DOE OSTI2016
Geologic storage of carbon dioxide (CO 2 ) has been proposed as a viable means for reducing anthropogenic CO 2 emissions. The means for geological sequestration of CO 2 is injection of supercritical CO 2 underground, which requires the CO 2 to remain either supercritical, or in solution in the water/brine present in the underground formation. However, there are aspects of geologic sequestration that need further study, particularly in regards to safety. To date, none of the geologic sequestration locations have been tested for storage integrity under the changing stress conditions that apply to the sequestration of very large amounts of CO 2 . Establishing environmental safety and addressing public concerns require widespread monitoring of the process in the deep subsurface. In addition, studies of subsurface carbon sequestration such as flow simulations, models of underground reactions and transports require a comprehensive monitoring process to accurately characterize and understand the storage process. Real-time information about underground CO 2 movement and concentration change is highly helpful for: (1) better understanding the uncertainties present in CO 2 geologic storage; (2) improvement of simulation models; and (3) evaluation of the feasibility of geologic CO 2 storage. Current methods to monitor underground CO 2 storage include seismic, geoelectric, isotope and tracer methods, and fluid sampling analysis. However, these methods commonly resulted low resolution, high cost, and the inability to monitor continuously over the long time scales of the CO 2 storage process. A preferred way of monitoring in-situ underground CO 2 migration is to continuous measure CO 2 concentration change in brine during the carbon storage process. An approach to obtain the real time information on CO 2 concentration change in formation solution is highly demanded in carbon storage to understand the CO 2 migration subsurface and to answer the public safety problem. The objective of the study is to develop a downhole CO 2 sensor that can in-situ, continuously monitor CO 2 concentration change in deep saline. The sensor is a Severinghaus-type CO 2 sensor with small size, which renders it can be embedded in monitoring well casing or integrated with pressure/temperature transducers, enabling the development of “smart” wells. The studies included: (1) prepare and characterize metal-oxide electrodes. Test the electrodes response to pH change. Investigate different ions and brine concentration effects on the electrode’s performance. Study the stability of the electrode in brine solution; (2) fabricate a downhole CO 2 sensor with the metal-oxide electrodes prepared in the laboratory. Test the performance of the CO 2 sensor in brine solutions. Study high pressure effects on the performance of the sensor; (3) design and conduct CO 2 /brine coreflooding experiments with the CO2 sensor. Monitor CO 2 movement along the core and test the performance of the sensor in coreflooding tests. Develop a data acquisition system that can digitize the sensor’s output voltage. Our completed research has resulted in deep understanding of downhole CO 2 sensor development and CO 2 monitoring in CO 2 storage process. The developed downhole CO 2 sensor included a metal-oxide electrode, a gas-permeable membrane, a porous steel cup, and a bicarbonate-based internal electrolyte solution. Iridium oxide-based electrode was prepared and used for preparation the CO 2 sensor. The prepared iridium oxide-based electrode displayed a linearly response to pH change. Different factors such as different ions and ions concentration, temperature, and pressure effects on the electrode performance on pH response were investigated. The results indicated that the electrode exhibited a good performance even in high salt concentration of produced water. To improve the electrode performance under high pressure, IrO 2 nanoparticles with the particle size in the range of 1-2 nm were prepared and electrodeposited on stainless steel substrate by cyclic voltammetry. It was observed that the thin film of iridium oxide was formed on the substrate surface and such iridium oxide-based electrode displayed excellent performance under high pressure for longer term. A downhole CO 2 sensor with the iridium oxide-based electrode was prepared. The working principle of the CO 2 sensor is based on the measurement of the pH change of the internal electrolyte solution caused by the hydrolysis of CO 2 and then determination of the CO 2 concentration in water. The prepared downhole CO 2 sensor had the size of diameter of 0.7 in. and length of 1.5 in. The sensor was tested under the pressures of 500 psi, 2,000 psi, and 3,000 psi. A linear correlation was observed between the sensor potential change and dissolved CO 2 concentration in water. The response time of the CO 2 sensor was in the range of 60-100 minutes. Further tests indicated that the CO 2 sensor exhibited good reproducibility under high pressure. A CO 2 /brine coreflooding system was constructed to simulate the real-world CO 2 storage process. The prepared downhole CO 2 sensor was loaded in the system to monitor CO 2 movement during CO 2 /brine coreflooding test. The results indicated that the sensor could detect CO 2 movement in the tests. Further studies showed that the sensor could be recovered by brine flooding after CO 2 /brine flushed the core. The results of the coreflooding tests demonstrated that the sensor had potential application for CO 2 monitoring in carbon sequestration. A data acquisition system for the downhoe CO 2 sensor was developed and coded. The system converted the sensor output signal into digital data and transported the data from downhole to wellhead surface. The data acquisition system was tested and evaluated in the laboratory with the prepared sensor for data collection.