failure

36 MATERIALS SCIENCE↗

Effect of pressure on high-temperature oxidation of Ni alloys in supercritical CO 2 containing impurities

Direct supercritical CO 2 (sCO 2 ) power cycles require structural materials compatible with hot sCO 2 containing high levels of water and oxygen impurities. Chromia-forming Ni-based superalloys, which are leading candidates at temperatures > 600 °C, have shown good compatibility in pure sCO 2 , however potential impurity effects are not well understood. In this report we exposed several commercial Ni-based alloys to 95%CO 2 -4%H 2 O-(1-3)%O 2 at 750 °C and 0.1 or 20 MPa for 2500 h. Protective chromia scales formed in all cases. Nevertheless, water vapor-assisted oxide volatilization clearly occurred at high pressure. The volatilization rates decreased with time, but still represent a potentially serious compatibility issue in real, high-velocity, sCO 2 systems.

36 MATERIALS SCIENCE↗

Advanced supercritical water-based process concepts for treatment and beneficial reuse of brine in oil/gas production

Produced water generated from oil/gas reservoirs is a cost burden for oil/gas producers, with over 21 billion barrels of the waste generated in 2019. Average disposal costs range from 4.00–8.00·bbl -1 , with up to 20·bbl -1 spent on transportation alone. Dissolved solids content is a contributing factor which limits economical treatment options for this waste stream. This work proposes a novel technique that can handle high salinity waste, employing favorable properties past the critical point of water. In this study, process simulation of two supercritical water desalination (SCWD) scenarios was completed. Zero liquid discharge (ZLD) and brine concentration operating scenarios were compared, weighing the associated economics and benefits for each case. The results were shown to be economically feasible for brines with a high dissolved solids content, ranging from 3.49 to 17.28·bbl -1 in an expanded sensitivity analysis.

42 ENGINEERING↗

Energy efficient supercritical water desalination using a high-temperature heat pump: A zero liquid discharge desalination

Supercritical water desalination (SCWD) is zero liquid discharge technology that can potentially control the solubility of different electrolytes. However, SCWD is an energy-intensive process and requires high-quality thermal heat (> 450 °C). This study proposes the integration of a high-temperature heat pump to reduce the SCWD energy requirement. The integrated system energy consumption improves by 36% for 3.5% feed concentration and 14% for 20% feed, and the distillate cost reduces by 15% and 10%. Another benefit of the proposed integration is the system can be operated using only electricity as a heat source, as is the case with commonly used high-recovery thermal desalination technology. The integrated SCWD-heat pump system shows superior performance compared to the commercially used brine concentrator and crystallizer system. It is approximately 20% more energy-efficient for 25% feed concentration and 8% cheaper. Hence, the integrated SCWD-heat pump has the potential to outperform the pre-existing high-recovery desalination technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A novel triple power cycle featuring a gas turbine cycle with supercritical carbon dioxide and organic Rankine cycles: Thermoeconomic analysis and optimization

In this study, a novel triple power cycle is proposed where waste heat from a gas turbine cycle is utilized to drive a supercritical carbon dioxide (s-CO 2 ) recompression cycle and a recuperative organic Rankine cycle (ORC) in sequence. A detailed thermoeconomic model is developed and implemented in MATLAB to evaluate the performance of the proposed cycle under different operating conditions. Optimization using a particle swarm optimization (PSO) algorithm is performed to minimize the levelized cost of electricity (LCOE) and determine the optimum design conditions of the cycle. The optimization results show that for a 100 MW cycle, the overall thermal efficiency and LCOE are 0.521 and $\$52.819$/MWh, respectively. The turbine inlet temperature of the gas turbine and s-CO 2 cycles are found as the most influential parameters on the thermoeconomic performance of the triple cycle. The proposed triple cycle shows an excellent waste energy recovery potential and superiority over a very thermodynamically efficient cycle from the literature, which included a gas turbine topping cycle and a complex cascade s-CO 2 power cycle used a bottoming cycle. As a result, the proposed triple cycle shows up to 0.9% points higher efficiency while it has fewer heat exchangers and turbomachinery than the cycle from the literature.

30 DIRECT ENERGY CONVERSION↗