DOE OSTI2018
The main goal of this project was to evaluate the feasibility of an integrated supercritical (SC) water desalination and power generation system for treatment of produced waters from CO 2 sequestration, oil production, and coal-bed methane recovery. This system may offer a transformative approach to generating power from coal or natural gas (NG) and purifying saline water or produced water with high total dissolved solids (TDS) in a zero-liquid discharge plant. The closed-loop steam cycle of conventional power plants was replaced with an open-loop steam cycle that heated the pretreated produced water above the SC point of water (374 °C and 221 bar) to precipitate and separate the salts dissolved in the water. After separation of the precipitated salt, the SC steam required further treatment to reduce the salt content from ~100 mg/L (ppm) to <1 ppm to make it suitable for use in turbines for power generation. A SC membrane distillation unit was used to polish the SC steam, which could be sent through a series of turbines for power generation, and the steam exiting the low-pressure turbine could be condensed by cooling water to produce pure water. Project tasks included a process simulation and a techno-economic evaluation of the integrated system; design and assembly of SC salt precipitation and membrane distillation systems; development and characterization of advanced carbon membranes for SC membrane distillation; and pretreatment, desalination, and purification of different produced water samples with salt concentrations of 30,000–200,000 ppm to a high-purity (<1 ppm) level. Process simulations were performed for 550 MW SC coal-fired or NG baseline cases and various scenarios for the proposed integrated SC system using produced water as the water source and coal or NG as the fuel source. Simulation results indicated that the net plant efficiency loss of the proposed SC cogeneration process would be in the range of <1% to ~4%, in which NG and lower TDS produced water cases would have higher efficiencies. The proposed process for coal-fired cases could provide all water needs for the power generation process and generate additional pure water for beneficial use. A techno-economic analysis was performed to estimate the cost of produced water treatment (dollars /kgal of treated water) by conventional treatment processes compared with the proposed cogeneration process. The cost estimation for the proposed cogeneration system included the cost of pretreatment, the cost of power loss to integrate the water desalination process into the power generation system, and the cost of plant modification or retrofitting. The cost of produced water treatment was calculated by assuming three different scenarios in which converting a baseline power plant to the proposed cogeneration plant would increase the cost of the boiler and feed water system by 10%, 50%, and 100%. Results indicated that the cost of produced water treatment, even with a 100% cost increase, was in the range of $8.6–11.6 dollars per kgal, which is about half of the treatment cost by conventional methods. The cost of produced water treatment by the proposed cogeneration system could be further reduced or a considerable income could be generated if the values of saltwater and freshwater products are considered. Overall, the techno-economic analysis results indicated that the proposed integrated SC system could potentially treat produced water at a cost significantly lower than the cost of produced water treatment by conventional technologies. To evaluate the feasibility of the proposed treatment system at a laboratory scale, a SC salt precipitation and membrane distillation system was designed and fabricated to treat a simulated brine or pretreated produced water by precipitating salts and further polishing the SC steam containing ~100 ppm salts to a high-purity steam. Through baseline tests with NaCl solutions, with concentrations ranging from 30,000 to 200,000 ppm, it was demonstrated that concentrated feed solutions could be treated by precipitating salt at SC conditions to a TDS level of 130 ppm. Produced water samples were collected from a potential CO 2 sequestration site, a coal-bed methane site, and an oilfield in Illinois. Representative samples were characterized for various water quality parameters, including pH; turbidity; conductivity; and concentrations of selected anions, cations, alkalinity, dissolved organic carbon, total suspended solids, TDS, and total petroleum hydrocarbons. The produced water samples were first treated by conventional pretreatment methods to remove residual oil, dissolved organic matter, and scale-forming species. Pretreatment methods included coagulation, sedimentation, filtration, activated carbon adsorption, and ion-exchange adsorption. Pretreated produced waters were treated at SC conditions in which salts were precipitated. Analysis of treated samples revealed that the concentration of Na (the main cation) in produced waters was reduced dramatically from 14,000–47,400 ppm in the feed to 21–80 ppm in treated waters. Concentrations of other main cations (Ca, Mg, Sr, K) also decreased significantly from initial values of ~1,000–22,000 ppm to ~1 ppm or less. However, a significant increase in the concentrations of Fe, Ni, Cu, and Co was observed, mainly caused by leaching of these elements from the system (vessels, filters, tubing), which is manufactured from alloys containing Fe, Ni, Cu, and Co. To polish the SC steam containing a salt content of ~100 ppm to a high-purity level of <1 ppm, a SC membrane distillation treatment using carbon membranes was employed. Different types of self-standing or supported carbon membranes were developed from graphite, graphene, carbon nanotubes, carbon nanofibers, and pyrolytic carbon. Screening tests revealed that only a limited number of developed carbon membranes were suitable for the purification of steam at SC conditions. Membranes that were either fragile and lacked mechanical strength or had large pores and showed limited salt rejection (<20%) were found to be unsuitable for the purification of SC steam. Promising carbon membranes that were successfully tested for purifying SC steam included two graphite membranes (i.e., AF-5, a porous graphite material, and FGS, a flexible graphite sheet) and a carbon nanotube membrane grown on a Hastelloy substrate and then further modified using a proprietary method (i.e., membrane C). The AF-5 membrane exhibited a stable water flux of ~50 kg/m 2 ∙h and ~40% salt rejection. The FGS membrane had a high salt rejection of 95%–98% but a lower water flux of ~15 kg/m 2 ∙h. Membrane C showed an extremely high flux of 200-800 kg/m 2 ∙h, which is one order of magnitude higher than the water flux of conventional membranes. Membrane C also exhibited 87%–93% salt rejection. Overall, a two-stage or multistage polishing treatment by these membranes could lower the salt content of the SC steam from initial values of ~100–200 ppm to the steam quality of <1 ppm or to parts per billion levels required for the power cycle.
20 FOSSIL-FUELED POWER PLANTS↗