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Title: Automated high-pressure titration system with in situ infrared spectroscopic detection

A fully automated titration system with infrared detection was developed for investigating interfacial chemistry at high pressures. The apparatus consists of a high-pressure fluid generation and delivery system coupled to a high-pressure cell with infrared optics. A manifold of electronically actuated valves is used to direct pressurized fluids into the cell. Precise reagent additions to the pressurized cell are made with calibrated tubing loops that are filled with reagent and placed in-line with the cell and a syringe pump. The cell's infrared optics facilitate both transmission and attenuated total reflection (ATR) measurements to monitor bulk-fluid composition and solid-surface phenomena such as adsorption, desorption, complexation, dissolution, and precipitation. Switching between the two measurement modes is accomplished with moveable mirrors that direct the light path of a Fourier transform infrared spectrometer into the cell along transmission or ATR light paths. The versatility of the high-pressure IR titration system was demonstrated with three case studies. First, we titrated water into supercritical CO{sub 2} (scCO{sub 2}) to generate an infrared calibration curve and determine the solubility of water in CO{sub 2} at 50 °C and 90 bar. Next, we characterized the partitioning of water between a montmorillonite clay and scCO{sub 2} at 50 °C and 90more » bar. Transmission-mode spectra were used to quantify changes in the clay's sorbed water concentration as a function of scCO{sub 2} hydration, and ATR measurements provided insights into competitive residency of water and CO{sub 2} on the clay surface and in the interlayer. Finally, we demonstrated how time-dependent studies can be conducted with the system by monitoring the carbonation reaction of forsterite (Mg{sub 2}SiO{sub 4}) in water-bearing scCO{sub 2} at 50 °C and 90 bar. Immediately after water dissolved in the scCO{sub 2}, a thin film of adsorbed water formed on the mineral surface, and the film thickness increased with time as the forsterite began to dissolve. However, after approximately 2.5 h, the trend reversed, and a carbonate precipitate began to form on the forsterite surface, exposing dramatic chemical changes in the thin-water film. Collectively, these applications illustrate how the high-pressure IR titration system can provide molecular-level information about the interactions between variably wet scCO{sub 2} and minerals relevant to underground storage of CO{sub 2} (geologic carbon sequestration). The apparatus could also be utilized to study high-pressure interfacial chemistry in other areas such as catalysis, polymerization, food processing, and oil and gas recovery.« less
Authors:
; ; ; ; ; ;  [1] ;  [2]
  1. Pacific Northwest National Laboratory, Richland, Washington 99352 (United States)
  2. Géosciences Environnement Toulouse (GET), CNRS-Université de Toulouse, 31400 Toulouse (France)
Publication Date:
OSTI Identifier:
22254931
Resource Type:
Journal Article
Resource Relation:
Journal Name: Review of Scientific Instruments; Journal Volume: 85; Journal Issue: 4; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADSORPTION; CARBON DIOXIDE; CARBON SEQUESTRATION; CARBONATES; FOOD PROCESSING; FOURIER TRANSFORMATION; INFRARED SPECTROMETERS; MONTMORILLONITE; OPTICS; POLYMERIZATION; PRECIPITATION; PUMPS; THIN FILMS; TIME DEPENDENCE; TITRATION; UNDERGROUND STORAGE